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Sample records for time-resolved ir spectroscopy

  1. Time-resolved ESR spectroscopy

    International Nuclear Information System (INIS)

    Beckert, D.

    1986-06-01

    The time-resolved ESR spectroscopy is one of the modern methods in radiospectroscopy and plays an important role in solving various problems in chemistry and biology. Proceeding from the basic ideas of time-resolved ESR spectroscopy the experimental equipment is described generally including the equipment developed at the Central Institute of Isotope and Radiation Research. The experimental methods applied to the investigation of effects of chemically induced magnetic polarization of electrons and to kinetic studies of free radicals in polymer systems are presented. The theory of radical pair mechanism is discussed and theoretical expressions are summarized in a computer code to compute the theoretical polarization for each pair of the radicals

  2. Time-resolved vibrational spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Tokmakoff, Andrei [Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Champion, Paul [Northeastern Univ., Boston, MA (United States); Heilweil, Edwin J. [National Inst. of Standards and Technology (NIST), Boulder, CO (United States); Nelson, Keith A. [Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Ziegler, Larry [Boston Univ., MA (United States)

    2009-05-14

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

  3. Kinetics of the reaction F+NO+M->FNO+M studied by pulse radiolysis combined with time-resolved IR and UV spectroscopy

    DEFF Research Database (Denmark)

    Pagsberg, Palle Bjørn; Sillesen, A.; Jodkowski, J.T.

    1996-01-01

    The title reaction was initiated by pulse radiolysis of SF6/NO gas mixtures, and the formation of FNO was studied by time-resolved IR and UV spectroscopy. At SF6 pressures of 10-320 mbar at 298 K, the formation of FNO was studied by infrared diode laser spectroscopy at 1857.324 cm(-1). Comparative...

  4. Time-resolved photoelectron spectroscopy of IR-driven electron dynamics in a charge transfer model system.

    Science.gov (United States)

    Falge, Mirjam; Fröbel, Friedrich Georg; Engel, Volker; Gräfe, Stefanie

    2017-08-02

    If the adiabatic approximation is valid, electrons smoothly adapt to molecular geometry changes. In contrast, as a characteristic of diabatic dynamics, the electron density does not follow the nuclear motion. Recently, we have shown that the asymmetry in time-resolved photoelectron spectra serves as a tool to distinguish between these dynamics [Falge et al., J. Phys. Chem. Lett., 2012, 3, 2617]. Here, we investigate the influence of an additional, moderately intense infrared (IR) laser field, as often applied in attosecond time-resolved experiments, on such asymmetries. This is done using a simple model for coupled electronic-nuclear motion. We calculate time-resolved photoelectron spectra and their asymmetries and demonstrate that the spectra directly map the bound electron-nuclear dynamics. From the asymmetries, we can trace the IR field-induced population transfer and both the field-driven and intrinsic (non-)adiabatic dynamics. This holds true when considering superposition states accompanied by electronic coherences. The latter are observable in the asymmetries for sufficiently short XUV pulses to coherently probe the coupled states. It is thus documented that the asymmetry is a measure for phases in bound electron wave packets and non-adiabatic dynamics.

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

    Energy Technology Data Exchange (ETDEWEB)

    Li, Deyong; Li, Yunliang; Li, Hao; Weng, Yuxiang, E-mail: yxweng@iphy.ac.cn [Key Laboratory of Soft Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190 (China); Wu, Xianyou [Anhui Institute of Optics and Fine Mechanics, Chinese Academy of Sciences, Hefei 230031 (China); Yu, Qingxu [School of Physics and Optoelectronic Technology, Dalian University of Technology, No. 2, Linggong Road, Dalian 116023 (China)

    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 that 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.

  6. Time-resolved fluorescence spectroscopy

    International Nuclear Information System (INIS)

    Gustavsson, Thomas; Mialocq, Jean-Claude

    2007-01-01

    This article addresses the evolution in time of light emitted by a molecular system after a brief photo-excitation. The authors first describe fluorescence from a photo-physical point of view and discuss the characterization of the excited state. Then, they explain some basic notions related to fluorescence characterization (lifetime and decays, quantum efficiency, so on). They present the different experimental methods and techniques currently used to study time-resolved fluorescence. They discuss basic notions of time resolution and spectral reconstruction. They briefly present some conventional methods: intensified Ccd cameras, photo-multipliers and photodiodes associated with a fast oscilloscope, and phase modulation. Other methods and techniques are more precisely presented: time-correlated single photon counting (principle, examples, and fluorescence lifetime imagery), streak camera (principle, examples), and optical methods like the Kerr optical effect (principle and examples) and fluorescence up-conversion (principle and theoretical considerations, examples of application)

  7. Time-resolved spectroscopy in synchrotron radiation

    International Nuclear Information System (INIS)

    Rehn, V.; Stanford Univ., CA

    1980-01-01

    Synchrotron radiation (SR) from large-diameter storage rings has intrinsic time structure which facilitates time-resolved measurements form milliseconds to picoseconds and possibly below. The scientific importance of time-resolved measurements is steadily increasing as more and better techniques are discovered and applied to a wider variety of scientific problems. This paper presents a discussion of the importance of various parameters of the SR facility in providing for time-resolved spectroscopy experiments, including the role of beam-line optical design parameters. Special emphasis is placed on the requirements of extremely fast time-resolved experiments with which the effects of atomic vibrational or relaxation motion may be studied. Before discussing the state-of-the-art timing experiments, we review several types of time-resolved measurements which have now become routine: nanosecond-range fluorescence decay times, time-resolved emission and excitation spectroscopies, and various time-of-flight applications. These techniques all depend on a short SR pulse length and a long interpulse period, such as is provided by a large-diameter ring operating in a single-bunch mode. In most cases, the pulse shape and even the stability of the pulse shape is relatively unimportant as long as the pulse length is smaller than the risetime of the detection apparatus, typically 1 to 2 ns. For time resolution smaller than 1 ns, the requirements on the pulse shape become more stringent. (orig./FKS)

  8. ESIPT and photodissociation of 3-hydroxychromone in solution: photoinduced processes studied by static and time-resolved UV/Vis, fluorescence, and IR spectroscopy.

    Science.gov (United States)

    Chevalier, Katharina; Grün, Anneken; Stamm, Anke; Schmitt, Yvonne; Gerhards, Markus; Diller, Rolf

    2013-11-07

    The spectral properties of fluorescence sensors such as 3-hydroxychromone (3-HC) and its derivatives are sensitive to interaction with the surrounding medium as well as to substitution. 3-HC is a prototype system for other derivatives because it is the basic unit of all flavonoides undergoing ESIPT and is not perturbed by a substituent. In this study, the elementary processes and intermediate states in the photocycle of 3-HC as well as its anion were identified and characterized by the use of static and femtosecond time-resolved spectroscopy in different solvents (methylcyclohexane, acetonitrile, ethanol, and water at different pH). Electronic absorption and fluorescence spectra and lifetimes of the intermediate states were obtained for the normal, tautomer and anionic excited state, while mid-IR vibrational spectra yielded structural information on ground and excited states of 3-HC. A high sensitivity on hydrogen-bonding perturbations was observed, leading to photoinduced anion formation in water, while in organic solvents, different processes are suggested, including slow picosecond ESIPT and contribution of the trans-structure excited state or a different stable solvation state with different direction of OH. The formation of the latter could be favored by the lack of a substituent increasing contact points for specific solute-solvent interactions at the hydroxyl group compared to substituted derivatives. The effect of substituents has to be considered for the design of future fluorescence sensors based on 3-HC.

  9. Impulsive IR-multiphoton dissociation of acrolein: observation of non-statistical product vibrational excitation in CO ( v=1-12) by time resolved IR fluorescence spectroscopy

    Science.gov (United States)

    Chowdhury, P. K.

    2000-10-01

    On IR-multiphoton excitation, vibrationally highly excited acrolein molecules undergo concerted dissociation generating CO and ethylene. The vibrationally excited products, CO and ethylene, are detected immediately following the CO 2 laser pulse by observing IR fluorescence at 4.7 and 3.2 μm, respectively. The nascent CO is formed with significant vibrational excitation, with a Boltzmann population distribution for v=1-12 levels corresponding to T v=12 950±50 K. The average vibrational energy in the product CO is found to be 26 kcal mol -1, in contrast to its statistical share of 5 kcal mol -1, available from the product energy distribution. The nascent vibrationally excited ethylene either dissociates by absorbing further infrared laser photons from the tail of the CO 2 laser pulse or relaxes by collisional deactivation. Ethylene IR-fluorescence excitation spectrum showed a structure in the quasi-continuum, with a facile resonance at 10.53 μm corresponding to the 10P(14) CO 2 laser line, which explains the higher acetylene yield observed at a higher pressure. A hydrogen atom transfer mechanism followed by C-C impulsive break in the acrolein transition state may be responsible for such non-statistical product energy distribution.

  10. Kinetics of the F+NO2+M->FNO2+M reaction studied by pulse radiolysis combined with time-resolved IR and UV spectroscopy

    DEFF Research Database (Denmark)

    Pagsberg, Palle Bjørn; Sillesen, A.; Jodkowski, J.T.

    1996-01-01

    was studied with SF6 pressures of 5-1000 mbar at 298 K. Comparative studies were carried out by monitoring the decay kinetics of NO2 at 445 nm using pressures of 100-1000 mbar at 295 and 341 K. The observed pressure dependence is represented in terms of a fall-off curve with the following values......The title reaction was initiated by the pulse radiolysis of SF6/NO2 gas mixtures, and the formation of FNO2 was studied by time-resolved infrared spectroscopy employing strong rotational transitions within the nu(1) and nu(4) bands of FNO2. The pressure dependence of the formation kinetics...

  11. Excited-State Dynamics of a DNA Duplex in a Deep Eutectic Solvent Probed by Femtosecond Time-Resolved IR Spectroscopy.

    Science.gov (United States)

    de La Harpe, Kimberly; Kohl, Forrest R; Zhang, Yuyuan; Kohler, Bern

    2018-03-08

    To better understand how the solvent influences excited-state deactivation in DNA strands, femtosecond time-resolved IR (fs-TRIR) pump-probe measurements were performed on a d(AT) 9 ·d(AT) 9 duplex dissolved in a deep eutectic solvent (DES) made from choline chloride and ethylene glycol in a 1:2 mol ratio. This solvent, known as ethaline, is a member of a class of ionic liquids capable of solubilizing DNA with minimal disruption to its secondary structure. UV melting analysis reveals that the duplex studied here melts at 18 °C in ethaline compared to 50 °C in aqueous solution. Ethaline has an excellent transparency window that facilitates TRIR measurements in the double-bond stretching region. Transient spectra recorded in deuterated ethaline at room temperature indicate that photoinduced intrastrand charge transfer occurs from A to T, yielding the same exciplex state previously detected in aqueous solution. This state decays via charge recombination with a lifetime of 380 ± 10 ps compared to the 300 ± 10 ps lifetime measured earlier in D 2 O solution. The TRIR data strongly suggest that the long-lived exciplex forms exclusively in the solvated duplex, and not in the denatured single strands, which appear to have little, if any, base stacking. The longer lifetime of the exciplex state in the DES compared to aqueous solution is suggested to arise from reduced stabilization of the charge transfer state, resulting in slower charge recombination on account of Marcus inverted behavior.

  12. TIME-RESOLVED INFRARED SPECTROSCOPY IN THE U121R BEAMLINE AT THE NSLS

    International Nuclear Information System (INIS)

    CARR, G.L.; LAVEIGNE, J.D.; LOBO, R.P.S.M.; REITZE, D.H.; TANNER, D.B.

    1999-01-01

    A facility for performing time-resolved infrared spectroscopy has been developed at the NSLS, primarily at beamline U12IR. The pulsed IR light from the synchrotron is used to perform pump-probe spectroscopy. The authors present here a description of the facility and results for the relaxation of photoexcitations in both a semiconductor and superconductor

  13. Excited-state relaxation dynamics of Re(I) tricarbonyl complexes with macrocyclic phenanthroline ligands studied by time-resolved IR spectroscopy

    Czech Academy of Sciences Publication Activity Database

    Blanco-Rodríguez, A. M.; Towrie, M.; Collin, J.; P.; Záliš, Stanislav; Vlček, Antonín

    -, č. 20 (2009), s. 3941-3949 ISSN 1477-9226 R&D Projects: GA MŠk OC09043; GA MŠk OC 139 Institutional research plan: CEZ:AV0Z40400503 Keywords : Raman spectroscopy * molecular machine prototypes * infrared spectroscopy Subject RIV: CG - Electrochemistry Impact factor: 4.081, year: 2009

  14. Seventh international conference on time-resolved vibrational spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

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

    1997-04-01

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

  15. Time resolved spectroscopy of GRB 030501 using INTEGRAL

    DEFF Research Database (Denmark)

    Beckmann, V.; Borkowski, J.; Courvoisier, T.J.L.

    2003-01-01

    The gamma-ray instruments on-board INTEGRAL offer an unique opportunity to perform time resolved analysis on GRBs. The imager IBIS allows accurate positioning of GRBs and broad band spectral analysis, while SPI provides high resolution spectroscopy. GRB 030501 was discovered by the INTEGRAL Burst...... the Ulysses and RHESSI experiments....

  16. Emerging biomedical applications of time-resolved fluorescence spectroscopy

    Science.gov (United States)

    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.

  17. Time-resolved terahertz spectroscopy of semiconductor nanostructures

    DEFF Research Database (Denmark)

    Porte, Henrik

    This thesis describes time-resolved terahertz spectroscopy measurements on various semiconductor nanostructures. The aim is to study the carrier dynamics in these nanostructures on a picosecond timescale. In a typical experiment carriers are excited with a visible or near-infrared pulse and by me......This thesis describes time-resolved terahertz spectroscopy measurements on various semiconductor nanostructures. The aim is to study the carrier dynamics in these nanostructures on a picosecond timescale. In a typical experiment carriers are excited with a visible or near-infrared pulse...... and by measuring the transmission of a terahertz probe pulse, the photoconductivity of the excited sample can be obtained. By changing the relative arrival time at the sample between the pump and the probe pulse, the photoconductivity dynamics can be studied on a picosecond timescale. The rst studied semiconductor...

  18. Time resolved IR-LIGS experiments for gas-phase trace detection and temperature measurements

    Energy Technology Data Exchange (ETDEWEB)

    Fantoni, R.; Giorgi, M. [ENEA, Centro Ricerche Frascati, Rome (Italy). Dip. Innovazione; Snels, M. [CNR, Tito Scalo, Potenza (Italy). Istituto per i Materiali Speciali; Latzel, H.

    1997-01-01

    Time resolved Laser Induced Grating Spectroscopy (LIGS) has been performed to detect different gases in mixtures at atmospheric pressure or higher. The possibility of trace detection of minor species and of temperature measurements has been demonstrated for various molecular species either of environmental interest or involved in combustion processes. In view of the application of tracing unburned hydrocarbons in combustion chambers, the coupling of the IR-LIGS technique with imaging detection has been considered and preliminary results obtained in small size ethylene/air flames are shown.

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

    Science.gov (United States)

    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 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.

  20. Time-resolved photoelectron spectroscopy of nitrobenzene and its aldehydes

    Science.gov (United States)

    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.

  1. Time-resolved spectroscopy defines perturbation in molecules

    International Nuclear Information System (INIS)

    Ahmed, K.

    1998-01-01

    Time-resolved LIF spectroscopy is employed in order to investigate perturbations in different excited electronic state of alkali molecules. Dunham Coefficients are used to search the selected excited ro-vibrational level, which is overlap with the other nearby excited states. Lifetime measurement has been performed of more than 50 ro-vibrational levels. Out of these 25 levels were observed drastically different lifetimes from the other unperturbed levels. In this report, influence of different perturbations on this anomalous behavior is investigated and discussed. (author)

  2. Examining Electron-Boson Coupling Using Time-Resolved Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Sentef, Michael; Kemper, Alexander F.; Moritz, Brian; Freericks, James K.; Shen, Zhi-Xun; Devereaux, Thomas P.

    2013-12-26

    Nonequilibrium pump-probe time-domain spectroscopies can become an important tool to disentangle degrees of freedom whose coupling leads to broad structures in the frequency domain. Here, using the time-resolved solution of a model photoexcited electron-phonon system, we show that the relaxational dynamics are directly governed by the equilibrium self-energy so that the phonon frequency sets a window for “slow” versus “fast” recovery. The overall temporal structure of this relaxation spectroscopy allows for a reliable and quantitative extraction of the electron-phonon coupling strength without requiring an effective temperature model or making strong assumptions about the underlying bare electronic band dispersion.

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

    Science.gov (United States)

    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…

  4. Application of microfluidic devices for time resolved FTIR spectroscopy

    International Nuclear Information System (INIS)

    Wagner, C.

    2012-01-01

    Within this thesis, micro fluidic mixers, operated in continuous flow mode, were used for time resolved FTIR studies of chemical reactions in aqueous solution. Any chemical reaction, that can be started upon mixing two reagents, can be examined with this technique. The mixing channel also serves as the observation window for the IR measurements. The actual measurements take place at well defined spots along this channel, corresponding to specific reaction times: moving the measurement spot (100 × 100 μm 2 ) towards the entry yields shorter reaction times, moving it towards the channel's end gives longer reaction times. The temporal resolution of the experiment depends on the flow rate inside the mixing channel and the spacing between subsequent measurement points. Fast flow rates, limited by the back pressure of the mixer leading to leakages, allow time resolutions in the sub-millisecond time range using a standard FTIR microscope, whereas slow flow rates allow the measurement of reaction times up to 1000 ms. Evaluating the mixer using a fast chemical reaction resulted in mixing times of approximately 5 ms and a homogeneous distribution of the liquids across the width of the mixing channel. The mixer was then used for the measurement of the H/D exchange on carbohydrates, the complex formaldehyde sulfite clock reaction, and the folding of the protein ubiquitin from its native to the ''A'' state, induced by mixing it with an acidified methanol solution. For cleaning the mixer a software tool, called ATLAS, was developed in LabVIEW, which was used to automatize the necessary cleaning steps performed by a dedicated flow system. Additionally, the micro mixer technology was combined with the step scan measurement technique using a beam condenser focusing the IR beam of an FTIR spectrometer down to a spot size of 1 mm diameter and through the mixer. The laser light, initiating the chemical reaction inside the mixing channel, was coupled into the focusing unit using a

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

    Science.gov (United States)

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

    2008-03-20

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

  6. Ultrafast time-resolved spectroscopy of lead halide perovskite films

    Science.gov (United States)

    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.

  7. Femtosecond time-resolved transient absorption spectroscopy of xanthophylls.

    Science.gov (United States)

    Niedzwiedzki, Dariusz M; Sullivan, James O; Polívka, Tomás; Birge, Robert R; Frank, Harry A

    2006-11-16

    Xanthophylls are a major class of photosynthetic pigments that participate in an adaptation mechanism by which higher plants protect themselves from high light stress. In the present work, an ultrafast time-resolved spectroscopic investigation of all the major xanthophyll pigments from spinach has been performed. The molecules are zeaxanthin, lutein, violaxanthin, and neoxanthin. beta-Carotene was also studied. The experimental data reveal the inherent spectral properties and ultrafast dynamics including the S(1) state lifetimes of each of the pigments. In conjunction with quantum mechanical computations the results address the molecular features of xanthophylls that control the formation and decay of the S* state in solution. The findings provide compelling evidence that S* is an excited state with a conformational geometry twisted relative to the ground state. The data indicate that S* is formed via a branched pathway from higher excited singlet states and that its yield depends critically on the presence of beta-ionylidene rings in the polyene system of pi-electron conjugated double bonds. The data are expected to be beneficial to researchers employing ultrafast time-resolved spectroscopic methods to investigate the mechanisms of both energy transfer and nonphotochemical quenching in higher plant preparations.

  8. Plasma polarization spectroscopy. Time resolved spectroscopy in soft x-ray region on recombining plasma

    International Nuclear Information System (INIS)

    Iwamae, Atsushi; Hasuo, Masahiro; Atake, Makoto; Hasegawa, Noboru; Kawachi, Tetsuya

    2007-01-01

    We present an experimental study of polarization of emission radiations from recombining plasmas generated by the interaction of 60 fs ultra-short laser pulses with a gas jet. Time-resolved spectroscopy with a temporal resolution of 5 ps with repetitive accumulation is used to follow the recombination time histories. (author)

  9. Determination of quenching coefficients by time resolved emission spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Gans, T.; Schulz-von der Gathen, V.; Doebele, H.F. [Essen Univ. (Gesamthochschule) (Germany). Inst. fuer Laser- und Plasmaphysik

    2001-07-01

    Capacitively coupled RF discharges (CCRF discharges) at 13.56 MHz in hydrogen exhibit a field reversal phase of about 10 ns during which an intense electron current provides collisional excitation, within the sheath region. After this strongly dominant short pulsed electron impact excitation, it is possible to determine quenching coefficients from the lifetime of the fluorescence at various pressures by time resolved OES even for high energy levels and without any restrictions of optical selection rules. This novel technique allows the measurement of quenching coefficients for atomic and molecular emission lines of hydrogen itself, as well as for emission lines of small admixtures (e.g. noble gases) to the hydrogen discharge, since with a fast gate-able ICCD camera operating at 13.56 MHz it is possible to measure even faint emission lines temporally resolved.

  10. Determination of quenching coefficients by time resolved emission spectroscopy

    International Nuclear Information System (INIS)

    Gans, T.; Schulz-von der Gathen, V.; Doebele, H.F.

    2001-01-01

    Capacitively coupled RF discharges (CCRF discharges) at 13.56 MHz in hydrogen exhibit a field reversal phase of about 10 ns during which an intense electron current provides collisional excitation, within the sheath region. After this strongly dominant short pulsed electron impact excitation, it is possible to determine quenching coefficients from the lifetime of the fluorescence at various pressures by time resolved OES even for high energy levels and without any restrictions of optical selection rules. This novel technique allows the measurement of quenching coefficients for atomic and molecular emission lines of hydrogen itself, as well as for emission lines of small admixtures (e.g. noble gases) to the hydrogen discharge, since with a fast gate-able ICCD camera operating at 13.56 MHz it is possible to measure even faint emission lines temporally resolved

  11. Femtosecond time-resolved transient absorption spectroscopy of xanthophylls

    Czech Academy of Sciences Publication Activity Database

    Niedzwiedzki, D.; Sullivan, J.O.; Polívka, Tomáš; Birge, R.R.; Frank, H.A.

    2006-01-01

    Roč. 110, č. 45 (2006), s. 22872-22885 ISSN 1520-6106 Institutional research plan: CEZ:AV0Z50510513 Keywords : xanthophyll * spectroscopy study Subject RIV: BO - Biophysics Impact factor: 4.115, year: 2006

  12. Time-resolved photoelectron spectroscopy and ab initio multiple spawning studies of hexamethylcyclopentadiene

    DEFF Research Database (Denmark)

    Wolf, T. J. A.; Kuhlman, Thomas Scheby; Schalk, O.

    2014-01-01

    Time-resolved photoelectron spectroscopy and ab initio multiple spawning were applied to the ultrafast non-adiabatic dynamics of hexamethylcyclopentadiene. The high level of agreement between experiment and theory associates wavepacket motion with a distinct degree of freedom.......Time-resolved photoelectron spectroscopy and ab initio multiple spawning were applied to the ultrafast non-adiabatic dynamics of hexamethylcyclopentadiene. The high level of agreement between experiment and theory associates wavepacket motion with a distinct degree of freedom....

  13. Time-resolved photoelectron spectroscopy using synchrotron radiation time structure

    International Nuclear Information System (INIS)

    Bergeard, N.; Silly, M.G.; Chauvet, C.; Guzzo, M.; Ricaud, J.P.; Izquierdo, M.; Sirotti, F.; Krizmancic, D.; Guzzo, M.; Stebel, L.; Pittana, P.; Sergo, R.; Cautero, G.; Dufour, G.; Rochet, F.

    2011-01-01

    Synchrotron radiation time structure is becoming a common tool for studying dynamic properties of materials. The main limitation is often the wide time domain the user would like to access with pump-probe experiments. In order to perform photoelectron spectroscopy experiments over time scales from milliseconds to picoseconds it is mandatory to measure the time at which each measured photoelectron was created. For this reason the usual CCD camera based two-dimensional detection of electron energy analyzers has been replaced by a new delay-line detector adapted to the time structure of the SOLEIL synchrotron radiation source. The new two-dimensional delay-line detector has a time resolution of 5 ns and was installed on a Scienta SES 2002 electron energy analyzer. The first application has been to characterize the time of flight of the photo emitted electrons as a function of their kinetic energy and the selected pass energy. By repeating the experiment as a function of the available pass energy and of the kinetic energy, a complete characterization of the analyzer behaviour in the time domain has been obtained. Even for kinetic energies as low as 10 eV at 2 eV pass energy, the time spread of the detected electrons is lower than 140 ns. These results and the time structure of the SOLEIL filling modes assure the possibility of performing pump-probe photoelectron spectroscopy experiments with the time resolution given by the SOLEIL pulse width, the best performance of the beamline and of the experimental station. (authors)

  14. Time-resolved diode laser infrared absorption spectroscopy of the nascent HCl in the infrared laser chemistry of 1,2-dichloro-1,1-difluoroethane

    Science.gov (United States)

    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.

  15. Mobile charge generation dynamics in P3HT: PCBM observed by time-resolved terahertz spectroscopy

    DEFF Research Database (Denmark)

    Cooke, D. G.; Krebs, Frederik C; Jepsen, Peter Uhd

    2012-01-01

    Ultra-broadband time-resolved terahertz spectroscopy is used to examine the sub-ps conductivity dynamics of a conjugated polymer bulk heterojunction film P3HT:PCBM. We directly observe mobile charge generation dynamics on a sub-100 fs time scale.......Ultra-broadband time-resolved terahertz spectroscopy is used to examine the sub-ps conductivity dynamics of a conjugated polymer bulk heterojunction film P3HT:PCBM. We directly observe mobile charge generation dynamics on a sub-100 fs time scale....

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

    International Nuclear Information System (INIS)

    Hedqvist, A.; Rachlew-Kaellne, E.

    1998-01-01

    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 Z eff together with a description of the interpretation and the equipment are presented. (author)

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

    Science.gov (United States)

    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.

  18. Finite-difference time-domain analysis of time-resolved terahertz spectroscopy experiments

    DEFF Research Database (Denmark)

    Larsen, Casper; Cooke, David G.; Jepsen, Peter Uhd

    2011-01-01

    In this paper we report on the numerical analysis of a time-resolved terahertz (THz) spectroscopy experiment using a modified finite-difference time-domain method. Using this method, we show that ultrafast carrier dynamics can be extracted with a time resolution smaller than the duration of the T...

  19. Hexamethylcyclopentadiene: time-resolved photoelectron spectroscopy and ab initio multiple spawning simulations

    DEFF Research Database (Denmark)

    Wolf, T. J. A.; Kuhlman, Thomas Scheby; Schalk, O.

    2014-01-01

    comparing time-resolved photoelectron spectroscopy (TRPES) with ab initio multiple spawning (AIMS) simulations on the MS-MR-CASPT2 level of theory. We disentangle the relationship between two phenomena that dominate the immediate molecular response upon light absorption: a spectrally dependent delay...

  20. Speciation of actinides in aqueous solution by time-resolved laser-induced fluorescence spectroscopy (TRLFS)

    International Nuclear Information System (INIS)

    Kimura, Takaumi; Kato, Yoshiharu; Meinrath, G.; Yoshida, Zenko; Choppin, G.R.

    1995-01-01

    Time-resolved laser-induced fluorescence spectroscopy (TRLFS) as a sensitive and selective method has been applied to the speciation of actinides in aqueous solution. Studies on hydrolysis and carbonate complexation of U(VI) and on determination of hydration number of Cm(III) are reported. (author)

  1. Time resolved optical emission spectroscopy of cross-beam pulsed laser ablation on graphite targets

    International Nuclear Information System (INIS)

    Sangines, R.; Sanchez Ake, C.; Sobral, H.; Villagran-Muniz, M.

    2007-01-01

    Cross-beam pulsed laser ablation with two delayed lasers is performed on two perpendicular graphite targets. The time delay between lasers is varied by up to 5 μs, and physical changes on the second plasma, due to the interaction with the first generated one, are determined by time resolved optical emission spectroscopy

  2. Laser induced breakdown spectroscopy of the uranium including calcium. Time resolved measurement spectroscopic analysis (Contract research)

    International Nuclear Information System (INIS)

    Akaoka, Katsuaki; Maruyama, Youichiro; Oba, Masaki; Miyabe, Masabumi; Otobe, Haruyoshi; Wakaida, Ikuo

    2010-05-01

    For the remote analysis of low DF TRU (Decontamination Factor Transuranic) fuel, Laser Breakdown Spectroscopy (LIBS) was applied to uranium oxide including a small amount of calcium oxide. The characteristics, such as spectrum intensity and plasma excitation temperature, were measured using time-resolved spectroscopy. As a result, in order to obtain the stable intensity of calcium spectrum for the uranium spectrum, it was found out that the optimum observation delay time of spectrum is 4 microseconds or more after laser irradiation. (author)

  3. Femtosecond time-resolved vibrational SFG spectroscopy of CO/Ru( 0 0 1 )

    Science.gov (United States)

    Hess, Ch.; Wolf, M.; Roke, S.; Bonn, M.

    2002-04-01

    Vibrational sum-frequency generation (SFG) employing femtosecond infrared (IR) laser pulses is used to study the dynamics of the C-O stretch vibration on Ru(0 0 1). Time-resolved measurements of the free induction decay (FID) of the IR-polarization for 0.33 ML CO/Ru(0 0 1) exhibit single exponential decays over three decades corresponding to dephasing times of T2=1.94 ps at 95 K and T2=1.16 ps at 340 K. This is consistent with pure homogeneous broadening due to anharmonic coupling with the thermally activated low-frequency dephasing mode together with a contribution from saturation of the IR transition. In pump-probe SFG experiments using a strong visible (VIS) pump pulse the perturbation of the FID leads to transient line shifts even at negative delay times, i.e. when the IR-VIS SFG probe pair precedes the pump pulse. Based on an analysis of the time-dependent polarization we discuss the influence of the perturbed FID on time-resolved SFG spectra. We investigate how coherent effects affect the SFG spectra and we examine the time resolution in these experiments, in particular in dependence of the dephasing time.

  4. Time-resolved resonance fluorescence spectroscopy for study of chemical reactions in laser-induced plasmas.

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  6. Charge transport in nanostructured materials for solar energy conversion studied by time-resolved terahertz spectroscopy

    Czech Academy of Sciences Publication Activity Database

    Němec, Hynek; Kužel, Petr; Sundström, V.

    2010-01-01

    Roč. 215, 2-3 (2010), s. 123-139 ISSN 1010-6030 R&D Projects: GA ČR(CZ) GP202/09/P099; GA AV ČR(CZ) IAA100100902; GA MŠk LC512 Institutional research plan: CEZ:AV0Z10100520 Keywords : time-resolved terahertz spectroscopy * ultrafast dynamics * bulk heterojunction * semiconductor nanostructures * transport * mobility Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.243, year: 2010

  7. Ionic classification of Xe laser lines: A new approach through time resolved spectroscopy

    International Nuclear Information System (INIS)

    Schinca, D.; Duchowicz, R.; Gallardo, M.

    1992-01-01

    Visible and UV laser emission from a highly ionized pulsed Xe plasma was studied in relation to the ionic assignment of the laser lines. Time-resolved spectroscopy was used to determine the ionic origin of the studied lines. The results are in agreement with an intensity versus pressure analysis performed over the same wavelength range. From the temporal behaviour of the spontaneous emission, a probable classification can be obtained. (author). 7 refs, 7 figs, 1 tab

  8. Time-resolved tunable diode laser absorption spectroscopy of pulsed plasma

    Czech Academy of Sciences Publication Activity Database

    Adámek, Petr; Olejníček, Jiří; Čada, Martin; Kment, Š.; Hubička, Zdeněk

    2013-01-01

    Roč. 38, č. 14 (2013), s. 2428-2430 ISSN 0146-9592 R&D Projects: GA MŠk LH12045; GA ČR(CZ) GAP205/11/0386; GA MŠk LD12002; GA MŠk LH12043 Institutional support: RVO:68378271 Keywords : diode laser s * plasma diagnostics * absorption spectroscopy * time resolved Subject RIV: BL - Plasma and Gas Discharge Physics Impact factor: 3.179, year: 2013

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

    Science.gov (United States)

    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.

  10. Photophysical characterization and time-resolved spectroscopy of a anthradithiophene dimer: exploring the role of conformation in singlet fission

    KAUST Repository

    Dean, Jacob C.; Zhang, Ruomeng; Hallani, Rawad K.; Pensack, Ryan D.; Sanders, Samuel N.; Oblinsky, Daniel G.; Parkin, Sean R.; Campos, Luis M.; Anthony, John E.; Scholes, Gregory D.

    2017-01-01

    carried out in toluene and acetone solution via absorption and fluorescence spectroscopy, and their photo-initiated dynamics were investigated with time-resolved fluorescence (TRF) and transient absorption (TA) spectroscopy. In accordance

  11. Time-resolved x-ray laser induced photoelectron spectroscopy of isochoric heated copper

    International Nuclear Information System (INIS)

    Nelson, A.J.; Dunn, J.; Hunter, J.; Widmann, K.

    2005-01-01

    Time-resolved x-ray photoelectron spectroscopy is used to probe the nonsteady-state evolution of the valence band electronic structure of laser heated ultrathin (50 nm) copper. A metastable phase is studied using a 527 nm wavelength 400 fs laser pulse containing 0.1-2.5 mJ laser energy focused in a large 500x700 μm 2 spot to create heated conditions of 0.07-1.8x10 12 W cm -2 intensity. Valence band photoemission spectra are presented showing the changing occupancy of the Cu 3d level with heating are presented. These picosecond x-ray laser induced time-resolved photoemission spectra of laser-heated ultrathin Cu foil show dynamic changes in the electronic structure. The ultrafast nature of this technique lends itself to true single-state measurements of shocked and heated materials

  12. Broad-band time-resolved near infrared spectroscopy in the TJ-II stellarator

    Energy Technology Data Exchange (ETDEWEB)

    Rodriguez, M.C.; Pastor, I.; Cal, E. de la; McCarthy, K.J. [Laboratorio Nacional de Fusion, CIEMAT, Madrid (Spain); Diaz, D. [Universidad Autonoma de Madrid, Dept Quimica Fisica Aplicada, Madrid (Spain)

    2014-11-15

    First experimental results on broad-band, time-resolved Near Infrared (NIR;here loosely defined as covering from 750 to 1650 nm) passive spectroscopy using a high sensitivity InGaAs detector are reported for the TJ-II Stellarator. Experimental set-up is described together with its main characteristics, the most remarkable ones being its enhanced NIR response, broadband spectrum acquisition in a single shot, and time-resolved measurements with up to 1.8 kHz spectral rate. Prospects for future work and more extended physics studies in this newly open spectral region in TJ-II are discussed. (copyright 2014 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  13. Liver Status Assessment by Spectrally and Time Resolved IR Detection of Drug Induced Breath Gas Changes

    Directory of Open Access Journals (Sweden)

    Tom Rubin

    2016-05-01

    Full Text Available The actual metabolic capacity of the liver is crucial for disease identification, liver therapy, and liver tumor resection. By combining induced drug metabolism and high sensitivity IR spectroscopy of exhaled air, we provide a method for quantitative liver assessment at bedside within 20 to 60 min. Fast administration of 13C-labelled methacetin induces a fast response of liver metabolism and is tracked in real-time by the increase of 13CO2 in exhaled air. The 13CO2 concentration increase in exhaled air allows the determination of the metabolic liver capacity (LiMAx-test. Fluctuations in CO2 concentration, pressure and temperature are minimized by special gas handling, and tracking of several spectrally resolved CO2 absorption bands with a quantum cascade laser. Absorption measurement of different 12CO2 and 13CO2 rotation-vibration transitions in the same time window allows for multiple referencing and reduction of systematic errors. This FLIP (Fast liver investigation package setup is being successfully used to plan operations and determine the liver status of patients.

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

    International Nuclear Information System (INIS)

    Wang, Shicong; Wendt, Amy E.; Boffard, John B.; Lin, Chun C.

    2015-01-01

    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 pulsed 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

  15. Hole emission from Ge/Si quantum dots studied by time-resolved capacitance spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Kapteyn, C.M.A.; Lion, M.; Heitz, R.; Bimberg, D. [Technische Univ. Berlin (Germany). Inst. fuer Festkoerperphysik; Miesner, C.; Asperger, T.; Brunner, K.; Abstreiter, G. [Technische Univ. Muenchen, Garching (Germany). Walter-Schottky-Inst. fuer Physikalische Grundlagen der Halbleiterelektronik

    2001-03-01

    Emission of holes from self-organized Ge quantum dots (QDs) embedded in Si Schottky diodes is studied by time-resolved capacitance spectroscopy (DLTS). The DLTS signal is rather broad and depends strongly on the filling and detection bias conditions. The observed dependence is interpreted in terms of carrier emission from many-hole states of the QDs. The activation energies obtained from the DLTS measurements are a function of the amount of stored charge and the position of the Fermi level in the QDs. (orig.)

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

    Science.gov (United States)

    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.

  17. Time-resolved spectroscopy of plasma resonances in highly excited silicon and germanium

    International Nuclear Information System (INIS)

    Huang, C.Y.; Malvezzi, A.M.; Bloembergen, N.; Kurz, H.

    1985-01-01

    The dynamics of the electron-hole plasma in silicon and germanium samples irradiated by 20 ps. 532 nm laser pulses has been investigated in the near infrared by the time-resolved picosecond optical spectroscopy. The experimental reflectivities and transmission are compared with the predictions of the thermal model for degenerate carrier distributions through the Drude formalism. Above a certain fluence, a significant deviation between measured and calculated values indicates a strong increase of the recombination rate as soon as the plasma resonances become comparable with the band gaps. These new plasmon-aided recombination channels are particularly pronounced in germanium. 15 refs., 8 figs

  18. Time-resolved terahertz spectroscopy of conjugated polymer/CdSe nanorod composites

    DEFF Research Database (Denmark)

    Cooke, David; Lek, Jun Y.; Krebs, Frederik C

    2010-01-01

    report ultrafast carrier dynamics in hybrid CdSe nanorod / poly(3-hexythiophene) (P3HT) bulk heterojunction films measured by time-resolved terahertz spectroscopy, and compare to the well studied P3HT/phenyl-C61-butyric acid methyl ester (PCBM) blend. Both films show an improved peak...... photoconductivity compared to P3HT alone, consistent with efficient charge transfer. The photoconductivity dynamics show fast, picosecond trapping or recombination in the hybrid blend while the all-organic film shows no such loss of mobile charge over ns time scales. The ac conductivity for all samples is well...

  19. Time-resolved luminescent spectroscopy of YAG:Ce single crystal and single crystalline films

    International Nuclear Information System (INIS)

    Zorenko, Yu.; Gorbenko, V.; Savchyn, V.; Vozniak, T.; Puzikov, V.; Danko, A.; Nizhankovski, S.

    2010-01-01

    The peculiarities of the luminescence and energy transfer from YAG host to the emission centers formed by the Y Al antisite defects and Ce 3+ ions have been studied in YAG:Ce single crystals, grown from the melt by modified Bridgman method in Ar and CO 2 + H 2 atmospheres, and YAG:Ce single crystalline film, grown by liquid phase epitaxy method, using the comparative time-resolved luminescent spectroscopy under excitation by synchrotron radiation in the range of fundamental adsorption of this garnet.

  20. Time-resolved and doppler-reduced laser spectroscopy on atoms

    International Nuclear Information System (INIS)

    Bergstroem, H.

    1991-10-01

    Radiative lifetimes have been studied in neutral boron, carbon, silicon and strontium, in singly ionized gadolinium and tantalum and in molecular carbon monoxide and C 2 . The time-resolved techniques were based either on pulsed lasers or pulse-modulated CW lasers. Several techniques have been utilized for the production of free atoms and ions such as evaporation into an atomic beam, sputtering in hollow cathodes and laser-produced plasmas. Hyperfine interactions in boron, copper and strontium have been examined using quantum beat spectroscopy, saturation spectroscopy and collimated atomic beam spectroscopy. Measurement techniques based on effusive hollow cathodes as well as laser produced plasmas in atomic physics have been developed. Investigations on laser produced plasmas using two colour beam deflection tomography for determination of electron densities have been performed. Finally, new possibilities for view-time-expansion in light-in-flight holography using mode-locked CW lasers have been demonstrated. (au)

  1. Time-resolved pump and probe x-ray absorption fine structure spectroscopy at beamline P11 at PETRA III

    Energy Technology Data Exchange (ETDEWEB)

    Göries, D., E-mail: dennis.goeries@desy.de; Roedig, P.; Stübe, N.; Meyer, J.; Warmer, M.; Weckert, E.; Meents, A., E-mail: alke.meents@desy.de [DESY Photon Science, Deutsches Elektronen-Synchrotron (DESY), Notkestraße 85, 22607 Hamburg (Germany); Dicke, B.; Naumova, M.; Rübhausen, M. [Center for Free-Electron Laser Science (CFEL), Luruper Chaussee 149, 22761 Hamburg (Germany); Galler, A.; Gawelda, W.; Geßler, P.; Sotoudi Namin, H.; Beckmann, A. [European XFEL, Albert-Einstein Ring 19, 22761 Hamburg (Germany); Britz, A.; Bressler, C. [European XFEL, Albert-Einstein Ring 19, 22761 Hamburg (Germany); The Hamburg Centre for Ultrafast Imaging, Luruper Chaussee 149, 22761 Hamburg (Germany); Schlie, M. [Institut für Experimentalphysik, University of Hamburg, Luruper Chaussee 149, 22761 Hamburg (Germany)

    2016-05-15

    We report about the development and implementation of a new setup for time-resolved X-ray absorption fine structure spectroscopy at beamline P11 utilizing the outstanding source properties of the low-emittance PETRA III synchrotron storage ring in Hamburg. Using a high intensity micrometer-sized X-ray beam in combination with two positional feedback systems, measurements were performed on the transition metal complex fac-Tris[2-phenylpyridinato-C2,N]iridium(III) also referred to as fac-Ir(ppy){sub 3}. This compound is a representative of the phosphorescent iridium(III) complexes, which play an important role in organic light emitting diode (OLED) technology. The experiment could directly prove the anticipated photoinduced charge transfer reaction. Our results further reveal that the temporal resolution of the experiment is limited by the PETRA III X-ray bunch length of ∼103 ps full width at half maximum (FWHM).

  2. Time-resolved X-ray photoelectron spectroscopy techniques for the study of interfacial charge dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Neppl, Stefan, E-mail: sneppl@lbl.gov; Gessner, Oliver

    2015-04-15

    Highlights: • Ultrafast interfacial charge transfer is probed with atomic site specificity. • Femtosecond X-ray photoelectron spectroscopy using a free electron laser. • Efficient and flexible picosecond X-ray photoelectron pump–probe scheme using synchrotron radiation. - Abstract: X-ray photoelectron spectroscopy (XPS) is one of the most powerful techniques to quantitatively analyze the chemical composition and electronic structure of surfaces and interfaces in a non-destructive fashion. Extending this technique into the time domain has the exciting potential to shed new light on electronic and chemical dynamics at surfaces by revealing transient charge configurations with element- and site-specificity. Here, we describe prospects and challenges that are associated with the implementation of picosecond and femtosecond time-resolved X-ray photoelectron spectroscopy at third-generation synchrotrons and X-ray free-electron lasers, respectively. In particular, we discuss a series of laser-pump/X-ray-probe photoemission experiments performed on semiconductor surfaces, molecule-semiconductor interfaces, and films of semiconductor nanoparticles that demonstrate the high sensitivity of time-resolved XPS to light-induced charge carrier generation, diffusion and recombination within the space charge layers of these materials. Employing the showcase example of photo-induced electronic dynamics in a dye-sensitized semiconductor system, we highlight the unique possibility to probe heterogeneous charge transfer dynamics from both sides of an interface, i.e., from the perspective of the molecular electron donor and the semiconductor acceptor, simultaneously. Such capabilities will be crucial to improve our microscopic understanding of interfacial charge redistribution and associated chemical dynamics, which are at the heart of emerging energy conversion, solar fuel generation, and energy storage technologies.

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

    Science.gov (United States)

    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

  4. Time-resolved ultraviolet laser-induced breakdown spectroscopy for organic material analysis

    Energy Technology Data Exchange (ETDEWEB)

    Baudelet, Matthieu; Boueri, Myriam [Laboratoire de Spectrometrie Ionique et Moleculaire, Universite Claude Bernard Lyon 1, UMR CNRS 5579, 43, Bd. du 11 Novembre 1918, F-69622 Villeurbanne Cedex (France); Yu Jin [Laboratoire de Spectrometrie Ionique et Moleculaire, Universite Claude Bernard Lyon 1, UMR CNRS 5579, 43, Bd. du 11 Novembre 1918, F-69622 Villeurbanne Cedex (France)], E-mail: jin.yu@lasim.univ-lyon1.fr; Mao, Samuel S; Piscitelli, Vincent; Xianglei, Mao; Russo, Richard E [Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States)

    2007-12-15

    Ultraviolet pulses (266 nm) delivered by a quadrupled Nd:YAG laser were used to analyze organic samples with laser-induced breakdown spectroscopy (LIBS). We present characteristics of the spectra obtained from organic samples with special attentions on the emissions of organic elements, O and N, and molecular bonds CN. The choice of these atomic or molecular species is justified on one hand, by the importance of these species to specify organic or biological materials; and on the other hand by the possible interferences with ambient air when laser ablation takes place in the atmosphere. Time-resolved LIBS was used to determine the time-evolution of line intensity emitted from these species. We demonstrate different kinetic behaviors corresponding to different origins of emitters: native atomic or molecular species directly vaporized from the sample or those generated through dissociation or recombination due to interaction between laser-induced plasma and air molecules. Our results show the ability of time-resolved UV-LIBS for detection and identification of native atomic or molecular species from an organic sample.

  5. Time-resolved pump-probe X-ray absorption fine structure spectroscopy of Gaq3

    International Nuclear Information System (INIS)

    Dicke, Benjamin

    2013-01-01

    Gallium(tris-8-hydroxyquinoline) (Gaq 3 ) belongs to a class of metal organic compounds, used as electron transport layer and emissive layer in organic light emitting diodes. Many research activities have concentrated on the optical and electronic properties, especially of the homologue molecule aluminum(tris-8-hydroxyquinoline) (Alq 3 ). Knowledge of the first excited state S 1 structure of these molecules could provide deeper insight into the processes involved into the operation of electronic devices, such as OLEDs and, hence, it could further improve their efficiency and optical properties. Until now the excited state structure could not be determined experimentally. Most of the information about this structure mainly arises from theoretical calculations. X-ray absorption fine structure (XAFS) spectroscopy is a well developed technique to determine both, the electronic and the geometric properties of a sample. The connection of ultrashort pulsed X-ray sources with a pulsed laser system offers the possibility to use XAFS as a tool for studying the transient changes of a sample induced by a laser pulse. In the framework of this thesis a new setup for time-resolved pump-probe X-ray absorption spectroscopy at PETRA III beamline P11 was developed for measuring samples in liquid form. In this setup the sample is pumped into its photo-excited state by a femtosecond laser pump pulse with 343 nm wavelength and after a certain time delay probed by an X-ray probe pulse. In this way the first excited singlet state S 1 of Gaq 3 dissolved in benzyl alcohol was analyzed. A structural model for the excited state structure of the Gaq 3 molecule based on the several times reproduced results of the XAFS experiments is proposed. According to this model it was found that the Ga-N A bond length is elongated, while the Ga-O A bond length is shortened upon photoexcitation. The dynamics of the structural changes were not the focus of this thesis. Nevertheless the excited state lifetime

  6. The application of time-resolved luminescence spectroscopy to a remote uranyl sensor

    International Nuclear Information System (INIS)

    Varineau, P.T.; Duesing, R.; Wangen, L.E.

    1991-01-01

    Time resolved luminescence spectroscopy is an effective method for the determination of a wide range of uranyl concentrations in aqueous samples. We have applied this technique to the development of a remote sensing device using fiber optic cables coupled with a micro flow cell in order to probe for uranyl in aqueous samples. This sensor incorporates a Nafion membrane through which UO 2 2+ can diffuse in to a reaction/analysis chamber which holds phosphoric acid, a reagent which enhances the uranyl luminescence intensity and lifetime. With this device, anionic and fluorescing organic interferences could be eliminated, allowing for the determination of uranyl over a concentration range of 10 4 to 10 -9 M. 17 refs., 5 figs

  7. Structure-activity relationships of heterogeneous catalysts from time-resolved X-ray absorption spectroscopy

    International Nuclear Information System (INIS)

    Ressler, T.; Jentoft, R.E.; Wienold, J.; Girgsdies, F.; Neisius, T.; Timpe, O.

    2003-01-01

    Knowing the composition and the evolution of the bulk structure of a heterogeneous catalyst under working conditions (in situ) is a pre-requisite for understanding structure-activity relationships. X-ray absorption spectroscopy can be employed to study a catalytically active material in situ. In addition to steady-state investigations, the technique permits experiments with a time-resolution in the sub-second range to elucidate the solid-state kinetics of the reactions involved. Combined with mass spectrometry, the evolution of the short-range order structure of a heterogeneous catalyst, the average valence of the constituent metals, and the phase composition can be obtained. Here we present results obtained from time-resolved studies on the reduction of MoO 3 in propene and in propene and oxygen

  8. Femtosecond time-resolved impulsive stimulated Raman spectroscopy using sub-7-fs pulses: Apparatus and applications

    Energy Technology Data Exchange (ETDEWEB)

    Kuramochi, Hikaru [Molecular Spectroscopy Laboratory, RIKEN, 2-1 Hirosawa, Wako 351-0198 (Japan); Takeuchi, Satoshi; Tahara, Tahei, E-mail: tahei@riken.jp [Molecular Spectroscopy Laboratory, RIKEN, 2-1 Hirosawa, Wako 351-0198 (Japan); Ultrafast Spectroscopy Research Team, RIKEN Center for Advanced Photonics (RAP), 2-1 Hirosawa, Wako 351-0198 (Japan)

    2016-04-15

    We describe details of the setup for time-resolved impulsive stimulated Raman spectroscopy (TR-ISRS). In this method, snapshot molecular vibrational spectra of the photoreaction transients are captured via time-domain Raman probing using ultrashort pulses. Our instrument features transform-limited sub-7-fs pulses to impulsively excite and probe coherent nuclear wavepacket motions, allowing us to observe vibrational fingerprints of transient species from the terahertz to 3000-cm{sup −1} region with high sensitivity. Key optical components for the best spectroscopic performance are discussed. The TR-ISRS measurements for the excited states of diphenylacetylene in cyclohexane are demonstrated, highlighting the capability of our setup to track femtosecond dynamics of all the Raman-active fundamental molecular vibrations.

  9. Isotope effect on hydrated electron relaxation dynamics studied with time-resolved liquid jet photoelectron spectroscopy

    Science.gov (United States)

    Elkins, Madeline H.; Williams, Holly L.; Neumark, Daniel M.

    2016-05-01

    The excited state relaxation dynamics of the solvated electron in H2O and D2O are investigated using time-resolved photoelectron spectroscopy in a liquid microjet. The data show that the initial excited state decays on a time scale of 75 ± 12 fs in H2O and 102 ± 8 fs in D2O, followed by slower relaxation on time scales of 400 ± 70 fs and 390 ± 70 fs that are isotopically invariant within the precision of our measurements. Based on the time evolution of the transient signals, the faster and slower time constants are assigned to p → s internal conversion (IC) of the hydrated electron and relaxation on the ground electronic state, respectively. This assignment is consistent with the non-adiabatic mechanism for relaxation of the hydrated electron and yields an isotope effect of 1.4 ± 0.2 for IC of the hydrated electron.

  10. Exploring the Dynamics of Superconductors by Time-Resolved Far-Infrared Spectroscopy

    International Nuclear Information System (INIS)

    Carr, G. L.; Lobo, R. P. S. M.; LaVeigne, J.; Reitze, D. H.; Tanner, D. B.

    2000-01-01

    We have examined the recombination of excess quasiparticles in superconducting Pb by time-resolved far-infrared spectroscopy using a pulsed synchrotron source. The energy gap shift calculated by Owen and Scalapino [Phys. Rev. Lett. 28, 1559 (1972)] is directly observed, as is the associated reduction in the Cooper pair density. The relaxation process involves a two-component decay; the faster (∼200 ps) is associated with the actual (effective) recombination process, while the slower (∼10 to 100ns) is due to heat transport across the film/substrate interface. The temperature dependence of the recombination process between 0.5T c and 0.85T c is in good agreement with theory

  11. Frame-Transfer Gating Raman Spectroscopy for Time-Resolved Multiscalar Combustion Diagnostics

    Science.gov (United States)

    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

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

    Science.gov (United States)

    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.

  13. Probing specific molecular processes and intermediates by time-resolved Fourier transform infrared spectroscopy: application to the bacteriorhodopsin photocycle.

    Science.gov (United States)

    Lórenz-Fonfría, Víctor A; Kandori, Hideki; Padrós, Esteve

    2011-06-23

    We present a general approach for probing the kinetics of specific molecular processes in proteins by time-resolved Fourier transform infrared (IR) spectroscopy. Using bacteriorhodopsin (bR) as a model we demonstrate that by appropriately monitoring some selected IR bands it is possible obtaining the kinetics of the most important events occurring in the photocycle, namely changes in the chromophore and the protein backbone conformation, and changes in the protonation state of the key residues implicated in the proton transfers. Besides confirming widely accepted views of the bR photocycle, our analysis also sheds light into some disputed issues: the degree of retinal torsion in the L intermediate to respect the ground state; the possibility of a proton transfer from Asp85 to Asp212; the relationship between the protonation/deprotonation of Asp85 and the proton release complex; and the timing of the protein backbone dynamics. By providing a direct way to estimate the kinetics of photocycle intermediates the present approach opens new prospects for a robust quantitative kinetic analysis of the bR photocycle, which could also benefit the study of other proteins involved in photosynthesis, in phototaxis, or in respiratory chains.

  14. Studies of Minerals, Organic and Biogenic Materials through Time-Resolved Raman Spectroscopy

    Science.gov (United States)

    Garcia, Christopher S.; Abedin, M. Nurul; Ismail, Syed; Sharma, Shiv K.; Misra, Anupam K.; Nyugen, Trac; Elsayed-Ali, hani

    2009-01-01

    A compact remote Raman spectroscopy system was developed at NASA Langley Research center and was previously demonstrated for its ability to identify chemical composition of various rocks and minerals. In this study, the Raman sensor was utilized to perform time-resolved Raman studies of various samples such as minerals and rocks, Azalea leaves and a few fossil samples. The Raman sensor utilizes a pulsed 532 nm Nd:YAG laser as excitation source, a 4-inch telescope to collect the Raman-scattered signal from a sample several meters away, a spectrograph equipped with a holographic grating, and a gated intensified CCD (ICCD) camera system. Time resolved Raman measurements were carried out by varying the gate delay with fixed short gate width of the ICCD camera, allowing measurement of both Raman signals and fluorescence signals. Rocks and mineral samples were characterized including marble, which contain CaCO3. Analysis of the results reveals the short (approx.10-13 s) lifetime of the Raman process, and shows that Raman spectra of some mineral samples contain fluorescence emission due to organic impurities. Also analyzed were a green (pristine) and a yellow (decayed) sample of Gardenia leaves. It was observed that the fluorescence signals from the green and yellow leaf samples showed stronger signals compared to the Raman lines. Moreover, it was also observed that the fluorescence of the green leaf was more intense and had a shorter lifetime than that of the yellow leaf. For the fossil samples, Raman shifted lines could not be observed due the presence of very strong short-lived fluorescence.

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

    Directory of Open Access Journals (Sweden)

    Majed Chergui

    2016-05-01

    Full Text Available 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.

  16. Time-resolved spectroscopy of the probe fluorescence in the study of human blood protein dynamic structure on SR beam

    International Nuclear Information System (INIS)

    Dobretsov, G.E.; Kurek, N.K.; Syrejshchikova, T.I.; Yakimenko, M.N.; Clarke, D.T.; Jones, G.R.; Munro, I.H.

    2000-01-01

    Time-resolved spectroscopy on the SRS of the Daresbury Laboratory was used for the study of the human serum lipoproteins and human blood albumins with fluorescent probes K-37 and K-35, developed in Russia. The probe K-37 was found sensitive to the difference in dynamic properties of the lipid objects. Two sets of the parameters were used for the description of lipid dynamic structure: (1) time-resolved fluorescence spectra and (2) time-resolved fluorescence depolarization as a function of rotational mobility of lipid molecules. Each measured dynamic parameter reflected the monotonous changes of dynamic properties in the range: lipid spheres-very low density lipoproteins-low density lipoproteins-high density lipoproteins-phospholipid liposomes. The range is characterized by the increase of the ratio polar/ nonpolar lipids. Thus, time-resolved fluorescence could be used to detect some structural modifications in lipoproteins related to atherosclerosis and subsequent cardiovascular diseases development

  17. Time-resolved spectroscopy of nonequilibrium ionization in laser-produced plasmas

    International Nuclear Information System (INIS)

    Marjoribanks, R.S.

    1988-01-01

    The highly transient ionization characteristic of laser-produced plasmas at high energy densities has been investigated experimentally, using x-ray spectroscopy with time resolution of less than 20 ps. Spectroscopic diagnostics of plasma density and temperature were used, including line ratios, line profile broadening and continuum emission, to characterize the plasma conditions without relying immediately on ionization modeling. The experimentally measured plasma parameters were used as independent variables, driving an ionization code, as a test of ionization modeling, divorced from hydrodynamic calculations. Several state-of-the-art streak spectrographs, each recording a fiducial of the laser peak along with the time-resolved spectrum, characterized the laser heating of thin signature layers of different atomic numbers imbedded in plastic targets. A novel design of crystal spectrograph, with a conically curved crystal, was developed. Coupled with a streak camera, it provided high resolution (λ/ΔΛ > 1000) and a collection efficiency roughly 20-50 times that of planar crystal spectrographs, affording improved spectra for quantitative reduction and greater sensitivity for the diagnosis of weak emitters. Experimental results were compared to hydrocode and ionization code simulations, with poor agreement. The conclusions question the appropriateness of describing electron velocity distributions by a temperature parameter during the time of laser illumination and emphasis the importance of characterizing the distribution more generally

  18. Creation of free excitons in solid krypton investigated by time-resolved luminescence spectroscopy

    International Nuclear Information System (INIS)

    Kisand, Vambola; Kirm, Marco; Negodin, Evgeni; Sombrowski, Elke; Steeg, Barbara; Vielhauer, Sebastian; Zimmerer, Georg

    2003-01-01

    The creation and relaxation of secondary excitons in solid Kr was investigated using energy-and time-resolved luminescence spectroscopy in the vacuum ultraviolet region. The spectrally selected emission of the free exciton (FE) was used as a probe for an investigation of the different exciton creation processes. Delayed FE creation via electron-hole recombination and 'prompt' (in terms of the time-resolution of the experiment) creation of excitons were separated. The 'prompt' creation of a FE appears in the region above threshold energy E th , which is equal to the sum of the band gap energy and the free exciton energy. 'Prompt' creation of excitons above E th is ascribed to a superposition of two processes: (i) creation of the electronic polaron complex (one-step process) and (ii) inelastic scattering of photoelectrons described in the framework of the multiple-parabolic-branch band model (two-step process). In addition, the ratio spectrum of the time-integrated FE and self-trapped exciton (STE) emission was analysed. The behaviour of the ratio spectrum is a proof that electron-hole recombination leads to STE states through FE states as precursors

  19. Time-resolved laser fluorescence spectroscopy of organic ligands by europium: Fluorescence quenching and lifetime properties

    Science.gov (United States)

    Nouhi, A.; Hajjoul, H.; Redon, R.; Gagné, J. P.; Mounier, S.

    2018-03-01

    Time-resolved Laser Fluorescence Spectroscopy (TRLFS) has proved its usefulness in the fields of biophysics, life science and geochemistry to characterize the fluorescence probe molecule with its chemical environment. The purpose of this study is to demonstrate the applicability of this powerful technique combined with Steady-State (S-S) measurements. A multi-mode factor analysis, in particular CP/PARAFAC, was used to analyze the interaction between Europium (Eu) and Humic substances (HSs) extracted from Saint Lawrence Estuary in Canada. The Saint Lawrence system is a semi-enclosed water stream with connections to the Atlantic Ocean and is an excellent natural laboratory. CP/PARAFAC applied to fluorescence S-S data allows introspecting ligands-metal interactions and the one-site 1:1 modeling gives information about the stability constants. From the spectral signatures and decay lifetimes data given by TRLFS, one can deduce the fluorescence quenching which modifies the fluorescence and discuss its mechanisms. Results indicated a relatively strong binding ability between europium and humic substances samples (Log K value varies from 3.38 to 5.08 at pH 7.00). Using the Stern-Volmer plot, it has been concluded that static and dynamic quenching takes places in the case of salicylic acid and europium interaction while for HSs interaction only a static quenching is observed.

  20. Improved Fast, Deep Record Length, Time-Resolved Visible Spectroscopy of Plasmas Using Fiber Grids

    Science.gov (United States)

    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.

  1. Studies of the reactions of hydrogen atoms by time-resolved E. S. R. spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Fessenden, R W; Verma, N C [Carnegie-Mellon Univ., Pittsburgh, Pa. (USA). Dept. of Chemistry

    1977-01-01

    Time-resolved e.s.r. spectroscopy has been used to follow directly the reactions of H atoms produced by pulse radiolysis of acid solutions. Detailed analysis of the time profile of the e.s.r. signal was carried out by means of modified Bloch equations. The increased signal found when a scavenger for OH such as t-butyl alcohol is present is shown to be mainly the result of slower H atom decay by radical-radical reaction. The reaction H + OH does not appear to produce any signal polarization. The decay curves observed in the presence of solute are readily accounted for by the treatment, and good plots of pseudo first-order rate constant against solute concentration are obtained. The absolute rate constants for reaction with H atoms are for methanol 2.5 x10/sup 6/, for ethanol 2.1 X 10/sup 7/, for isopropanol 6.8 x 10/sup 7/, and for succinic acid 3.0 x 10/sup 6/ dm/sup 3/ mol/sup -1/s/sup -1/. These values are in good agreement with the earlier chemical measurements.

  2. Isotope effect on hydrated electron relaxation dynamics studied with time-resolved liquid jet photoelectron spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Elkins, Madeline H.; Williams, Holly L. [Department of Chemistry, University of California, Berkeley, California 94720 (United States); Neumark, Daniel M., E-mail: dneumark@berkeley.edu [Department of Chemistry, University of California, Berkeley, California 94720 (United States); Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States)

    2016-05-14

    The excited state relaxation dynamics of the solvated electron in H{sub 2}O and D{sub 2}O are investigated using time-resolved photoelectron spectroscopy in a liquid microjet. The data show that the initial excited state decays on a time scale of 75 ± 12 fs in H{sub 2}O and 102 ± 8 fs in D{sub 2}O, followed by slower relaxation on time scales of 400 ± 70 fs and 390 ± 70 fs that are isotopically invariant within the precision of our measurements. Based on the time evolution of the transient signals, the faster and slower time constants are assigned to p → s internal conversion (IC) of the hydrated electron and relaxation on the ground electronic state, respectively. This assignment is consistent with the non-adiabatic mechanism for relaxation of the hydrated electron and yields an isotope effect of 1.4 ± 0.2 for IC of the hydrated electron.

  3. Time resolved infrared spectroscopy of femtosecond proton dynamics in the liquid phase

    International Nuclear Information System (INIS)

    Amir, W.

    2003-12-01

    This work of thesis aims to understand the strong mobility of protons in water. Water is fundamental to life and mediates many chemical and biological processes. However this liquid is poorly understood at the molecular level. The richness of interdisciplinary sciences allows us to study the properties which make it so unique. The technique used for this study was the femtosecond time resolved vibrational spectroscopy. Several experiments were carried out to characterize the femtosecond proton dynamics in water. The visualization of the rotation of water molecules obtained by anisotropy measurements will be presented. This experiment is carried out in isotopic water HDO/D 2 O for reasons of experimental and theoretical suitability. However this is not water. Pure water H 2 O was also studied without thermal effects across vibrations modes. An intermolecular energy resonant transfer was observed. Finally the localized structure of the proton in water (called Eigen form) was clearly experimentally observed. This molecule is implicated in the abnormal mobility of the proton in water (Grotthuss mechanism). (author)

  4. Light adaptation of the unicellular red alga, Cyanidioschyzon merolae, probed by time-resolved fluorescence spectroscopy.

    Science.gov (United States)

    Ueno, Yoshifumi; Aikawa, Shimpei; Kondo, Akihiko; Akimoto, Seiji

    2015-08-01

    Photosynthetic organisms change the quantity and/or quality of their pigment-protein complexes and the interactions among these complexes in response to light conditions. In the present study, we analyzed light adaptation of the unicellular red alga Cyanidioschyzon merolae, whose pigment composition is similar to that of cyanobacteria because its phycobilisomes (PBS) lack phycoerythrin. C. merolae were grown under different light qualities, and their responses were measured by steady-state absorption, steady-state fluorescence, and picosecond time-resolved fluorescence spectroscopies. Cells were cultivated under four monochromatic light-emitting diodes (blue, green, yellow, and red), and changes in pigment composition and energy transfer were observed. Cells grown under blue and green light increased their relative phycocyanin levels compared with cells cultured under white light. Energy-transfer processes to photosystem I (PSI) were sensitive to yellow and red light. The contribution of direct energy transfer from PBS to PSI increased only under yellow light, while red light induced a reduction in energy transfer from photosystem II to PSI and an increase in energy transfer from light-harvesting chlorophyll protein complex I to PSI. Differences in pigment composition, growth, and energy transfer under different light qualities are discussed.

  5. Hemodynamic measurements in deep brain tissues of humans by near-infrared time-resolved spectroscopy

    Science.gov (United States)

    Suzuki, Hiroaki; Oda, Motoki; Yamaki, Etsuko; Suzuki, Toshihiko; Yamashita, Daisuke; Yoshimoto, Kenji; Homma, Shu; Yamashita, Yutaka

    2014-03-01

    Using near-infrared time-resolved spectroscopy (TRS), we measured the human head in transmittance mode to obtain the optical properties, tissue oxygenation, and hemodynamics of deep brain tissues in 50 healthy adult volunteers. The right ear canal was irradiated with 3-wavelengths of pulsed light (760, 795, and 835nm), and the photons passing through the human head were collected at the left ear canal. Optical signals with sufficient intensity could be obtained from 46 of the 50 volunteers. By analyzing the temporal profiles based on the photon diffusion theory, we successfully obtained absorption coefficients for each wavelength. The levels of oxygenated hemoglobin (HbO2), deoxygenated hemoglobin (Hb), total hemoglobin (tHb), and tissue oxygen saturation (SO2) were then determined by referring to the hemoglobin spectroscopic data. Compared with the SO2 values for the forehead measurements in reflectance mode, the SO2 values of the transmittance measurements of the human head were approximately 10% lower, and tHb values of the transmittance measurements were always lower than those of the forehead reflectance measurements. Moreover, the level of hemoglobin and the SO2 were strongly correlated between the human head measurements in transmittance mode and the forehead measurements in the reflectance mode, respectively. These results demonstrated a potential application of this TRS system in examining deep brain tissues of humans.

  6. Nonadiabatic Dynamics May Be Probed through Electronic Coherence in Time-Resolved Photoelectron Spectroscopy.

    Science.gov (United States)

    Bennett, Kochise; Kowalewski, Markus; Mukamel, Shaul

    2016-02-09

    We present a hierarchy of Fermi golden rules (FGRs) that incorporate strongly coupled electronic/nuclear dynamics in time-resolved photoelectron spectroscopy (TRPES) signals at different levels of theory. Expansion in the joint electronic and nuclear eigenbasis yields the numerically most challenging exact FGR (eFGR). The quasistatic Fermi Golden Rule (qsFGR) neglects nuclear motion during the photoionization process but takes into account electronic coherences as well as populations initially present in the pumped matter as well as those generated internally by coupling between electronic surfaces. The standard semiclassical Fermi Golden Rule (scFGR) neglects the electronic coherences and the nuclear kinetic energy during the ionizing pulse altogether, yielding the classical Condon approximation. The coherence contributions depend on the phase-profile of the ionizing field, allowing coherent control of TRPES signals. The photoelectron spectrum from model systems is simulated using these three levels of theory. The eFGR and the qsFGR show temporal oscillations originating from the electronic or vibrational coherences generated as the nuclear wave packet traverses a conical intersection. These oscillations, which are missed by the scFGR, directly reveal the time-evolving splitting between electronic states of the neutral molecule in the curve-crossing regime.

  7. Mobile Charge Generation Dynamics in P3HT:PCBM Observed by Time-Resolved Terahertz Spectroscopy

    DEFF Research Database (Denmark)

    Cooke, D. G.; Krebs, Frederik C; Jepsen, Peter Uhd

    2012-01-01

    Ultra-broadband time-resolved terahertz spectroscopy is used to examine the sub-ps conductivity dynamics of a conjugated polymer bulk heterojunction film P3HT:PCBM. We directly observe mobile charge generation dynamics on a sub-100 fs time scale.......Ultra-broadband time-resolved terahertz spectroscopy is used to examine the sub-ps conductivity dynamics of a conjugated polymer bulk heterojunction film P3HT:PCBM. We directly observe mobile charge generation dynamics on a sub-100 fs time scale....

  8. Transient photoconductivity in InGaN/GaN multiple quantum wells, measured by time-resolved terahertz spectroscopy

    DEFF Research Database (Denmark)

    Porte, Henrik; Turchinovich, Dmitry; Cooke, David

    2009-01-01

    Terahertz conductivity of InGaN/GaN MQWs was studied by time-resolved terahertz spectroscopy. Restoration of the built-in piezoelectric field leads to a nonexponential carrier density decay. Terahertz conductivity spectrum is described by the Drude-Smith......Terahertz conductivity of InGaN/GaN MQWs was studied by time-resolved terahertz spectroscopy. Restoration of the built-in piezoelectric field leads to a nonexponential carrier density decay. Terahertz conductivity spectrum is described by the Drude-Smith...

  9. Laser plasma x-ray source for ultrafast time-resolved x-ray absorption spectroscopy

    Directory of Open Access Journals (Sweden)

    L. Miaja-Avila

    2015-03-01

    Full Text Available We describe a laser-driven x-ray plasma source designed for ultrafast x-ray absorption spectroscopy. The source is comprised of a 1 kHz, 20 W, femtosecond pulsed infrared laser and a water target. We present the x-ray spectra as a function of laser energy and pulse duration. Additionally, we investigate the plasma temperature and photon flux as we vary the laser energy. We obtain a 75 μm FWHM x-ray spot size, containing ∼106 photons/s, by focusing the produced x-rays with a polycapillary optic. Since the acquisition of x-ray absorption spectra requires the averaging of measurements from >107 laser pulses, we also present data on the source stability, including single pulse measurements of the x-ray yield and the x-ray spectral shape. In single pulse measurements, the x-ray flux has a measured standard deviation of 8%, where the laser pointing is the main cause of variability. Further, we show that the variability in x-ray spectral shape from single pulses is low, thus justifying the combining of x-rays obtained from different laser pulses into a single spectrum. Finally, we show a static x-ray absorption spectrum of a ferrioxalate solution as detected by a microcalorimeter array. Altogether, our results demonstrate that this water-jet based plasma source is a suitable candidate for laboratory-based time-resolved x-ray absorption spectroscopy experiments.

  10. Rare Earth Elements as Potential Biosignatures on Mars in SuperCam Time Resolved Laser Fluorescence Spectroscopy Data

    Science.gov (United States)

    Ollila, A.; Beyssac, O.; Sharma, S. K.; Misra, A. K.; Clegg, S. M.; Gauthier, M.; Wiens, R. C.; Maurice, S.; Gasnault, O.; Lanza, N.

    2017-12-01

    The rare earth elements (REE, La to Lu) are a group of elements with similar chemical properties that are generally present in geologic materials at trace concentrations. REEs may be concentrated via processes such as igneous fractional crystallization in accessory minerals, e.g. apatite, zircon, and titanite. Additionally, however, concentrations of REE may serve to identify regions of high astrobiological interest. For example, Fe-oxyhydroxide deposits in hydrothermal vent systems and biologically related manganese nodules may be enriched in REEs. REEs have not been measured in situ on Mars, therefore their prevalence and distribution on Mars is as yet unknown, except as observed in martian meteorites. SuperCam is a survey instrument that will analyze materials around the Mars 2020 rover using a variety of spectral techniques including laser-induced breakdown spectroscopy (LIBS), Raman, VIS-IR, and time-resolved laser fluorescence (TRLF) spectroscopy. Recently, the SuperCam Engineering Development Unit was tested at the Los Alamos National Laboratory for its capabilities to detect REEs in minerals using TRLF spectroscopy. While this instrument was not designed to precisely replicate the flight model, the spectral resolution and light transmission was sufficient to obtain TRLF spectra on a number of minerals demonstrating a variety of REE luminescent centers. These include apatite (Sm3+, Nd3+, Eu3+, Dy3+), fluorite (Ho3+, Sm3+, Dy3+, Nd3+), and zircon (Er3+, Pr3+, Nd3+). Future work includes expanding this suite to include minerals associated with biological activities, for example Mn-oxides (desert varnish and manganese nodules), hydrothermal Fe-oxides, and stromatolite-associated carbonates. In this way and in combination with its other techniques, SuperCam may direct the rover team to perform further analyses of similar samples by the in situ chemical and mineralogical suite of instruments, or aid in prioritization for sample return.

  11. New techniques of time-resolved infrared and Raman spectroscopy using ultrashort laser pulses

    International Nuclear Information System (INIS)

    Laubereau, A.

    1986-01-01

    Considerable progress has been made in recent years in the field of spectroscopic applications of ultrashort laser pulses. This paper examines two approaches toward studying ultrafast relaxation processes in condensed matter: an IR technique which complements coherent Raman scattering; and a Fourier Raman method with high frequency resolution. The time domain IR spectroscopy technique has been applied to various vibration-rotation transitions of pure HCl gas and in mixtures with Ar buffer gas. The advantage of the time domain measurements instead of frequency spectroscopy is readily visualized when one recalls that a frequency resolution of 10 -3 cm -1 corresponds to time observations over 10 -8 , which are readily feasible. As a first demonstration of the FT-Raman technique the author presents experimental data on the Q-branch of the v 1 -vibrational mode of methane. An example for the experimental data obtained approximately 2 mm behind the nozzle is presented; the coherent anti-Stokes Raman signal is plotted versus delay time. A complicated beating structure and the decay of the signal envelope are readily seen. The desired spectroscopic information is obtained by numerical Fourier transformation of the experimental points presented

  12. Investigations of suspension stability of iron oxide nanoparticles using time-resolved UV–visible spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Vikram, S.; Vasanthakumari, R. [B. S. Abdur Rahman University, Polymer Nanotechnology Centre (India); Tsuzuki, Takuya [Australian National University, Research School of Engineering, College of Engineering and Computer Science (Australia); Rangarajan, Murali, E-mail: r-murali@cb.amrita.edu [Amrita University, Center of Excellence in Advanced Materials and Green Technologies, Amrita School of Engineering Coimbatore (India)

    2016-09-15

    This study examines the suspension stability of iron oxide nanoparticles of different sizes, magnetic susceptibility, and saturation magnetization over long time scales in dilute systems using time-resolved UV–visible spectroscopy. The effects of citric acid as a chelating agent and applied external magnetic field are also studied. UV–visible spectra are obtained at different times for citric-acid-stabilized nanoparticles dispersed in water, and the peak absorbance is tracked with time, in the presence and absence of external magnetic fields. It is seen that the nanoparticles sediment slowly even in the absence of chain formation, with the phenomenon occurring in two-to-three regimes for the systems studied. Sedimentation exhibits either exponential or power-law behavior of maximum absorbance with time. In the dilute dispersions studied, thermal dispersion is about two orders of magnitude stronger than van der Waals interactions, and chain formation is not easy. Yet, it is likely that local anisotropic structures of the nanoparticles form, through which the attractive interactions result in sedimentation. Citric acid gradually stabilizes the aggregating particles; after an initial faster sedimentation, electrostatic repulsion causes the particles to segregate, as observed by a linear increase in the concentration of the nanoparticles at long times. In the presence of magnetic field, stabilization effects are significantly reduced. It is seen that though the attractive force between the nanoparticles and the external field is smaller than Brownian forces, together with van der Waals interactions, these attractive forces likely act as directing agents facilitating sedimentation. This study demonstrates that aggregation-induced sedimentation of magnetic nanoparticles is likely to play a significant role in magnetic drug targeting even when the particles are stabilized with chelating agents.Graphical abstract.

  13. Investigations of suspension stability of iron oxide nanoparticles using time-resolved UV–visible spectroscopy

    International Nuclear Information System (INIS)

    Vikram, S.; Vasanthakumari, R.; Tsuzuki, Takuya; Rangarajan, Murali

    2016-01-01

    This study examines the suspension stability of iron oxide nanoparticles of different sizes, magnetic susceptibility, and saturation magnetization over long time scales in dilute systems using time-resolved UV–visible spectroscopy. The effects of citric acid as a chelating agent and applied external magnetic field are also studied. UV–visible spectra are obtained at different times for citric-acid-stabilized nanoparticles dispersed in water, and the peak absorbance is tracked with time, in the presence and absence of external magnetic fields. It is seen that the nanoparticles sediment slowly even in the absence of chain formation, with the phenomenon occurring in two-to-three regimes for the systems studied. Sedimentation exhibits either exponential or power-law behavior of maximum absorbance with time. In the dilute dispersions studied, thermal dispersion is about two orders of magnitude stronger than van der Waals interactions, and chain formation is not easy. Yet, it is likely that local anisotropic structures of the nanoparticles form, through which the attractive interactions result in sedimentation. Citric acid gradually stabilizes the aggregating particles; after an initial faster sedimentation, electrostatic repulsion causes the particles to segregate, as observed by a linear increase in the concentration of the nanoparticles at long times. In the presence of magnetic field, stabilization effects are significantly reduced. It is seen that though the attractive force between the nanoparticles and the external field is smaller than Brownian forces, together with van der Waals interactions, these attractive forces likely act as directing agents facilitating sedimentation. This study demonstrates that aggregation-induced sedimentation of magnetic nanoparticles is likely to play a significant role in magnetic drug targeting even when the particles are stabilized with chelating agents.Graphical abstract

  14. Generation of pulsed far-infrared radiation and its application for far-infrared time-resolved spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Kondo, Yasuhiro [Tohoku Univ., Sendai (Japan). Faculty of Engineering

    1996-07-01

    So-called time-resolved spectroscopy technique has been used from old time as the means for studying the dynamic optical property, light-induced reaction and so on of matters. As an example, there is the method called pump and probe, and here, the wavelength of this probe light is the problem. If the object energy region is limited to about 0.1 eV, fast time-resolved spectroscopy is feasible relatively easily. However, energy region is extended to low energy region, the light source which is available as the pulsed probe light having sufficient intensity is limited. In this paper, the attempt of time-resolved spectroscopy utilizing coherent radiation, which has ended in failure, and the laser pulse-induced far-infrared radiation which can be utilized as new far-infrared probe light are reported. The reason why far-infrared radiation is used is explained. The attempt of time-resolved spectroscopy using NaCl crystals is reported on the equipment, the method of measuring absorption spectra and the results. Laser pulse-induced far-infrared radiation and the method of generating it are described. The multi-channel detector for far-infrared radiation which was made for trial is shown. (K.I.)

  15. NO kinetics in pulsed low-pressure nitrogen plasmas studied by time resolved quantum cascade laser absorption spectroscopy

    NARCIS (Netherlands)

    Welzel, S.; Guaitella, O.; Lazzaroni, C.; Pintassilgo, C.; Rousseau, A.; Röpcke, J.

    2011-01-01

    Time-resolved quantum cascade laser absorption spectroscopy at 1897 cm-1 (5.27 µm) has been applied to study the NO(X) kinetics on the micro- and millisecond time scale in pulsed low-pressure N2/NO dc discharges. Experiments have been performed under flowing and static gas conditions to infer the

  16. Time-resolved terahertz spectroscopy of electrically conductive metal-organic frameworks doped with redox active species

    Science.gov (United States)

    Alberding, Brian G.; Heilweil, Edwin J.

    2015-09-01

    Metal-Organic Frameworks (MOFs) are three-dimensional coordination polymers that are well known for large pore surface area and their ability to adsorb molecules from both the gaseous and solution phases. In general, MOFs are electrically insulating, but promising opportunities for tuning the electronic structure exist because MOFs possess synthetic versatility; the metal and organic ligand subunits can be exchanged or dopant molecules can be introduced into the pore space. Two such MOFs with demonstrated electrical conductivity are Cu3(1,3,5-benzenetricarboxylate)2, a.k.a HKUST-1, and Cu[Ni(pyrazine-2,3-dithiolate)2]. Herein, these two MOFs have been infiltrated with the redox active species 7,7,8,8-tetracyanoquinodimethane (TCNQ) and iodine under solution phase conditions and shown to produce redox products within the MOF pore space. Vibrational bands assignable to TCNQ anion and triiodide anion have been observed in the Mid-IR and Terahertz ranges using FTIR Spectroscopy. The MOF samples have been further investigated by Time-Resolved Terehertz Spectroscopy (TRTS). Using this technique, the charge mobility, separation, and recombination dynamics have been followed on the picosecond time scale following photoexcitation with visible radiation. The preliminary results show that the MOF samples have small inherent photoconductivity with charge separation lifetimes on the order of a few picoseconds. In the case of HKUST-1, the MOF can also be supported by a TiO2 film and initial results show that charge injection into the TiO2 layer occurs with a comparable efficiency to the dye sensitizer N3, [cis-Bis(isothiocyanato)-bis(2,2'-bipyridyl-4,4'-dicarboxylato ruthenium(II)], and therefore this MOF has potential as a new light absorbing and charge conducting material in photovoltaic devices.

  17. Time-resolved photoluminescence spectroscopy of semiconductors for optical applications beyond the visible spectral range

    Energy Technology Data Exchange (ETDEWEB)

    Chernikov, Alexey A.

    2011-07-01

    The work discussed in this thesis is focused on the experimental studies regarding these three steps: (1) investigation of the fundamental effects, (2) characterization of new material systems, and (3) optimization of the semiconductor devices. In all three cases, the experimental technique of choice is photoluminescence (PL) spectroscopy. The thesis is organized as follows. Chapter 2 gives a summary of the PL properties of semiconductors relevant for this work. The first section deals with the intrinsic processes in an ideal direct band gap material, starting with a brief summary of the theoretical background followed by the overview of a typical PL scenario. In the second part of the chapter, the role of the lattice-vibrations, the internal electric fields as well as the influence of the band-structure and the dielectric environment are discussed. Finally, extrinsic PL properties are presented in the third section, focusing on defects and disorder in real materials. In chapter 3, the experimental realization of the spectroscopic studies is discussed. The time-resolved photoluminescence (TRPL) setup is presented, focusing on the applied excitation source, non-linear frequency mixing, and the operation of the streak camera used for the detection. In addition, linear spectroscopy setup for continous-wave (CW) PL and absorption measurements is illustrated. Chapter 4 aims at the study of the interactions between electrons and lattice-vibrations in semiconductor crystals relevant for the proper description of carrier dynamics as well as the heat-transfer processes. The presented discussion covers the experimental studies of many-body effects in phonon-assisted emission of semiconductors due to the carriercarrier Coulomb-interaction. The corresponding theoretical background is discussed in detail in chapter 2. The investigations are focused on the two main questions regarding electron-hole plasma contributions to the phonon-assisted light-matter interaction as well as

  18. Time-resolved resonance Raman spectroscopy of radiation-chemical processes

    International Nuclear Information System (INIS)

    Tripathi, G.N.R.

    1983-01-01

    A tunable pulsed laser Raman spectrometer for time resolved Raman studies of radiation-chemical processes is described. This apparatus utilizes the state of art optical multichannel detection and analysis techniques for data acquisition and electron pulse radiolysis for initiating the reactions. By using this technique the resonance Raman spectra of intermediates with absorption spectra in the 248-900 nm region, and mean lifetimes > 30 ns can be examined. This apparatus can be used to time resolve the vibrational spectral overlap between transients absorbing in the same region, and to follow their decay kinetics by monitoring the well resolved Raman peaks. For kinetic measurements at millisecond time scale, the Raman technique is preferable over optical absorption method where low frequency noise is quite bothersome. A time resolved Raman study of the pulse radiolytic oxidation of aqueous tetrafluorohydroquinone and p-methoxyphenol is briefly discussed. 15 references, 5 figures

  19. Detecting aromatic compounds on planetary surfaces using ultraviolet time-resolved fluorescence spectroscopy

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    Smith, Adam W

    2015-01-01

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

  1. System for time-resolved laser absorption spectroscopy and its application to high-power impulse magnetron sputtering

    Czech Academy of Sciences Publication Activity Database

    Adámek, Petr; Olejníček, Jiří; Hubička, Zdeněk; Čada, Martin; Kment, Štěpán; Kohout, Michal; Do, H.T.

    2017-01-01

    Roč. 88, č. 2 (2017), 1-8, č. článku 023105. ISSN 0034-6748 R&D Projects: GA TA ČR(CZ) TF01000084; GA ČR(CZ) GA15-00863S Institutional support: RVO:68378271 Keywords : plasma diagnostics * HiPIMS * time resolved measurement * laser absorption spectroscopy Subject RIV: BL - Plasma and Gas Discharge Physics OBOR OECD: Fluids and plasma physics (including surface physics) Impact factor: 1.515, year: 2016

  2. Ultrafast optical responses of {beta}-carotene and lycopene probed by sub-20-fs time-resolved coherent spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Fujiwara, M.; Sugisaki, M. [CREST-JST and Department of Physics, Osaka City University, Osaka 558-8585 (Japan); Gall, A.; Robert, B. [CEA, Institut de Biologie et Technologies de Saclay, and CNRS, Gif-sur-Yvette F-91191 (France); Cogdell, R.J. [IBLS, Glasgow Biomedical Research Centre, University of Glasgow, Glasgow G12 8QQ, Scotland (United Kingdom); Hashimoto, H., E-mail: hassy@sci.osaka-cu.ac.j [CREST-JST and Department of Physics, Osaka City University, Osaka 558-8585 (Japan)

    2009-12-15

    We investigate how structural distortions in carotenoid cause decoherences of its high-frequency vibrational modes by applying the sub-20-fs time-resolved transient grating spectroscopy to {beta}-carotene and lycopene. The results indicate that the C=C central stretching mode shows significant loss of coherence under the effects of the steric hindrance between {beta}-ionone ring and polyene backbone, whereas the other high-frequency modes do not show such dependency on the structural distortions.

  3. Ultrafast optical responses of β-carotene and lycopene probed by sub-20-fs time-resolved coherent spectroscopy

    International Nuclear Information System (INIS)

    Fujiwara, M.; Sugisaki, M.; Gall, A.; Robert, B.; Cogdell, R.J.; Hashimoto, H.

    2009-01-01

    We investigate how structural distortions in carotenoid cause decoherences of its high-frequency vibrational modes by applying the sub-20-fs time-resolved transient grating spectroscopy to β-carotene and lycopene. The results indicate that the C=C central stretching mode shows significant loss of coherence under the effects of the steric hindrance between β-ionone ring and polyene backbone, whereas the other high-frequency modes do not show such dependency on the structural distortions.

  4. DFT and time-resolved IR investigation of electron transfer between photogenerated 17- and 19-electron organometallic radicals

    Energy Technology Data Exchange (ETDEWEB)

    Cahoon, James B.; Kling, Matthias F.; Sawyer, Karma R.; Andersen, Lars K.; Harris, Charles B.

    2008-04-30

    The photochemical disproportionation mechanism of [CpW(CO){sub 3}]{sub 2} in the presence of Lewis bases PR{sub 3} was investigated on the nano- and microsecond time-scales with Step-Scan FTIR time-resolved infrared spectroscopy. 532 nm laser excitation was used to homolytically cleave the W-W bond, forming the 17-electron radicals CpW(CO){sub 3} and initiating the reaction. With the Lewis base PPh{sub 3}, disproportionation to form the ionic products CpW(CO){sub 3}PPh{sub 3}{sup +} and CpW(CO){sub 3}{sup -} was directly monitored on the microsecond time-scale. Detailed examination of the kinetics and concentration dependence of this reaction indicates that disproportionation proceeds by electron transfer from the 19-electron species CpW(CO){sub 3}PPh{sub 3} to the 17-electron species CpW(CO){sub 3}. This result is contrary to the currently accepted disproportionation mechanism which predicts electron transfer from the 19-electron species to the dimer [CpW(CO){sub 3}]{sub 2}. With the Lewis base P(OMe){sub 3} on the other hand, ligand substitution to form the product [CpW(CO){sub 2}P(OMe){sub 3}]{sub 2} is the primary reaction on the microsecond time-scale. Density Functional Theory (DFT) calculations support the experimental results and suggest that the differences in the reactivity between P(OMe){sub 3} and PPh{sub 3} are due to steric effects. The results indicate that radical-to-radical electron transfer is a previously unknown but important process for the formation of ionic products with the organometallic dimer [CpW(CO){sub 3}]{sub 2} and may also be applicable to the entire class of organometallic dimers containing a single metal-metal bond.

  5. Time-resolved study of formate on Ni( 1 1 1 ) by picosecond SFG spectroscopy

    Science.gov (United States)

    Kusafuka, K.; Noguchi, H.; Onda, K.; Kubota, J.; Domen, K.; Hirose, C.; Wada, A.

    2002-04-01

    Time-resolved vibrational measurements were carried out on formate (HCOO) adsorbed on Ni(1 1 1) surface by combining the sum-frequency generation method and picosecond laser system (time resolution of 6 ps). Rapid intensity decrease (within the time resolution) followed by intensity recovery (time constant of several tens of ps) of CH stretching signal was observed when picosecond 800 nm pulse was irradiated on the sample surface. From the results of temperature and pump fluence dependences of temporal behaviour of signal intensity, we concluded that the observed intensity change was induced by non-thermal process. Mechanism of the temporal intensity change was discussed.

  6. Characterization of type I, II, III, IV, and V collagens by time-resolved laser-induced fluorescence spectroscopy

    Science.gov (United States)

    Marcu, Laura; Cohen, David; Maarek, Jean-Michel I.; Grundfest, Warren S.

    2000-04-01

    The relative proportions of genetically distinct collagen types in connective tissues vary with tissue type and change during disease progression, development, wound healing, aging. This study aims to 1) characterize the spectro- temporal fluorescence emission of fiber different types of collagen and 2) assess the ability of time-resolved laser- induced fluorescence spectroscopy to distinguish between collagen types. Fluorescence emission of commercially available purified samples was induced with nitrogen laser excitation pulses and detected with a MCP-PMT connected to a digital storage oscilloscope. The recorded time-resolved emission spectra displayed distinct fluorescence emission characteristics for each collagen type. The time domain information complemented the spectral domain intensity data for improved discrimination between different collagen types. Our results reveal that analysis of the fluorescence emission can be used to characterize different species of collagen. Also, the results suggest that time-resolved spectroscopy can be used for monitoring of connective tissue matrix composition changes due to various pathological and non-pathological conditions.

  7. Time-resolved spectroscopy of laser-induced breakdown in water

    Science.gov (United States)

    Thomas, Robert J.; Hammer, Daniel X.; Noojin, Gary D.; Stolarski, David J.; Rockwell, Benjamin A.; Roach, William P.

    1996-05-01

    Laser pulses of 60-ps and 80-ps at a wavelength of 532-nm and 1064-nm respectively were used to produce laser induced breakdown in triple-distilled water. The resulting luminescent flash from the plasma was captured with an imaging spectrograph coupled to a streak camera with a 5-ps time resolution. The wavelength range was 350 to 900-nm. We present the resulting experimental data which gives plasma duration and time-resolved spectral information. Plasma temperature is also computed from the data. All parameters are presented at a pulse energy of 1-mJ and are compared with time-integrated spectra at the same pulse duration and at 5 to 7-ns pulse duration in a similar energy range.

  8. Metalation of positively charged water soluble mesoporphyrins studied via time-resolved SERRS spectroscopy

    Science.gov (United States)

    Procházka, Marek; Hanzliková, Jana; Štěpánek, Josef; Baumruk, Vladimir

    1997-06-01

    Time-resolved SERRS spectra of 5,10,15,20-tetrakis[4-(trimethylammonio)phenyl]21 H,23 H-porphine (TMAP) were recorded (using a multichannel Raman spectrometer) in various SERS-active Ag colloid/porphyrin systems. Data treatment based on a factor analysis was used to decompose all the SERRS spectra into two main components: SERRS spectrum of the free base TMAP and that of its Ag metalated form. The metalation kinetics obtained in this way was found to be highly dependent on the presence of phosphate anions, citrate and/or Triton X-100 in the colloidal system. The results are analogous to those previously obtained for 5,10,15,20-tetrakis(1-methyl-4-pyridyl)21 H,23 H-porphine, a porphyrin with a substantially stronger tendency towards metalation.

  9. Time-resolved UV spectroscopy on ammonia excited by a pulsed CO2 laser

    International Nuclear Information System (INIS)

    Holbach, H.

    1980-07-01

    This work investigates the excitation of ammonia by a pulsed CO 2 laser, in particular the processes associated with collisions with argon. It was prompted by two previous observations: the previously reported infrared multiphoton dissociation of NH 3 under nearly collisionless conditions, and the ill understood excitation mechanism of apparently nonresonant low vibrational levels in the presence of Ar. Based on recent spectroscopic data, all vibrational-rotational levels were determined which are simultaneously excited by different CO 2 laser lines. Transitions between the 1 + and 2 - vibrational levels were also taken into account. The linewidth in these calculations was dominated by power broadening, which generates a half width at half maximum of 0.36 cm -1 at the typical power density of 10 MW/cm 2 . In order to reproduce published experimental absorption data, it proved necessary to take account all transitions within a distance of 20 cm -1 from the laser line. This fact implies in most cases the simultaneous population of a large number of vibrational-rotational levels. The population of levels by absorption or by subsequent collisional processes was probed by time-resolved absorption measurement of vibrational bands and their rotational envelope in the near UV. Time resolution (5...10) was sufficient to observe rotational relaxation within individual vibrational levels. Characteristic differences were found for the various excitation lines. (orig.) [de

  10. TIME-RESOLVED SPECTROSCOPY OF THE POLAR EU CANCRI IN THE OPEN CLUSTER MESSIER 67

    International Nuclear Information System (INIS)

    Williams, Kurtis A.; Howell, Steve B.; Liebert, James; Smith, Paul S.; Bellini, Andrea; Rubin, Kate H. R.; Bolte, Michael

    2013-01-01

    We present time-resolved spectroscopic and polarimetric observations of the AM Her system EU Cnc. EU Cnc is located near the core of the old open cluster Messier 67; new proper motion measurements indicate that EU Cnc is indeed a member of the star cluster, and this system therefore is useful to constrain the formation and evolution of magnetic cataclysmic variables. The spectra exhibit two-component emission features with independent radial velocity variations as well as time-variable cyclotron emission indicating a magnetic field strength of 41 MG. The period of the radial velocity and cyclotron hump variations are consistent with the previously known photometric period, and the spectroscopic flux variations are consistent in amplitude with previous photometric amplitude measurements. The secondary star is also detected in the spectrum. We also present polarimetric imaging measurements of EU Cnc that show a clear detection of polarization, and the degree of polarization drops below our detection threshold at phases when the cyclotron emission features are fading or not evident. The combined data are all consistent with the interpretation that EU Cnc is a low-state polar in the cluster Messier 67. The mass function of the system gives an estimate of the accretor mass of M WD ≥ 0.68 M ☉ with M WD ≈ 0.83 M ☉ for an average inclination. We are thus able to place a lower limit on the progenitor mass of the accreting white dwarf of ≥1.43 M ☉ .

  11. Time-resolved photoion imaging spectroscopy: Determining energy distribution in multiphoton absorption experiments

    Science.gov (United States)

    Qian, D. B.; Shi, F. D.; Chen, L.; Martin, S.; Bernard, J.; Yang, J.; Zhang, S. F.; Chen, Z. Q.; Zhu, X. L.; Ma, X.

    2018-04-01

    We propose an approach to determine the excitation energy distribution due to multiphoton absorption in the case of excited systems following decays to produce different ion species. This approach is based on the measurement of the time-resolved photoion position spectrum by using velocity map imaging spectrometry and an unfocused laser beam with a low fluence and homogeneous profile. Such a measurement allows us to identify the species and the origin of each ion detected and to depict the energy distribution using a pure Poisson's equation involving only one variable which is proportional to the absolute photon absorption cross section. A cascade decay model is used to build direct connections between the energy distribution and the probability to detect each ionic species. Comparison between experiments and simulations permits the energy distribution and accordingly the absolute photon absorption cross section to be determined. This approach is illustrated using C60 as an example. It may therefore be extended to a wide variety of molecules and clusters having decay mechanisms similar to those of fullerene molecules.

  12. Exciplex formation in bimolecular photoinduced electron-transfer investigated by ultrafast time-resolved infrared spectroscopy.

    Science.gov (United States)

    Koch, Marius; Letrun, Romain; Vauthey, Eric

    2014-03-12

    The dynamics of bimolecular photoinduced electron-transfer reactions has been investigated with three donor/acceptor (D/A) pairs in tetrahydrofuran (THF) and acetonitrile (ACN) using a combination of ultrafast spectroscopic techniques, including time-resolved infrared absorption. For the D/A pairs with the highest driving force of electron transfer, all transient spectroscopic features can be unambiguously assigned to the excited reactant and the ionic products. For the pair with the lowest driving force, three additional transient infrared bands, more intense in THF than in ACN, with a time dependence that differs from those of the other bands are observed. From their frequency and solvent dependence, these bands can be assigned to an exciplex. Moreover, polarization-resolved measurements point to a relatively well-defined mutual orientation of the constituents and to a slower reorientational time compared to those of the individual reactants. Thanks to the minimal overlap of the infrared signature of all transient species in THF, a detailed reaction scheme including the relevant kinetic and thermodynamic parameters could be deduced for this pair. This analysis reveals that the formation and recombination of the ion pair occur almost exclusively via the exciplex.

  13. Multiplexed measurements by time resolved spectroscopy using colloidal CdSe/ZnS quantum dots

    Energy Technology Data Exchange (ETDEWEB)

    Kaiser, U.; Jimenez de Aberasturi, D.; Malinowski, R.; Amin, F.; Parak, W. J.; Heimbrodt, W., E-mail: Wolfram.Heimbrodt@physik.uni-marburg.de [Department of Physics and Materials Sciences Center, Philipps-University of Marburg, Renthof 5, D-35032 Marburg (Germany)

    2014-01-27

    Multiplexed measurements of analytes in parallel is a topical demand in bioanalysis and bioimaging. An interesting alternative to commonly performed spectral multiplexing is lifetime multiplexing. In this Letter, we present a proof of principle of single-color lifetime multiplexing by coupling the same fluorophore to different nanoparticles. The effective lifetime of the fluorophores can be tuned by more than one order of magnitude due to resonance energy transfer from donor states. Measurements have been done on a model systems consisting of ATTO-590 dye molecules linked to either gold particles or to CdSe/ZnS core shell quantum dots. Both systems show the same luminescence spectrum of ATTO-590 dye emission in continuous wave excitation, but can be distinguished by means of time resolved measurements. The dye molecules bound to gold particles exhibit a mono-exponential decay with a lifetime of 4.5 ns, whereas the dye molecules bound to CdSe/ZnS dots show a nonexponential decay with a slow component of about 135 ns due to the energy transfer from the quantum dots. We demonstrate the fundamental possibility to determine the mixing ratio for dyes with equal luminescence spectra but very different transients. This opens up a pathway independent of the standard optical multiplexing with many different fluorophores emitting from the near ultraviolet to the near infrared spectral region.

  14. Development of time-resolved electron momentum spectroscopy. Toward real-time imaging of frontier electrons in molecular reactions

    International Nuclear Information System (INIS)

    Yamazaki, M.; Takahashi, M.

    2016-01-01

    This report will introduce a new experimental technique to readers, which we would like to propose towards advances in the field of molecular reaction dynamics. It is time-resolved electron momentum spectroscopy and aims to take in momentum space snapshots of the rapid change of molecular orbitals, which is the driving force behind any structural changes occurring in transient molecules. Following a description of the working principle of the technique, some preliminary result will be presented in order to illustrate the current performance of the apparatus. (author)

  15. IR Spectroscopy. An introduction

    International Nuclear Information System (INIS)

    Guenzler, H.; Gremlich, H.U.

    2002-01-01

    The following topics are dealt with: absorption and molecular design, spectrometers, sample preparation, qualitative spectral interpretation and assertions, near-infrared and far-infrared spectroscopy, reference spectra and expert systems

  16. X-ray Crystal Structure and Time-resolved Spectroscopy of the Blue Carotenoid Violerythrin

    Czech Academy of Sciences Publication Activity Database

    Polívka, Tomáš; Frank, H.A.; Enriquez, M.M.; Niedzwiedzki, D.M.; Liaaen-Jensen, S.; Hemming, J.; Helliwell, J.R.; Helliwell, M.

    2010-01-01

    Roč. 114, č. 26 (2010), s. 8760-8769 ISSN 1520-6106 Institutional research plan: CEZ:AV0Z50510513 Keywords : carotenoids * excited states * spectroscopy Subject RIV: BO - Biophysics Impact factor: 3.603, year: 2010

  17. Time-resolved laser spectroscopy in the UV/VUV spectral region

    International Nuclear Information System (INIS)

    Bengtsson, J.

    1992-01-01

    Radiative lifetimes ranging from 3 to 500 ns were measured on various states of Ag, N, Se, Te and As, by recording the fluorescence light decay after excitation by a laser pulse. Ag was supplied by a collimated atomic beam while Se, Te and As were contained in quartz cells. Pulsed laser radiation, with a wavelength down to 185 nm, was generated by different set-ups, using Nd-YAG pumped dye lasers combined with non-linear crystals and Raman shifting. Short laser pulses were produced by a nitrogen laser or a distributed feedback dye laser. Two-photon processes and stepwise excitation were used to populate high-lying levels. Depletion spectroscopy, quantum-beat spectroscopy and optical double resonance spectroscopy were also performed

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

    Science.gov (United States)

    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

  19. New methods and applications in time-resolved X-ray absorption spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Stoetzel, Jan Eric

    2012-07-01

    Recent experimental advances and developments in the QEXAFS technique were presented along with new applications in the disciplines of catalysis and surface science. Both performance and user-friendliness of the QEXAFS method were significantly improved, while the applicability of QEXAFS was extended by newly designed mechanics. The application of a fast angular encoder proved to be capable to sample the continuously changing Bragg angle of the monochromator crystal synchronized to the acquired absorption data. A new data acquisition system was designed, based on a multifunctional ADC board, which provides high acquisition frequencies, while low noise acquisition could be achieved due to the provided differential acquisition mode. Additionally, control of all experimental devices as current amplifiers, monochromator motors and sample stages were implemented to further increase the efficiency of the experimental setup for QEFAS measurements. In order to simplify the processing of the huge generated QEXAFS raw data files, a completely new software tool for data analysis was designed, which provides not only the basic procedures of QEXAFS data analysis, but also many approaches customized for time-resolved data. Apart from technical advances, various experiments were performed with QEXAFS to gain new insights into the complex processes of several catalytic reactions, the thermal decomposition of metal oxalates, as well as layer growth processes and reactions on rough surfaces. Supported Pd catalysts were investigated during catalytic partial oxidation of methane, whereby oscillations in the conversion were linked to structural changes of the catalyst. Kinetic oscillations were also investigated on a supported Pt catalyst during the extinction of CO oxidation induced by decreasing temperature. Modulated experiments were investigated (i) on supported Pt-Rh/Al{sub 2}O{sub 3} catalysts during active catalytic partial oxidation in switching gas atmospheres of methane and

  20. Ultrabroadband time-resolved THz spectroscopy of polymer-based solar cells

    DEFF Research Database (Denmark)

    Cooke, David G.; Krebs, Frederik C; Jepsen, Peter Uhd

    2011-01-01

    We have developed ultrabroadband THz spectroscopy in reflection mode for characterization of conductivity dynamics in conductive polymer samples used in organic solar cells. The spectrometer is designed to have a time resolution limited only by the duration of the optical pump pulse, thus enabling...

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

    Czech Academy of Sciences Publication Activity Database

    Votava, Ondřej; Mašát, Milan; Parker, A. E.; Jain, Ch.; Fittschen, Ch.

    2012-01-01

    Roč. 83, č. 4 (2012), 043110 ISSN 0034-6748 R&D Projects: GA ČR GA203/09/0422 Institutional support: RVO:61388955 Keywords : CW-DIODE-LASER * DOWN SPECTROSCOPY * KINETICS Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.602, year: 2012

  2. Temperature Measurements in Reacting Flows Using Time-Resolved Femtosecond Coherent Anti-Stokes Raman Scattering (fs-CARS) Spectroscopy (Postprint)

    National Research Council Canada - National Science Library

    Roy, Sukesh; Kinnius, Paul J; Lucht, Robert P; Gord, James R

    2007-01-01

    Time-resolved femtosecond coherent anti-Stokes Raman scattering (fs-CARS) spectroscopy of the nitrogen molecule is used for the measurement of temperature in atmospheric-pressure, near-adiabatic, hydrogen-air diffusion flames...

  3. Study of the Bulk Charge Carrier Dynamics in Anatase and Rutile TiO2 Single Crystals by Femtosecond Time Resolved Spectroscopy

    KAUST Repository

    Maity, Partha; Mohammed, Omar F.; Katsiev, Khabiboulakh; Idriss, Hicham

    2018-01-01

    as the best model for fundamental studies. Their ultrafast charge carrier dynamics especially on TiO2 anatase single crystal (the most active phase) are unresolved. Here femtosecond time resolved spectroscopy (TRS) was carried out to explore the dynamics

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

    Science.gov (United States)

    Blacksberg, J.; Rossman , G.R.

    2011-01-01

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

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

    Science.gov (United States)

    2010-02-03

    conferences covering the use of advanced vibrational spectroscopy for the use of studying time-dependent molecular processes in chemistry, physics ...Netherlands a.huertaviga@uva.nl Neil Hunt Dept of  Physics , University of Strathclyde United Kingdom nhunt@phys.strath.ac Koichi Iwata Gakushuin University...Dasgupta Mark Creelman Sangdeok Shim Biochemical Reaction Dynamics, , , UC B k ler e ey 11:50 AM C W. Zinth, W. J. Schreier, J. Kubon, N. Regner, K

  6. Time resolved super continuum Cavity Ring-Down Spectroscopy for multicomponent gas detection

    International Nuclear Information System (INIS)

    Nakaema, Walter Morinobu

    2010-01-01

    In this work, we present a variation of the technique CRDS (Cavity Ring-Down Spectroscopy) to obtain simultaneously a multicomponent absorption spectrum in a broad visible range. This new approach uses the Supercontinuum (SC) spectrum (resulting from irradiation of nonlinear media by femtosecond lasers, or simply generated by compact sources) as a light source to illuminate the cavity. In this context it is described the features of the modules assembling a MC-SC-CRDS (Multicomponent Supercontinuum Cavity Ring-Down Spectroscopy): a set of high reflectivity mirrors, the resonant cavity and the detection system. Some problems related to the multimode excitation, stray light, effective use of the dynamic range of the detector, the poor resolution of the instrument to resolve narrow absorption lines are issued. We present the absorption spectra of H 2 O (polyads 4υ, 4υ + δ) and O 2 (spin-forbidden b-X branch) measured simultaneously by this technique in the visible range and a comparison with the absorption lines based on HITRAN database is made to demonstrate the functionality of this method. (author)

  7. Dissociation dynamics of CH3I in electric spark induced breakdown revealed by time-resolved laser induced breakdown spectroscopy

    International Nuclear Information System (INIS)

    Wang, Yang; Liu, Wei-long; Song, Yun-fei; Duo, Li-ping; Liu, Yu-qiang; Yang, Yan-qiang

    2015-01-01

    Highlights: • Emission of electric spark dissociation of CH 3 I is similar to its fs LIBS. • We use fs laser induced breakdown as a simulation for electric spark dissociation. • The I 2 molecule formation is directly observed in the time-resolved LIBS. • Bimolecular collision of I ∗ and CH 3 I is responsible for the formation of I 2 . - Abstract: The electric discharge spark dissociation of gas CH 3 I is found to be similar to its femtosecond laser photodissociation. The almost identical spectra of the two processes show that their initial ionization conditions are very similar. The initial ionization followed by molecular fragmentation is proposed as the dissociation mechanism, in which the characteristic emissions of I + , CH 3 , CH 2 , CH, H, and I 2 are identified as the dissociation products. The emission band of 505 nm I 2 is clearly observed in the time-resolved laser induced breakdown spectroscopy (LIBS). The dynamic curve indicates that I 2 ∗ molecules are formed after the delay time of ∼4.7 ns. The formation of I 2 ∗ molecule results from the bimolecular collision of the highly excited iodine atom I ∗ ( 4 P) and CH 3 I molecule. This dynamical information can help understand the process of electric discharge spark dissociation of CH 3 I

  8. Time-resolved monitoring of enzyme activity with ultrafast Hyper-CEST spectroscopy.

    Science.gov (United States)

    Döpfert, Jörg; Schnurr, Matthias; Kunth, Martin; Rose, Honor May; Hennig, Andreas; Schröder, Leif

    2017-12-23

    We propose a method to dynamically monitor the progress of an enzymatic reaction using NMR of hyperpolarized 129 Xe in a host-guest system. It is based on a displacement assay originally designed for fluorescence experiments that exploits the competitive binding of the enzymatic product on the one hand and a reporter dye on the other hand to a supramolecular host. Recently, this assay has been successfully transferred to NMR, using xenon as a reporter, cucurbit[6]uril as supramolecular host, and chemical exchange saturation transfer with hyperpolarized Xe (Hyper-CEST) as detection technique. Its advantage is that the enzyme acts on the unmodified substrate and that only the product is detected through immediate inclusion into the host. We here apply a method that drastically accelerates the acquisition of Hyper-CEST spectra in vitro using magnetic field gradients. This allows monitoring the dynamic progress of the conversion of lysine to cadaverine with a temporal resolution of ~30 s. Moreover, the method only requires to sample the very early onset of the reaction (Hyper-CEST results correlate with xenon T 2 measurements performed during the enzymatic reaction. This suggests that ultrafast Hyper-CEST spectroscopy can be used for dynamically monitoring enzymatic activity with NMR. Copyright © 2017 John Wiley & Sons, Ltd.

  9. Variation in LOV Photoreceptor Activation Dynamics Probed by Time Resolved Infrared Spectroscopy

    KAUST Repository

    Iuliano, James N.

    2017-12-14

    The light, oxygen, voltage (LOV) domain proteins are blue light photoreceptors that utilize a non-covalently bound flavin mononucleotide (FMN) cofactor as the chromophore. The modular nature of these proteins has led to their wide adoption in the emerging fields of optogenetics and optobiology, where the LOV domain has been fused to a variety of output domains leading to novel light-controlled applications. In the present work, we extend our studies of the sub-picosecond to several hundred microsecond transient infrared spectroscopy of the isolated LOV domain AsLOV2 to three full-length photoreceptors in which the LOV domain is fused to an output domain: the LOV-STAS protein, YtvA, the LOV-HTH transcription factor, EL222, and the LOV-histidine kinase, LovK. Despite differences in tertiary structure, the overall pathway leading to cysteine adduct formation from the FMN triplet state is highly conserved, although there are slight variations in rate. However significant differences are observed in the vibrational spectra and kinetics after adduct formation, which are directly linked to the specific output function of the LOV domain. While the rate of adduct formation varies by only 3.6-fold amongst the proteins, the subsequent large-scale structural changes in the full-length LOV photoreceptors occur over the micro- to sub-millisecond timescales and vary by orders of magnitude depending on the different output function of each LOV domain.

  10. Diagnosis of laser ablated carbon particles measured by time-resolved X-ray absorption spectroscopy

    International Nuclear Information System (INIS)

    Miyashita, Atsumi; Yoda, Osamu; Ohyanagi, T.; Murakami, K.

    1995-01-01

    The time and space resolved properties of laser ablated carbon particles were measured by X-ray absorption spectroscopy using LPX as an X-ray source. The energy density of the irradiation laser on the sample was in the range of 0.5-20J/cm 2 and the time delay was varied between 0 and 120ns. The absorption spectra exhibited several peaks originated from level to level transitions and an intense broad absorption in the energy range of C-K edge. At a delay time of 120ns, the absorption peak from 1s→2p transition of neutral carbon atom (C 0 ), C - , C + and C 2+ ions were observed. The absorption peak from C 0 was stronger as the probing position was closer to the sample surface and decreased rapidly with distance from the sample surface. The absorption peak C 2+ ion was observed only at comparatively distant positions from surface. The maximum speeds of highly charged ions were faster than that of neutral atoms and negative charged ions. The neutral atom and lower charged ions were emitted from the sample even after laser irradiation. The spatial distributions of the laser ablated carbon particles in the localized helium gas environment were measured. In the helium gas environment, the ablation plume was depressed by the helium cloud generated on the top of ablation plume. (author)

  11. Time-Resolved Spectroscopy Diagnostic of Laser-Induced Optical Breakdown

    Directory of Open Access Journals (Sweden)

    Christian G. Parigger

    2010-01-01

    Full Text Available Transient laser plasma is generated in laser-induced optical breakdown (LIOB. Here we report experiments conducted with 10.6-micron CO2 laser radiation, and with 1.064-micron fundamental, 0.532-micron frequency-doubled, 0.355-micron frequency-tripled Nd:YAG laser radiation. Characterization of laser induced plasma utilizes laser-induced breakdown spectroscopy (LIBS techniques. Atomic hydrogen Balmer series emissions show electron number density of 1017 cm−3 measured approximately 10 μs and 1 μs after optical breakdown for CO2 and Nd:YAG laser radiation, respectively. Recorded molecular recombination emission spectra of CN and C2 Swan bands indicate an equilibrium temperature in excess of 7000 Kelvin, inferred for these diatomic molecules. Reported are also graphite ablation experiments where we use unfocused laser radiation that is favorable for observation of neutral C3 emission due to reduced C3 cation formation. Our analysis is based on computation of diatomic molecular spectra that includes accurate determination of rotational line strengths, or Hönl-London factors.

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

    Science.gov (United States)

    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.

  13. Variation in LOV Photoreceptor Activation Dynamics Probed by Time Resolved Infrared Spectroscopy

    KAUST Repository

    Iuliano, James N.; Gil, Agnieszka A.; Laptenok, Sergey P.; Hall, Christopher R.; Tolentino Collado, Jinnette; Lukacs, Andras; Hag Ahmed, Safaa A; Abyad, Jenna; Daryaee, Taraneh; Greetham, Gregory M.; Sazanovich, Igor V.; Illarionov, Boris; Bacher, Adelbert; Fischer, Markus; Towrie, Michael; French, Jarrod B.; Meech, Stephen R.; Tonge, Peter J

    2017-01-01

    The light, oxygen, voltage (LOV) domain proteins are blue light photoreceptors that utilize a non-covalently bound flavin mononucleotide (FMN) cofactor as the chromophore. The modular nature of these proteins has led to their wide adoption in the emerging fields of optogenetics and optobiology, where the LOV domain has been fused to a variety of output domains leading to novel light-controlled applications. In the present work, we extend our studies of the sub-picosecond to several hundred microsecond transient infrared spectroscopy of the isolated LOV domain AsLOV2 to three full-length photoreceptors in which the LOV domain is fused to an output domain: the LOV-STAS protein, YtvA, the LOV-HTH transcription factor, EL222, and the LOV-histidine kinase, LovK. Despite differences in tertiary structure, the overall pathway leading to cysteine adduct formation from the FMN triplet state is highly conserved, although there are slight variations in rate. However significant differences are observed in the vibrational spectra and kinetics after adduct formation, which are directly linked to the specific output function of the LOV domain. While the rate of adduct formation varies by only 3.6-fold amongst the proteins, the subsequent large-scale structural changes in the full-length LOV photoreceptors occur over the micro- to sub-millisecond timescales and vary by orders of magnitude depending on the different output function of each LOV domain.

  14. Ultrafast time-resolved absorption spectroscopy of geometric isomers of xanthophylls

    Science.gov (United States)

    Niedzwiedzki, Dariusz M.; Enriquez, Miriam M.; LaFountain, Amy M.; Frank, Harry A.

    2010-07-01

    This paper presents an ultrafast optical spectroscopic investigation of the excited state energies, lifetimes and spectra of specific geometric isomers of neoxanthin, violaxanthin, lutein, and zeaxanthin. All- trans- and 15,15'- cis-β-carotene were also examined. The spectroscopy was done on molecules purified by HPLC frozen immediately to inhibit isomerization. The spectra were taken at 77 K to maintain the configurations and to provide better spectral resolution than seen at room temperature. The kinetics reveal that for all of the molecules except neoxanthin, the S 1 state lifetime of the cis isomers is shorter than that of the all- trans isomers. The S 1 excited state energies of all the isomers were determined by recording S 1 → S 2 transient absorption spectra. The results obtained in this manner at cryogenic temperatures provide an unprecedented level of precision in the measurement of the S 1 energies of these xanthophylls, which are critical components in light-harvesting pigment-protein complexes of green plants.

  15. Time-Resolved Ultraviolet Spectroscopy of The M-Dwarf GJ 876 Exoplanetary System

    Science.gov (United States)

    France, Kevin; Linsky, Jeffrey L.; Tian, Feng; Froning, Cynthia S.; Roberge, Aki

    2012-01-01

    Extrasolar planets orbiting M-stars may represent our best chance to discover habitable worlds in the coming decade. The ultraviolet spectrum incident upon both Earth-like and Jovian planets is critically important for proper modeling of their atmospheric heating and chemistry. In order to provide more realistic inputs for atmospheric models of planets orbiting low-mass stars, we present new near- and far-ultraviolet (NUV and FUV) spectroscopy of the M-dwarf exoplanet host GJ 876 (M4V). Using the COS and STIS spectrographs on board the Hubble Space Telescope, we have measured the 1150-3140 A spectrum of GJ 876. We have reconstructed the stellar H1 Ly alpha emission line profile, and find that the integrated Ly alpha flux is roughly equal to the rest of the integrated flux (1150-1210 A + 1220-3140 A) in the entire ultraviolet bandpass (F(Ly alpha)/F(FUV+NUV) equals approximately 0.7). This ratio is approximately 2500x greater than the solar value. We describe the ultraviolet line spectrum and report surprisingly strong fluorescent emission from hot H2 (T(H2) greater than 2000 K). We show the light curve of a chromospheric + transition region flare observed in several far-UV emission lines, with flare/quiescent flux ratios greater than or equal to 10. The strong FUV radiation field of an M-star (and specifically Ly alpha) is important for determining the abundance of O2--and the formation of biomarkers-in the lower atmospheres of Earth-like planets in the habitable zones of low-mass stars.

  16. TIME-RESOLVED ULTRAVIOLET SPECTROSCOPY OF THE M-DWARF GJ 876 EXOPLANETARY SYSTEM

    International Nuclear Information System (INIS)

    France, Kevin; Froning, Cynthia S.; Linsky, Jeffrey L.; Tian, Feng; Roberge, Aki

    2012-01-01

    Extrasolar planets orbiting M-stars may represent our best chance to discover habitable worlds in the coming decade. The ultraviolet spectrum incident upon both Earth-like and Jovian planets is critically important for proper modeling of their atmospheric heating and chemistry. In order to provide more realistic inputs for atmospheric models of planets orbiting low-mass stars, we present new near- and far-ultraviolet (NUV and FUV) spectroscopy of the M-dwarf exoplanet host GJ 876 (M4V). Using the COS and STIS spectrographs on board the Hubble Space Telescope, we have measured the 1150-3140 Å spectrum of GJ 876. We have reconstructed the stellar H I Lyα emission line profile, and find that the integrated Lyα flux is roughly equal to the rest of the integrated flux (1150-1210 Å + 1220-3140 Å) in the entire ultraviolet bandpass (F(Lyα)/F(FUV+NUV) ≈ 0.7). This ratio is ∼2500× greater than the solar value. We describe the ultraviolet line spectrum and report surprisingly strong fluorescent emission from hot H 2 (T(H 2 ) > 2000 K). We show the light curve of a chromospheric + transition region flare observed in several far-UV emission lines, with flare/quiescent flux ratios ≥10. The strong FUV radiation field of an M-star (and specifically Lyα) is important for determining the abundance of O 2 —and the formation of biomarkers—in the lower atmospheres of Earth-like planets in the habitable zones of low-mass stars.

  17. In situ time-resolved X-ray near-edge absorption spectroscopy of selenite reduction by siderite

    International Nuclear Information System (INIS)

    Badaut, V.; Schlegel, M.L.; Descostes, M.; Moutiers, G.

    2012-01-01

    The reduction oxidation-reaction between aqueous selenite (SeO 3 2- ) and siderite (FeCO 3 (s)) was monitored by in situ, time-resolved X-ray absorption near-edge structure (XANES) spectroscopy at the selenium K edge in a controlled electrochemical environment. Spectral evolutions showed that more than 60% of selenite was reduced at the siderite surface after 20 h of experiment, at which time the reaction was still incomplete. Fitting of XANES spectra by linear combination of reference spectra showed that selenite reaction with siderite is essentially a two-step process, selenite ions being immobilized on siderite surface prior to their reduction. A kinetic model of the reduction step is proposed, allowing to identify the specific contribution of surface reduction. These results have strong implications for the retention of selenite by corrosion products in nuclear waste repositories and in a larger extent for the fate of selenium in the environment. (authors)

  18. Direct Structural and Chemical Characterization of the Photolytic Intermediates of Methylcobalamin Using Time-Resolved X-ray Absorption Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Subramanian, Ganesh; Zhang, Xiaoyi; Kodis, Gerdenis; Kong, Qingyu; Liu, Cunming; Chizmeshya, Andrew; Weierstall, Uwe; Spence, John

    2018-04-05

    Cobalt−carbon bond cleavage is crucial to most natural and synthetic applications of the cobalamin class of compounds, and here we present the first direct electronic and geometric structural characteristics of intermediates formed following photoexcitation of methylcobalamin (MeCbl) using time-resolved X-ray absorption spectroscopy (XAS). We catch transients corresponding to two intermediates, in the hundreds of picoseconds and a few microseconds. Highlights of the picosecond intermediate, which is reduced in comparison to the ground state, are elongation of the upper axial Co−C bond and relaxation of the corrin ring. This is not so with the recombining photocleaved products captured at a few microseconds, where the Co−C bond almost (yet not entirely) reverts to its ground state configuration and a substantially elongated lower axial Co−NIm bond is observed. The reduced cobalt site here confirms formation of methyl radical as the photoproduct.

  19. Wide-field time-resolved luminescence imaging and spectroscopy to decipher obliterated documents in forensic science

    Science.gov (United States)

    Suzuki, Mototsugu; Akiba, Norimitsu; Kurosawa, Kenji; Kuroki, Kenro; Akao, Yoshinori; Higashikawa, Yoshiyasu

    2016-01-01

    We applied a wide-field time-resolved luminescence (TRL) method with a pulsed laser and a gated intensified charge coupled device (ICCD) for deciphering obliterated documents for use in forensic science. The TRL method can nondestructively measure the dynamics of luminescence, including fluorescence and phosphorescence lifetimes, which prove to be useful parameters for image detection. First, we measured the TRL spectra of four brands of black porous-tip pen inks on paper to estimate their luminescence lifetimes. Next, we acquired the TRL images of 12 obliterated documents at various delay times and gate times of the ICCD. The obliterated contents were revealed in the TRL images because of the difference in the luminescence lifetimes of the inks. This method requires no pretreatment, is nondestructive, and has the advantage of wide-field imaging, which makes it is easy to control the gate timing. This demonstration proves that TRL imaging and spectroscopy are powerful tools for forensic document examination.

  20. Time-resolved spectroscopy and fluorescence resonance energy transfer in the study of excimer laser damage of chromatin

    Energy Technology Data Exchange (ETDEWEB)

    Radu, L. [Department of Molecular Genetics and Radiobiology, Babes National Institute, Bucharest (Romania)], E-mail: lilianajradu@yahoo.fr; Mihailescu, I. [Department of Lasers, Laser, Plasma and Radiation Physics Institute, Bucharest (Romania); Radu, S. [Department of Computer Science, Polytechnics University, Bucharest (Romania); Gazdaru, D. [Department of Biophysics, Bucharest University (Romania)

    2007-09-21

    The analysis of chromatin damage produced by a 248 nm excimer laser radiation, for doses of 0.3-3 MJ/m{sup 2} was carried out by time-resolved spectroscopy and fluorescence resonance energy transfer (FRET). The chromatin was extracted from a normal and a tumoral tissue of Wistar rats. The decrease with laser dose of the relative contribution of the excited state lifetimes of ethidium bromide (EtBr) bounded to chromatin constitutes an evidence of the reduction of chromatin deoxyribonucleic acid (DNA) double-strand structure. FRET was performed from dansyl chloride to acridine orange, both coupled to chromatin. The increase of the average distance between these ligands, under the action of laser radiation, reflects a loosening of the chromatin structure. The radiosensitivity of tumor tissue chromatin is higher than that of a normal tissue. The determination of the chromatin structure modification in an excimer laser field can be of interest in laser therapy.

  1. Time-resolved spectroscopy and fluorescence resonance energy transfer in the study of excimer laser damage of chromatin

    International Nuclear Information System (INIS)

    Radu, L.; Mihailescu, I.; Radu, S.; Gazdaru, D.

    2007-01-01

    The analysis of chromatin damage produced by a 248 nm excimer laser radiation, for doses of 0.3-3 MJ/m 2 was carried out by time-resolved spectroscopy and fluorescence resonance energy transfer (FRET). The chromatin was extracted from a normal and a tumoral tissue of Wistar rats. The decrease with laser dose of the relative contribution of the excited state lifetimes of ethidium bromide (EtBr) bounded to chromatin constitutes an evidence of the reduction of chromatin deoxyribonucleic acid (DNA) double-strand structure. FRET was performed from dansyl chloride to acridine orange, both coupled to chromatin. The increase of the average distance between these ligands, under the action of laser radiation, reflects a loosening of the chromatin structure. The radiosensitivity of tumor tissue chromatin is higher than that of a normal tissue. The determination of the chromatin structure modification in an excimer laser field can be of interest in laser therapy

  2. Time-Resolved Fluorescence Spectroscopy and Fluorescence Lifetime Imaging Microscopy for Characterization of Dendritic Polymer Nanoparticles and Applications in Nanomedicine

    Directory of Open Access Journals (Sweden)

    Alexander Boreham

    2016-12-01

    Full Text Available The emerging field of nanomedicine provides new approaches for the diagnosis and treatment of diseases, for symptom relief and for monitoring of disease progression. One route of realizing this approach is through carefully constructed nanoparticles. Due to the small size inherent to the nanoparticles a proper characterization is not trivial. This review highlights the application of time-resolved fluorescence spectroscopy and fluorescence lifetime imaging microscopy (FLIM for the analysis of nanoparticles, covering aspects ranging from molecular properties to particle detection in tissue samples. The latter technique is particularly important as FLIM allows for distinguishing of target molecules from the autofluorescent background and, due to the environmental sensitivity of the fluorescence lifetime, also offers insights into the local environment of the nanoparticle or its interactions with other biomolecules. Thus, these techniques offer highly suitable tools in the fields of particle development, such as organic chemistry, and in the fields of particle application, such as in experimental dermatology or pharmaceutical research.

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

    Science.gov (United States)

    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.

  4. Time-Resolved Fluorescence Spectroscopy and Fluorescence Lifetime Imaging Microscopy for Characterization of Dendritic Polymer Nanoparticles and Applications in Nanomedicine.

    Science.gov (United States)

    Boreham, Alexander; Brodwolf, Robert; Walker, Karolina; Haag, Rainer; Alexiev, Ulrike

    2016-12-24

    The emerging field of nanomedicine provides new approaches for the diagnosis and treatment of diseases, for symptom relief and for monitoring of disease progression. One route of realizing this approach is through carefully constructed nanoparticles. Due to the small size inherent to the nanoparticles a proper characterization is not trivial. This review highlights the application of time-resolved fluorescence spectroscopy and fluorescence lifetime imaging microscopy (FLIM) for the analysis of nanoparticles, covering aspects ranging from molecular properties to particle detection in tissue samples. The latter technique is particularly important as FLIM allows for distinguishing of target molecules from the autofluorescent background and, due to the environmental sensitivity of the fluorescence lifetime, also offers insights into the local environment of the nanoparticle or its interactions with other biomolecules. Thus, these techniques offer highly suitable tools in the fields of particle development, such as organic chemistry, and in the fields of particle application, such as in experimental dermatology or pharmaceutical research.

  5. Ultrafast time-resolved absorption spectroscopy of geometric isomers of carotenoids

    International Nuclear Information System (INIS)

    Niedzwiedzki, Dariusz M.; Sandberg, Daniel J.; Cong, Hong; Sandberg, Megan N.; Gibson, George N.; Birge, Robert R.; Frank, Harry A.

    2009-01-01

    The structures of a number of stereoisomers of carotenoids have been revealed in three-dimensional X-ray crystallographic investigations of pigment-protein complexes from photosynthetic organisms. Despite these structural elucidations, the reason for the presence of stereoisomers in these systems is not well understood. An important unresolved issue is whether the natural selection of geometric isomers of carotenoids in photosynthetic pigment-protein complexes is determined by the structure of the protein binding site or by the need for the organism to accomplish a specific physiological task. The association of cis isomers of a carotenoid with reaction centers and trans isomers of the same carotenoid with light-harvesting pigment-protein complexes has led to the hypothesis that the stereoisomers play distinctly different physiological roles. A systematic investigation of the photophysics and photochemistry of purified, stable geometric isomers of carotenoids is needed to understand if a relationship between stereochemistry and biological function exists. In this work we present a comparative study of the spectroscopy and excited state dynamics of cis and trans isomers of three different open-chain carotenoids in solution. The molecules are neurosporene (n = 9), spheroidene (n = 10), and spirilloxanthin (n = 13), where n is the number of conjugated π-electron double bonds. The spectroscopic experiments were carried out on geometric isomers of the carotenoids purified by high performance liquid chromatography (HPLC) and then frozen to 77 K to inhibit isomerization. The spectral data taken at 77 K provide a high resolution view of the spectroscopic differences between geometric isomers. The kinetic data reveal that the lifetime of the lowest excited singlet state of a cis-isomer is consistently shorter than that of its corresponding all-trans counterpart despite the fact that the excited state energy of the cis molecule is typically higher than that of the trans

  6. Distortion dependent intersystem crossing: A femtosecond time-resolved photoelectron spectroscopy study of benzene, toluene, and p-xylene

    Directory of Open Access Journals (Sweden)

    Anne B. Stephansen

    2017-07-01

    Full Text Available The competition between ultrafast intersystem crossing and internal conversion in benzene, toluene, and p-xylene is investigated with time-resolved photoelectron spectroscopy and quantum chemical calculations. By exciting to S2 out-of-plane symmetry breaking, distortions are activated at early times whereupon spin-forbidden intersystem crossing becomes (partly allowed. Natural bond orbital analysis suggests that the pinnacle carbon atoms distorting from the aromatic plane change hybridization between the planar Franck-Condon geometry and the deformed (boat-shaped S2 equilibrium geometry. The effect is observed to increase in the presence of methyl-groups on the pinnacle carbon-atoms, where largest extents of σ and π orbital-mixing are observed. This is fully consistent with the time-resolved spectroscopy data: Toluene and p-xylene show evidence for ultrafast triplet formation competing with internal conversion, while benzene appears to only decay via internal conversion within the singlet manifold. For toluene and p-xylene, internal conversion to S1 and intersystem crossing to T3 occur within the time-resolution of our instrument. The receiver triplet state (T3 is found to undergo internal conversion in the triplet manifold within ≈100–150 fs (toluene or ≈180–200 fs (p-xylene as demonstrated by matching rise and decay components of upper and lower triplet states. Overall, the effect of methylation is found to both increase the intersystem crossing probability and direct the molecular axis of the excited state dynamics.

  7. Observation of a Slater-type metal-to-insulator transition in Sr$_2$IrO$_4$ from time-resolved photo-carrier dynamics

    OpenAIRE

    Hsieh, D.; Mahmood, F.; Torchinsky, D. H.; Cao, G.; Gedik, N.

    2012-01-01

    We perform a time-resolved optical study of Sr$_2$IrO$_4$ to understand the influence of magnetic ordering on the low energy electronic structure of a strongly spin-orbit coupled $J_{eff}$=1/2 Mott insulator. By studying the recovery dynamics of photo-carriers excited across the Mott gap, we find that upon cooling through the N\\'{e}el temperature $T_N$ the system evolves continuously from a metal-like phase with fast ($\\sim$50 fs) and excitation density independent relaxation dynamics to a ga...

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

    Science.gov (United States)

    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.

  9. Factors affecting measurement of optic parameters by time-resolved near-infrared spectroscopy in breast cancer

    Science.gov (United States)

    Yoshizawa, Nobuko; Ueda, Yukio; Mimura, Tetsuya; Ohmae, Etsuko; Yoshimoto, Kenji; Wada, Hiroko; Ogura, Hiroyuki; Sakahara, Harumi

    2018-02-01

    The purpose of this study was to evaluate the effects of the thickness and depth of tumors on hemoglobin measurements in breast cancer by optical spectroscopy and to demonstrate tissue oxygen saturation (SO2) and reduced scattering coefficient (μs‧) in breast tissue and breast cancer in relation to the skin-to-chest wall distance. We examined 53 tumors from 44 patients. Total hemoglobin concentration (tHb), SO2, and μs‧ were measured by time-resolved spectroscopy (TRS). The skin-to-chest wall distance and the size and depth of tumors were measured by ultrasonography. There was a positive correlation between tHb and tumor thickness, and a negative correlation between tHb and tumor depth. SO2 in breast tissue decreased when the skin-to-chest wall distance decreased, and SO2 in tumors tended to be lower than in breast tissue. In breast tissue, there was a negative correlation between μs‧ and the skin-to-chest wall distance, and μs‧ in tumors was higher than in breast tissue. Measurement of tHb in breast cancer by TRS was influenced by tumor thickness and depth. Although SO2 seemed lower and μs‧ was higher in breast cancer than in breast tissue, the skin-to-chest wall distance may have affected the measurements.

  10. Dynamic Time-Resolved Chirped-Pulse Rotational Spectroscopy of Vinyl Cyanide Photoproducts in a Room Temperature Flow Reactor

    Science.gov (United States)

    Zaleski, Daniel P.; Prozument, Kirill

    2017-06-01

    Chirped-pulsed (CP) Fourier transform rotational spectroscopy invented by Brooks Pate and coworkers a decade ago is an attractive tool for gas phase chemical dynamics and kinetics studies. A good reactor for such a purpose would have well-defined (and variable) temperature and pressure conditions to be amenable to accurate kinetic modeling. Furthermore, in low pressure samples with large enough number of molecular emitters, reaction dynamics can be observable directly, rather than mediated by supersonic expansion. In the present work, we are evaluating feasibility of in situ time-resolved CP spectroscopy in a room temperature flow tube reactor. Vinyl cyanide (CH_2CHCN), neat or mixed with inert gasses, flows through the reactor at pressures 1-50 μbar (0.76-38 mTorr) where it is photodissociated by a 193 nm laser. Millimeter-wave beam of the CP spectrometer co-propagates with the laser beam along the reactor tube and interacts with nascent photoproducts. Rotational transitions of HCN, HNC, and HCCCN are detected, with ≥10 μs time-steps for 500 ms following photolysis of CH_2CHCN. The post-photolysis evolution of the photoproducts' rotational line intensities is investigated for the effects of rotational and vibrational thermalization of energized photoproducts. Possible contributions from bimolecular and wall-mediated chemistry are evaluated as well.

  11. Time-Resolved Spectroscopy and Near Infrared Imaging for Prostate Cancer Detection: Receptor-targeted and Native Biomarker

    Science.gov (United States)

    Pu, Yang

    Optical spectroscopy and imaging using near-infrared (NIR) light provides powerful tools for non-invasive detection of cancer in tissue. Optical techniques are capable of quantitative reconstructions maps of tissue absorption and scattering properties, thus can map in vivo the differences in the content of certain marker chromophores and/or fluorophores in normal and cancerous tissues (for example: water, tryptophan, collagen and NADH contents). Potential clinical applications of optical spectroscopy and imaging include functional tumor detection and photothermal therapeutics. Optical spectroscopy and imaging apply contrasts from intrinsic tissue chromophores such as water, collagen and NADH, and extrinsic optical contrast agents such as Indocyanine Green (ICG) to distinguish disease tissue from the normal one. Fluorescence spectroscopy and imaging also gives high sensitivity and specificity for biomedical diagnosis. Recent developments on specific-targeting fluorophores such as small receptor-targeted dye-peptide conjugate contrast agent offer high contrast between normal and cancerous tissues hence provide promising future for early tumour detection. This thesis focus on a study to distinguish the cancerous prostate tissue from the normal prostate tissues with enhancement of specific receptor-targeted prostate cancer contrast agents using optical spectroscopy and imaging techniques. The scattering and absorption coefficients, and anisotropy factor of cancerous and normal prostate tissues were investigated first as the basis for the biomedical diagnostic and optical imaging. Understanding the receptors over-expressed prostate cancer cells and molecular target mechanism of ligand, two small ICG-derivative dye-peptides, namely Cypate-Bombesin Peptide Analogue Conjugate (Cybesin) and Cypate-Octreotate Peptide Conjugate (Cytate), were applied to study their clinical potential for human prostate cancer detection. In this work, the steady-state and time-resolved

  12. Photophysical characterization and time-resolved spectroscopy of a anthradithiophene dimer: exploring the role of conformation in singlet fission

    KAUST Repository

    Dean, Jacob C.

    2017-08-18

    Quantitative singlet fission has been observed for a variety of acene derivatives such as tetracene and pentacene, and efforts to extend the library of singlet fission compounds is of current interest. Preliminary calculations suggest anthradithiophenes exhibit significant exothermicity between the first optically-allowed singlet state, S1, and 2 × T1 with an energy difference of >5000 cm−1. Given the fulfillment of this ingredient for singlet fission, here we investigate the singlet fission capability of a difluorinated anthradithiophene dimer (2ADT) covalently linked by a (dimethylsilyl)ethane bridge and derivatized by triisobutylsilylethynyl (TIBS) groups. Photophysical characterization of 2ADT and the single functionalized ADT monomer were carried out in toluene and acetone solution via absorption and fluorescence spectroscopy, and their photo-initiated dynamics were investigated with time-resolved fluorescence (TRF) and transient absorption (TA) spectroscopy. In accordance with computational predictions, two conformers of 2ADT were observed via fluorescence spectroscopy and were assigned to structures with the ADT cores trans or cis to one another about the covalent bridge. The two conformers exhibited markedly different excited state deactivation mechanisms, with the minor trans population being representative of the ADT monomer showing primarily radiative decay, while the dominant cis population underwent relaxation into an excimer geometry before internally converting to the ground state. The excimer formation kinetics were found to be solvent dependent, yielding time constants of ∼1.75 ns in toluene, and ∼600 ps in acetone. While the difference in rates elicits a role for the solvent in stabilizing the excimer structure, the rate is still decidedly long compared to most singlet fission rates of analogous dimers, suggesting that the excimer is neither a kinetic nor a thermodynamic trap, yet singlet fission was still not observed. The result

  13. Photoinduced charge transfer in a transition metal complex investigated by time-resolved X-ray absorption fine structure spectroscopy. Setup and experiment

    International Nuclear Information System (INIS)

    Goeries, Dennis

    2015-02-01

    In the framework of this thesis the development of a time-resolved X-ray absorption spectroscopy experiment and its application to fac-Ir(ppy) 3 is described. Such experiments require a very stable setup in terms of spatial and temporal accuracy. Therefore, the stability properties of the present installation were investigated in detail and continuously improved, in particular the synchronization of the ultrashort pulse laser system to the storage ring as well as the spatial stability of both X-ray and laser beam. Experiments utilizing the laser pump and X-ray probe configuration were applied on the green phosphorescence emitter complex fac-Ir(ppy) 3 dissolved in dimethyl sulfoxide. Structural and electronic changes were triggered by photoexcitation of the metal-to-ligand charge transfer band with ultrashort laser pulses at a wavelength of 343 nm. The excited triplet state spectrum was extracted from the measured pump-probe X-ray absorption spectrum using an ionic approximation. The results con rm the anticipated metal-to-ligand charge transfer as shown by an ionization potential shift of the iridium atom. The symmetry of the complex was found to be pseudo-octahedral. This allowed the first experimental determination of the bond length of fac-Ir(ppy) 3 in an octahedral approximation and revealed a decrease of bond length of the first coordination shell in the triplet state. The first and second-order decay kinetics of the triplet state were investigated in a combination of X-ray and laser based experiments and revealed self-quenching as well as triplet-triplet annihilation rate constants.

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

    Science.gov (United States)

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

    2015-06-22

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

  15. Interaction of europium and nickel with calcite studied by Rutherford Backscattering Spectrometry and Time-Resolved Laser Fluorescence Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Sabau, A. [Agence Nationale pour la gestion des Déchets RAdioactifs, 1-7 rue J. Monnet, Parc de la Croix Blanche, 92298 Châtenay-Malabry Cedex (France); Université de Nice Sophia Antipolis, Ecosystèmes Côtiers Marins et Réponses aux Stress (ECOMERS), 28 avenue Valrose, 06108 Nice Cedex 2 (France); Pipon, Y., E-mail: pipon@ipnl.in2p3.fr [Institut de Physique Nucléaire de Lyon (IPNL), Université Lyon 1, CNRS/IN2P3, 4 rue Enrico Fermi, 69 622 Villeurbanne Cedex (France); Institut Universitaire de Technologie (IUT) Lyon-1, Université Claude Bernard Lyon 1, 69 622 Villeurbanne Cedex (France); Toulhoat, N. [Institut de Physique Nucléaire de Lyon (IPNL), Université Lyon 1, CNRS/IN2P3, 4 rue Enrico Fermi, 69 622 Villeurbanne Cedex (France); CEA/DEN, Saclay, 91191 Gif sur Yvette (France); Lomenech, C. [Université de Nice Sophia Antipolis, Ecosystèmes Côtiers Marins et Réponses aux Stress (ECOMERS), 28 avenue Valrose, 06108 Nice Cedex 2 (France); Jordan, N. [Helmholtz Zentrum Dresden Rossendorf (HZDR), Institute of Resource Ecology (IRE) (Germany); Moncoffre, N. [Institut de Physique Nucléaire de Lyon (IPNL), Université Lyon 1, CNRS/IN2P3, 4 rue Enrico Fermi, 69 622 Villeurbanne Cedex (France); Barkleit, A. [Helmholtz Zentrum Dresden Rossendorf (HZDR), Institute of Resource Ecology (IRE) (Germany); and others

    2014-08-01

    This study aims at elucidating the mechanisms regulating the interaction of Eu and Ni with calcite (CaCO{sub 3}). Calcite powders or single crystals (some mm sized) were put into contact with Eu or Ni solutions at concentrations ranging from 10{sup −3} to 10{sup −5} mol L{sup −1} for Eu and 10{sup −3} mol L{sup −1} for Ni. The sorption durations ranged from 1 week to 1 month. Rutherford Backscattering Spectrometry (RBS) well adapted to discriminate incorporation processes such as: (i) adsorption or co precipitation at the mineral surfaces or, (ii) incorporation into the mineral structure (through diffusion for instance), has been carried out. Moreover, using the fluorescence properties of europium, the results have been compared to those obtained by Time-Resolved Laser Fluorescence Spectroscopy (TRLFS) on calcite powders. For the single crystals, complementary SEM observations of the mineral surfaces at low voltage were also performed. Results showed that Ni accumulates at the calcite surface whereas Eu is also incorporated at a greater depth. Eu seems therefore to be incorporated into two different states in calcite: (i) heterogeneous surface accumulation and (ii) incorporation at depth greater than 160 nm after 1 month of sorption. Ni was found to accumulate at the surface of calcite without incorporation.

  16. Time-Resolved Diffuse Optical Spectroscopy and Imaging Using Solid-State Detectors: Characteristics, Present Status, and Research Challenges.

    Science.gov (United States)

    Alayed, Mrwan; Deen, M Jamal

    2017-09-14

    Diffuse optical spectroscopy (DOS) and diffuse optical imaging (DOI) are emerging non-invasive imaging modalities that have wide spread potential applications in many fields, particularly for structural and functional imaging in medicine. In this article, we review time-resolved diffuse optical imaging (TR-DOI) systems using solid-state detectors with a special focus on Single-Photon Avalanche Diodes (SPADs) and Silicon Photomultipliers (SiPMs). These TR-DOI systems can be categorized into two types based on the operation mode of the detector (free-running or time-gated). For the TR-DOI prototypes, the physical concepts, main components, figures-of-merit of detectors, and evaluation parameters are described. The performance of TR-DOI prototypes is evaluated according to the parameters used in common protocols to test DOI systems particularly basic instrumental performance (BIP). In addition, the potential features of SPADs and SiPMs to improve TR-DOI systems and expand their applications in the foreseeable future are discussed. Lastly, research challenges and future developments for TR-DOI are discussed for each component in the prototype separately and also for the entire system.

  17. Excited state non-adiabatic dynamics of N-methylpyrrole: A time-resolved photoelectron spectroscopy and quantum dynamics study

    International Nuclear Information System (INIS)

    Wu, Guorong; Neville, Simon P.; Schalk, Oliver; Sekikawa, Taro; Ashfold, Michael N. R.; Worth, Graham A.; Stolow, Albert

    2016-01-01

    The dynamics of N-methylpyrrole following excitation at wavelengths in the range 241.5-217.0 nm were studied using a combination of time-resolved photoelectron spectroscopy (TRPES), ab initio quantum dynamics calculations using the multi-layer multi-configurational time-dependent Hartree method, as well as high-level photoionization cross section calculations. Excitation at 241.5 and 236.2 nm results in population of the A 2 (πσ ∗ ) state, in agreement with previous studies. Excitation at 217.0 nm prepares the previously neglected B 1 (π3p y ) Rydberg state, followed by prompt internal conversion to the A 2 (πσ ∗ ) state. In contrast with the photoinduced dynamics of pyrrole, the lifetime of the wavepacket in the A 2 (πσ ∗ ) state was found to vary with excitation wavelength, decreasing by one order of magnitude upon tuning from 241.5 nm to 236.2 nm and by more than three orders of magnitude when excited at 217.0 nm. The order of magnitude difference in lifetimes measured at the longer excitation wavelengths is attributed to vibrational excitation in the A 2 (πσ ∗ ) state, facilitating wavepacket motion around the potential barrier in the N–CH 3 dissociation coordinate

  18. Excited state non-adiabatic dynamics of N-methylpyrrole: A time-resolved photoelectron spectroscopy and quantum dynamics study

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Guorong [National Research Council Canada, 100 Sussex Drive, Ottawa, Ontario K1A 0R6 (Canada); State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, Liaoning 116023 (China); Synergetic Innovation Center of Quantum Information & Quantum Physics, University of Science and Technology of China, Hefei, Anhui 230026 (China); Neville, Simon P. [Department of Chemistry, University of Ottawa, 10 Marie Curie, Ottawa, Ontario K1N 6N5 (Canada); Schalk, Oliver [National Research Council Canada, 100 Sussex Drive, Ottawa, Ontario K1A 0R6 (Canada); Department of Physics, AlbaNova University Center, Stockholm University, Roslagstullsbacken 21, 106 91 Stockholm (Sweden); Sekikawa, Taro [Department of Applied Physics, Hokkaido University, Kita-13 Nishi-8, Kita-ku, Sapporo 060-8628 (Japan); Ashfold, Michael N. R. [School of Chemistry, University of Bristol, Bristol BS8 1TS (United Kingdom); Worth, Graham A. [School of Chemistry, University of Birmingham, Edgbaston, Birmingham B15 2TT (United Kingdom); Stolow, Albert, E-mail: astolow@uottawa.ca [National Research Council Canada, 100 Sussex Drive, Ottawa, Ontario K1A 0R6 (Canada); Department of Chemistry, University of Ottawa, 10 Marie Curie, Ottawa, Ontario K1N 6N5 (Canada); Department of Physics, University of Ottawa, 150 Louis Pasteur, Ottawa, Ontario K1N 6N5 (Canada)

    2016-01-07

    The dynamics of N-methylpyrrole following excitation at wavelengths in the range 241.5-217.0 nm were studied using a combination of time-resolved photoelectron spectroscopy (TRPES), ab initio quantum dynamics calculations using the multi-layer multi-configurational time-dependent Hartree method, as well as high-level photoionization cross section calculations. Excitation at 241.5 and 236.2 nm results in population of the A{sub 2}(πσ{sup ∗}) state, in agreement with previous studies. Excitation at 217.0 nm prepares the previously neglected B{sub 1}(π3p{sub y}) Rydberg state, followed by prompt internal conversion to the A{sub 2}(πσ{sup ∗}) state. In contrast with the photoinduced dynamics of pyrrole, the lifetime of the wavepacket in the A{sub 2}(πσ{sup ∗}) state was found to vary with excitation wavelength, decreasing by one order of magnitude upon tuning from 241.5 nm to 236.2 nm and by more than three orders of magnitude when excited at 217.0 nm. The order of magnitude difference in lifetimes measured at the longer excitation wavelengths is attributed to vibrational excitation in the A{sub 2}(πσ{sup ∗}) state, facilitating wavepacket motion around the potential barrier in the N–CH{sub 3} dissociation coordinate.

  19. Site-Specific Measurement of Water Dynamics in the Substrate Pocket of Ketosteroid Isomerase Using Time-Resolved Vibrational Spectroscopy

    Science.gov (United States)

    Jha, Santosh Kumar; Ji, Minbiao; Gaffney, Kelly J.; Boxer, Steven G.

    2012-01-01

    Little is known about the reorganization capacity of water molecules at the active sites of enzymes and how this couples to the catalytic reaction. Here, we study the dynamics of water molecules at the active site of a highly proficient enzyme, Δ5-3-ketosteroid isomerase (KSI), during a light-activated mimic of its catalytic cycle. Photo-excitation of a nitrile containing photo-acid, coumarin183 (C183), mimics the change in charge density that occurs at the active site of KSI during the first step of the catalytic reaction. The nitrile of C183 is exposed to water when bound to the KSI active site, and we used time-resolved vibrational spectroscopy as a site-specific probe to study the solvation dynamics of water molecules in the vicinity of the nitrile. We observed that water molecules at the active site of KSI are highly rigid, during the light-activated catalytic cycle, compared to the solvation dynamics observed in bulk water. Based upon this result we hypothesize that rigid water dipoles at the active site might help in the maintenance of the pre-organized electrostatic environment required for efficient catalysis. The results also demonstrate the utility of nitrile probes in measuring the dynamics of local (H-bonded) water molecules in contrast to the commonly used fluorescence methods which measure the average behavior of primary and subsequent spheres of solvation. PMID:22931297

  20. Studies on Ternary Complex Formation of U(VI)-salicylate by Using Time-resolved Fluorescence Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Cha, Wan Sik; Cho, H. R.; Park, K. K.; Kim, W. H.; Jung, E. C. [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

    2010-05-15

    Organic ligands containing carboxylic and phenolic functional groups naturally occur in groundwater environment, particularly in forms of polyelectrolytes such as humic and fulvic acids, from microbial degradation of biomass, e.g., plant and animal tissues. These ligands play important roles in dissolution and migration of actinide radionuclide species since they can form stable ternary actinide complexes with common inorganic ions like hydroxides and carbonates. Therefore, model ternary complexes of lanthanides and actinides have been targets of studies to understand their chemical behaviors under near-neutral pH groundwater conditions. Previous model carboxylic ligands include phthalates, maleic acids, or alpha- substituted carboxylic acids. However, majority of previous studies investigated binary systems or used potentiometric titration method that requires high ligand concentration in mM levels. Recently, highly sensitive time-resolved laserinduced fluorescence spectroscopy (TRLFS) has been used to investigate lower concentration (e.g., a few {mu}M levels) reactions of binary complexes between of ligands and metal ions. This technique provides information regarding electronic structures and complexation constants as well as fluorescence quenching mechanism. In the present study, we studied the U(VI)-OH-salicylate (SA) ternary complex formation at higher pH (> 4) via TRLF spectrum and UV-Vis absorbance measurement. Preliminary studies show that the fluorescence (FL) intensity of hydroxouranyl species at pH 4.5 decreases as SA concentration elevates in aqueous solution. Fluorescence quenching mechanism by SA is suggested based on FL intensity (I) and lifetime (tau) measurement via TRLFS

  1. Time-resolved and steady-state studies of biologically and chemically relevant systems using laser, absorption, and fluorescence spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Barnes, Charles Ashley [Iowa State Univ., Ames, IA (United States)

    2014-12-20

    In Chapter 2 several experimental and data analysis methods used in this thesis are described. In Chapter 3 steady-state fluorescence spectroscopy was used to determine the concentration of the efflux pump inhibitors (EPIs), pheophorbide a and pyropheophorbide a, in the feces of animals and it was found that their levels far exceed those reported to be inhibitory to efflux pumps. In Chapter 4 the solvation dynamics of 6-Propionyl-2-(N,Ndimethyl) aminonaphthalene (PRODAN) was studied in reverse micelles. The two fluorescent states of PRODAN solvate on different time scales and as such care must be exercised in solvation dynamic studies involving it and its analogs. In Chapter 5 we studied the experimental and theoretical solvation dynamics of coumarin 153 (C153) in wild-type (WT) and modified myoglobins. Based on the nuclear magnetic resonance (NMR) spectroscopy and time-resolved fluorescence studies, we have concluded that it is important to thoroughly characterize the structure of a protein and probe system before comparing the theoretical and experimental results. In Chapter 6 the photophysical and spectral properties of a derivative of the medically relevant compound curcumin called cyclocurcumin was studied. Based on NMR, fluorescence, and absorption studies, the ground- and excited-states of cyclocurcumin are complicated by the existence of multiple structural isomers. In Chapter 7 the hydrolysis of cellulose by a pure form of cellulase in an ionic liquid, HEMA, and its aqueous mixtures at various temperatures were studied with the goal of increasing the cellulose to glucose conversion for biofuel production. It was found that HEMA imparts an additional stability to cellulase and can allow for faster conversion of cellulose to glucose using a pre-treatment step in comparison to only buffer.

  2. Insights into the charge carrier terahertz mobility in polyfluorenes from large-scale atomistic simulations and time-resolved terahertz spectroscopy

    Czech Academy of Sciences Publication Activity Database

    Vukmirović, N.; Ponseca, C.S.; Němec, Hynek; Yartsev, A.; Sundström, V.

    2012-01-01

    Roč. 116, č. 37 (2012), s. 19665-1972 ISSN 1932-7447 Institutional research plan: CEZ:AV0Z10100520 Keywords : charge carrier mobility * time-resolved terahertz spectroscopy * multiscale atomistic calculations Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 4.814, year: 2012

  3. Isolated Gramicidin Peptides Probed by IR Spectroscopy

    NARCIS (Netherlands)

    Rijs, A. M.; Kabelac, M.; Abo-Riziq, A.; Hobza, P.; de Vries, M. S.

    2011-01-01

    We report double-resonant IR/UV ion-dip spectroscopy of neutral gramicidin peptides in the gas phase. The IR spectra of gramicidin A and C, recorded in both the 1000 cm(-1) to 1800 cm(-1) and the 2700 to 3750 cm(-1) region, allow structural analysis. By studying this broad IR range, various local

  4. Biochemical applications of FT-IR spectroscopy

    NARCIS (Netherlands)

    Pistorius, A.M.A.

    1996-01-01

    This thesis describes the use of (FT-)IR spectroscopy in general biochemical research. In chapter 3, IR spectroscopy is used in the quantitation of residual detergent after reconstitution of an integral membrane protein in a pre-defined lipid matrix. This chapter discusses the choice of the

  5. High-repetition-rate setup for pump-probe time-resolved XUV-IR experiments employing ion and electron momentum imaging

    Science.gov (United States)

    Pathak, Shashank; Robatjazi, Seyyed Javad; Wright Lee, Pearson; Raju Pandiri, Kanaka; Rolles, Daniel; Rudenko, Artem

    2017-04-01

    J.R. Macdonald Laboratory, Department of Physics, Kansas State University, Manhattan KS, USA We report on the development of a versatile experimental setup for XUV-IR pump-probe experiments using a 10 kHz high-harmonic generation (HHG) source and two different charged-particle momentum imaging spectrometers. The HHG source, based on a commercial KM Labs eXtreme Ultraviolet Ultrafast Source, is capable of delivering XUV radiation of less than 30 fs pulse duration in the photon energy range of 17 eV to 100 eV. It can be coupled either to a conventional velocity map imaging (VMI) setup with an atomic, molecular, or nanoparticle target; or to a novel double-sided VMI spectrometer equipped with two delay-line detectors for coincidence studies. An overview of the setup and results of first pump-probe experiments including studies of two-color double ionization of Xe and time-resolved dynamics of photoionized CO2 molecule will be presented. This project is supported in part by National Science Foundation (NSF-EPSCOR) Award No. IIA-1430493 and in part by the Chemical science, Geosciences, and Bio-Science division, Office of Basic Energy Science, Office of science, U.S. Department of Energy. K.

  6. Determination of blood oxygenation in the brain by time-resolved reflectance spectroscopy: influence of the skin, skull, and meninges

    Science.gov (United States)

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

    1994-07-01

    Near infrared light has been used for the determination of blood oxygenation in the brain but little attention has been paid to the fact that the states of blood oxygenation in arteries, veins, and capillaries differ substantially. In this study, Monte Carlo simulations for a heterogeneous system were conducted, and near infrared time-resolved reflectance measurements were performed on a heterogeneous tissue phantom model. The model was made of a solid polyester resin, which simulates the tissue background. A network of tubes was distributed uniformly through the resin to simulate the blood vessels. The time-resolved reflectance spectra were taken with different absorbing solutions filled in the network. Based on the simulation and experimental results, we investigated the dependence of the absorption coefficient obtained from the heterogeneous system on the absorption of the actual absorbing solution filled in the tubes. We show that light absorption by the brain should result from the combination of blood and blood-free tissue background.

  7. Equilibrium constants in aqueous lanthanide and actinide chemistry from time-resolved fluorescence spectroscopy: The role of ground and excited state reactions

    International Nuclear Information System (INIS)

    Billard, I.; Luetzenkirchen, K.

    2003-01-01

    Equilibrium constants for aqueous reactions between lanthanide or actinide ions and (in-) organic ligands contain important information for various radiochemical problems, such as nuclear reprocessing or the migration of radioelements in the geosphere. We study the conditions required to determine equilibrium constants by time-resolved fluorescence spectroscopy measurements. Based on a simulation study it is shown that the possibility to determine equilibrium constants depends upon the reaction rates in the photoexcited states of the lanthanide or actinide ions. (orig.)

  8. Dynamics of Al/Fe{sub 2}O{sub 3} MIC combustion from short single-pulse photothermal initiation and time-resolved spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Stiegman, Albert E.; Park, Chi-Dong; Mileham, Melissa; Van de Burgt, Lambertus J. [Department of Chemistry and Biochemistry, Florida State University Tallahassee, FL (United States); Kramer, Michael P. [AFRL/MNME Eglin AFB, FL (United States)

    2009-08-15

    Time-resolved spectroscopy was used to study the dynamics of the photothermal ignition of Al/Fe{sub 2}O{sub 3} metastable intermolecular composites after single short-pulse laser initiation. The dynamics were recorded in several time domains from nanosecond to microsecond to quantify the dynamics from initial laser excitation to combustion. Time-averaged spectral data were also collected for the overall emission occurring during combustion. (Abstract Copyright [2009], Wiley Periodicals, Inc.)

  9. Guest–Host Interactions Investigated by Time-Resolved X-ray Spectroscopies and Scattering at MHz Rates

    DEFF Research Database (Denmark)

    Haldrup, Martin Kristoffer; Vanko, G.; Gawelda, W.

    2012-01-01

    We have studied the photoinduced low spin (LS) to high spin (HS) conversion of [Fe(bipy)3]2+ in aqueous solution. In a laser pump/X-ray probe synchrotron setup permitting simultaneous, time-resolved X-ray diffuse scattering (XDS) and X-ray spectroscopic measurements at a 3.26 MHz repetition rate...... lifetime, allowing the detection of an ultrafast change in bulk solvent density. An analysis approach directly utilizing the spectroscopic data in the XDS analysis effectively reduces the number of free parameters, and both combined permit extraction of information about the ultrafast structural dynamics...

  10. Multichannel, time-resolved picosecond laser ultrasound imaging and spectroscopy with custom complementary metal-oxide-semiconductor detector

    International Nuclear Information System (INIS)

    Smith, Richard J.; Light, Roger A.; Johnston, Nicholas S.; Pitter, Mark C.; Somekh, Mike G.; Sharples, Steve D.

    2010-01-01

    This paper presents a multichannel, time-resolved picosecond laser ultrasound system that uses a custom complementary metal-oxide-semiconductor linear array detector. This novel sensor allows parallel phase-sensitive detection of very low contrast modulated signals with performance in each channel comparable to that of a discrete photodiode and a lock-in amplifier. Application of the instrument is demonstrated by parallelizing spatial measurements to produce two-dimensional thickness maps on a layered sample, and spectroscopic parallelization is demonstrated by presenting the measured Brillouin oscillations from a gallium arsenide wafer. This paper demonstrates the significant advantages of our approach to pump probe systems, especially picosecond ultrasonics.

  11. Multichannel, time-resolved picosecond laser ultrasound imaging and spectroscopy with custom complementary metal-oxide-semiconductor detector

    Energy Technology Data Exchange (ETDEWEB)

    Smith, Richard J.; Light, Roger A.; Johnston, Nicholas S.; Pitter, Mark C.; Somekh, Mike G. [Institute of Biophysics, Imaging and Optical Science, University of Nottingham, Nottinghamshire NG7 2RD (United Kingdom); Sharples, Steve D. [Applied Optics Group, Electrical Systems and Optics Research Division, University of Nottingham, Nottinghamshire NG7 2RD (United Kingdom)

    2010-02-15

    This paper presents a multichannel, time-resolved picosecond laser ultrasound system that uses a custom complementary metal-oxide-semiconductor linear array detector. This novel sensor allows parallel phase-sensitive detection of very low contrast modulated signals with performance in each channel comparable to that of a discrete photodiode and a lock-in amplifier. Application of the instrument is demonstrated by parallelizing spatial measurements to produce two-dimensional thickness maps on a layered sample, and spectroscopic parallelization is demonstrated by presenting the measured Brillouin oscillations from a gallium arsenide wafer. This paper demonstrates the significant advantages of our approach to pump probe systems, especially picosecond ultrasonics.

  12. Continuous wave and time resolved spectroscopy of InAsN/GaAsN based quantum dots

    International Nuclear Information System (INIS)

    Taliercio, T.; Valvin, P.; Intartaglia, R.; Guillet, T.; Lefebvre, P.; Bretagnon, T.; Gil, B.; Sallet, V.; Harmand, J.C.

    2005-01-01

    We present a study of the optical properties of quantum dots based on a new family of semiconductors: III-V dilute nitrides such as (In,Ga)(N,As). Continuous wave and time resolved photoluminescence (PL) experiments allowed us to evaluate the impact of N incorporation during the growth of InAs/GaAs quantum dots. Previous work [V. Sallet et al., to be submitted to J. Cryst. Growth (2005); O. Schumann et al., J. Appl. Phys. 96, 2832 (2004)] showed that increasing the flux of N atoms into the growth chamber modifies drastically the size of the dots which leads to a bimodal growth. Two populations of dots with different sizes appear. The quantum dot PL line broadens and a second PL line appears at higher energy. Time resolved PL allows us to identify the nature of this second PL line: second population of quantum dots. A second decay time is observed which we interpret as being the consequence of the perturbation of the electronic states of the quantum dots. (copyright 2005 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  13. Bond Shortening (1.4 Å) in the Singlet and Triplet Excited States of [Ir2(dimen)4]2+ in Solution Determined by Time-Resolved X-ray Scattering

    DEFF Research Database (Denmark)

    Haldrup, Martin Kristoffer; Harlang, Tobias; Christensen, Morten

    2011-01-01

    Ground- and excited-state structures of the bimetallic, ligand-bridged compound Ir2(dimen)42+ are investigated in acetonitrile by means of time-resolved X-ray scattering. Following excitation by 2 ps laser pulses at 390 nm, analysis of difference scattering patterns obtained at eight different ti...

  14. Lifetime measurements of odd-parity high-excitation levels of Sn I by time-resolved laser spectroscopy

    International Nuclear Information System (INIS)

    Zhang, Wei; Feng, Yanyan; Xu, Jiaxin; Dai, Zhenwen; Palmeri, Patrick; Quinet, Pascal; Biemont, Emile

    2010-01-01

    Natural radiative lifetimes of 38 odd-parity highly excited levels in neutral tin in the energy range from 43 682.737 to 56 838.68 cm -1 have been measured by a time-resolved laser-induced fluorescence technique in an atomic beam produced by laser ablation on a solid tin sample. All the levels were excited from the metastable 3 P 1, 2 and 1 D 2 levels in the ground configuration. The second and third harmonics of a dye laser were adopted as the tunable exciting source (207-250 nm). The lifetime results obtained in this paper are in the range from 4.6 to 292 ns and will be useful in extending the set of oscillator strengths available in Sn I.

  15. Lifetime measurements of odd-parity high-excitation levels of Sn I by time-resolved laser spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Wei; Feng, Yanyan; Xu, Jiaxin; Dai, Zhenwen [College of Physics, Jilin University and Key Lab of Coherent Light, Atomic and Molecular Spectroscopy, Ministry of Education, Changchun 130021 (China); Palmeri, Patrick; Quinet, Pascal; Biemont, Emile, E-mail: dai@jlu.edu.c [Astrophysique et Spectroscopie, Universite de Mons-UMONS, B-7000 Mons (Belgium)

    2010-10-28

    Natural radiative lifetimes of 38 odd-parity highly excited levels in neutral tin in the energy range from 43 682.737 to 56 838.68 cm{sup -1} have been measured by a time-resolved laser-induced fluorescence technique in an atomic beam produced by laser ablation on a solid tin sample. All the levels were excited from the metastable {sup 3}P{sub 1,} {sub 2} and {sup 1}D{sub 2} levels in the ground configuration. The second and third harmonics of a dye laser were adopted as the tunable exciting source (207-250 nm). The lifetime results obtained in this paper are in the range from 4.6 to 292 ns and will be useful in extending the set of oscillator strengths available in Sn I.

  16. Gauge invariance in the theoretical description of time-resolved angle-resolved pump/probe photoemission spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Freericks, J. K.; Krishnamurthy, H. R.; Sentef, M. A.; Devereaux, T. P.

    2015-10-01

    Nonequilibrium calculations in the presence of an electric field are usually performed in a gauge, and need to be transformed to reveal the gauge-invariant observables. In this work, we discuss the issue of gauge invariance in the context of time-resolved angle-resolved pump/probe photoemission. If the probe is applied while the pump is still on, one must ensure that the calculations of the observed photocurrent are gauge invariant. We also discuss the requirement of the photoemission signal to be positive and the relationship of this constraint to gauge invariance. We end by discussing some technical details related to the perturbative derivation of the photoemission spectra, which involve processes where the pump pulse photoexcites electrons due to nonequilibrium effects.

  17. Time resolved emission spectroscopy investigations of pulsed laser ablated plasmas of ZrO2 and Al2O3

    International Nuclear Information System (INIS)

    Hadoko, A D; Lee, P S; Lee, P; Mohanty, S R; Rawat, R S

    2006-01-01

    With the rising trend of synthesizing ultra thin films and/or quantum-confined materials using laser ablation, optimization of deposition parameters plays an essential role in obtaining desired film characteristics. This paper presents the initial step of plasma optimization study by examining temporal distribution of the plasma formation by pulsed laser ablation of materials. The emitted spectra of ZrO 2 and Al 2 O 3 are obtained ∼3mm above the ablated target to derive the ablated plasma characteristics. The plasma temperature is estimated to be at around 2.35 eV, with electron density of 1.14 x 10 16 (cm -3 ). Emission spectra with different gate delay time (40-270 ns) are captured to study the time resolved plume characteristics. Transitory elemental species are identified

  18. Investigation of verbal and visual working memory by multi-channel time-resolved functional near-infrared spectroscopy

    Science.gov (United States)

    Contini, D.; Caffini, M.; Re, R.; Zucchelli, L.; Spinelli, L.; Basso Moro, S.; Bisconti, S.; Ferrari, M.; Quaresima, V.; Cutini, S.; Torricelli, A.

    2013-03-01

    Working memory (WM) is fundamental for a number of cognitive processes, such as comprehension, reasoning and learning. WM allows the short-term maintenance and manipulation of the information selected by attentional processes. The goal of this study was to examine by time-resolved fNIRS neural correlates of the verbal and visual WM during forward and backward digit span (DF and DB, respectively) tasks, and symbol span (SS) task. A neural dissociation was hypothesised between the maintenance and manipulation processes. In particular, a dorsolateral/ventrolateral prefrontal cortex (DLPFC/VLPFC) recruitment was expected during the DB task, whilst a lateralised involvement of Brodmann Area (BA) 10 was expected during the execution of the DF task. Thirteen subjects were monitored by a multi-channel, dual-wavelength (690 and 829 nm) time-resolved fNIRS system during 3 minutes long DF and DB tasks and 4 minutes long SS task. The participants' mean memory span was calculated for each task: DF: 6.46+/-1.05 digits; DB: 5.62+/-1.26 digits; SS: 4.69+/-1.32 symbols. No correlation was found between the span level and the heart rate data (measured by pulse oximeter). As expected, DB elicited a broad activated area, in the bilateral VLPFC and the right DLPFC, whereas a more localised activation was observed over the right hemisphere during either DF (BA 10) or SS (BA 10 and 44). The robust involvement of the DLPFC during DB, compared to DF, is compatible with previous findings and with the key role of the central executive subserving in manipulating processes.

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

    Energy Technology Data Exchange (ETDEWEB)

    Kang, Zhitao [Georgia Tech Research Institute, Georgia Institute of Technology, Atlanta, Georgia 30332-0826 (United States); School of Materials Science and Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332-0245 (United States); Banishev, Alexandr A.; Christensen, James; Dlott, Dana D. [School of Chemical Sciences and Fredrick Seitz Materials Research Laboratory, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801 (United States); Lee, Gyuhyon; Scripka, David A.; Breidenich, Jennifer; Summers, Christopher J.; Thadhani, Naresh N., E-mail: naresh.thadhani@mse.gatech.edu [School of Materials Science and Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332-0245 (United States); Xiao, Pan [LNM, Institute of Mechanics, Chinese Academy of Sciences, Beijing 100190 (China); George W. Woodruff School of Mechanical Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332-0405 (United States); Zhou, Min [George W. Woodruff School of Mechanical Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332-0405 (United States)

    2016-07-28

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

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

    International Nuclear Information System (INIS)

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

    2016-01-01

    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.

  1. Decay time shortening of fluorescence from donor-acceptor pair proteins using ultrafast time-resolved fluorescence resonance energy transfer spectroscopy

    International Nuclear Information System (INIS)

    Baba, Motoyoshi; Suzuki, Masayuki; Ganeev, Rashid A.; Kuroda, Hiroto; Ozaki, Tsuneyuki; Hamakubo, Takao; Masuda, Kazuyuki; Hayashi, Masahiro; Sakihama, Toshiko; Kodama, Tatsuhiko; Kozasa, Tohru

    2007-01-01

    We improved an ultrafast time-resolved fluorescence resonance energy transfer (FRET) spectroscopy system and measured directly the decrease in the fluorescence decay time of the FRET signal, without any entanglement of components in the picosecond time scale from the donor-acceptor protein pairs (such as cameleon protein for calcium ion indicator, and ligand-activated GRIN-Go proteins pair). The drastic decrease in lifetime of the donor protein fluorescence under the FRET condition (e.g. a 47.8% decrease for a GRIN-Go protein pair) proves the deformation dynamics between donor and acceptor fluorescent proteins in an activated state of a mixed donor-acceptor protein pair. This study is the first clear evidence of physical contact of the GRIN-Go proteins pair using time-resolved FRET system. G protein-coupled receptors (GPCRs) are the most important protein family for the recognition of many chemical substances at the cell surface. They are the targets of many drugs. Simultaneously, we were able to observe the time-resolved spectra of luminous proteins at the initial stage under the FRET condition, within 10 ns from excitation. This new FRET system allows us to trace the dynamics of the interaction between proteins at the ligand-induced activated state, molecular structure change and combination or dissociation. It will be a key technology for the development of protein chip technology

  2. Steady state and time-resolved fluorescence spectroscopy of quinine sulfate dication bound to sodium dodecylsulfate micelles: Fluorescent complex formation

    Energy Technology Data Exchange (ETDEWEB)

    Joshi, Sunita; Pant, Debi D., E-mail: ddpant@pilani.bits-pilani.ac.in

    2014-01-15

    Interaction of quinine sulfate dication (QSD) with anionic, sodium dodecylsulphate (SDS) surfactant has been studied at different premicellar, micellar and postmicellar concentrations in aqueous phase using steady state, time-resolved fluorescence and fluorescence anisotropy techniques. At premicellar concentrations of SDS, the decrease in absorbance, appearance of an extra fluorescence band at lower wavelengths and tri-exponential decay behavior of fluorescence, are attributed to complex formation between QSD molecules and surfactant monomers. At postmicellar concentrations the red shift in fluorescence spectrum, increase in quantum yield and increase in fluorescence lifetimes are attributed to incorporation of solute molecules to micelles. At lower concentrations of SDS, a large shift in fluorescence is observed on excitation at the red edge of absorption spectrum and this is explained in terms of distribution of ion pairs of different energies in the ground state and the observed fluorescence lifetime behavior corroborates with this model. The temporal fluorescence anisotropy decay of QSD in SDS micelles allowed determination of restriction on the motion of the fluorophore. All the different techniques used in this study reveal that the photophysics of QSD is very sensitive to the microenvironments of SDS micelles and QSD molecules reside at the water-micelle interface. -- Highlights: • Probe molecule is very sensitive to microenvironment of micelles. • Highly fluorescent ion-pair formation has been observed. • Modulated photophysics of probe molecule in micellar solutions has been observed. • Probe molecules strongly bind with micelles and reside at probe–micelle interface.

  3. Time-resolved tunable diode laser absorption spectroscopy of excited argon and ground-state titanium atoms in pulsed magnetron discharges

    Czech Academy of Sciences Publication Activity Database

    Sushkov, V.; Do, H.T.; Čada, Martin; Hubička, Zdeněk; Hippler, R.

    2013-01-01

    Roč. 22, č. 1 (2013), 1-10 ISSN 0963-0252 R&D Projects: GA ČR(CZ) GAP205/11/0386; GA ČR GAP108/12/2104 Institutional research plan: CEZ:AV0Z10100522 Keywords : absorption spectroscopy * diode laser * magnetron * argon metastable * HiPIMS * titanium * time-resolved Subject RIV: BH - Optics, Masers, Lasers Impact factor: 3.056, year: 2013 http://iopscience.iop.org/0963-0252/22/1/015002/

  4. Visualizing Infrared (IR) Spectroscopy with Computer Animation

    Science.gov (United States)

    Abrams, Charles B.; Fine, Leonard W.

    1996-01-01

    IR Tutor, an interactive, animated infrared (IR) spectroscopy tutorial has been developed for Macintosh and IBM-compatible computers. Using unique color animation, complicated vibrational modes can be introduced to beginning students. Rules governing the appearance of IR absorption bands become obvious because the vibrational modes can be visualized. Each peak in the IR spectrum is highlighted, and the animation of the corresponding normal mode can be shown. Students can study each spectrum stepwise, or click on any individual peak to see its assignment. Important regions of each spectrum can be expanded and spectra can be overlaid for comparison. An introduction to the theory of IR spectroscopy is included, making the program a complete instructional package. Our own success in using this software for teaching and research in both academic and industrial environments will be described. IR Tutor consists of three sections: (1) The 'Introduction' is a review of basic principles of spectroscopy. (2) 'Theory' begins with the classical model of a simple diatomic molecule and is expanded to include larger molecules by introducing normal modes and group frequencies. (3) 'Interpretation' is the heart of the tutorial. Thirteen IR spectra are analyzed in detail, covering the most important functional groups. This section features color animation of each normal mode, full interactivity, overlay of related spectra, and expansion of important regions. This section can also be used as a reference.

  5. On the course of fusion processes occurring in the plasma focus - an investigation by using time-resolved neutron spectroscopy

    International Nuclear Information System (INIS)

    Schmidt, R.

    1987-01-01

    The plasma focus POSEIDON emits up to 2x10 11 neutrons during some 100 ns, if it is operated with deuterium. This very high neutron production cannot be explained by a thermal neutron production mechanism starting out from the measured values of temperature (about 1 KeV) and deuteron density (10 18 cm -3 ). There is no doubt, that there exist strong ''beam-target''-processes of the deuterons, which cause such a high suprathermal neutron production. The neutron emission of the plasma focus POSEIDON appears in two pulses, which are associated to the two main phases of the hot and dense plasma. The first is the pinch or quiescent phase, in which a stable plasma column over 100 or 150 ns exists. The second phase is characterized by turbulence processes and starts with the end of the stable phase with the on-set of the m=0-instabilities and ends with the decay of the plasma. Both phases of neutron production are studied by time-resolved analysis of the neutron anisotropy factor and by time and spatial-resolved measurements of the neutron emission. Hence it follows, that there exist during both phases different non thermal neutron production processes, which are caused by different deuteron acceleration mechanisms. To get information on these deuteron acceleration mechanisms it is appropriate to analyse the neutron spectra of the plasma focus, because the half-width and the shape of the measured spectra are related to the energy and the angular distribution of the accelerated deuterons. (orig./GG) [de

  6. Time resolved study of the emission enhancement mechanisms in orthogonal double-pulse laser-induced breakdown spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Sanginés, R., E-mail: roberto.sangines@ccadet.unam.mx; Sobral, H.

    2013-10-01

    The evolution of laser induced ablation plume on aluminum targets has been investigated in orthogonal pre-ablation double pulse scheme at atmospheric pressure from the earliest stages of plasma evolution. Time-resolved emission spectra from neutrals, singly- and doubly-ionized species obtained with the double pulse experiment have been compared with those from the single pulse configuration. Signal-to-noise enhancement reaches values of up to 15 depending on the analyzed species; and the lower the charge state the later its maximum signal-to-noise ratio is reached. Ablation plume dynamics was monitored from 10 ns after the plasma onset via shadowgraphy and fast-photography with narrow interference filters to follow the evolution of individual species. Results show that ionic species from the target are located at the plasma core while nitrogen from the background air is found at the plume peripheral. Initially both configurations exhibit similar ablation plume sizes and their expansions were successfully fitted with the strong explosion model for the first 500 ns. At later times a good agreement was obtained by using the drag model, which predicts that the plume expansion eventually stops due to interaction with the background gas particles. The emission enhancement measured in the double pulse scheme is discussed in terms of the models describing the plume dynamics. - Highlights: • Production of 2 + ions at the earliest stages of plasma evolution • The higher the charge state the inner the location within the ablation plume. • The expansion rate of the second (ablation) plume was measured. • Shock and drag models successfully fit the ablation shock front expansion.

  7. Time-resolved plasma spectroscopy of thin foils heated by a relativistic-intensity short-pulse laser

    International Nuclear Information System (INIS)

    Audebert, P.; Gauthier, J.-C.; Shepherd, R.; Fournier, K.B.; Price, D.; Lee, R.W.; Springer, P.; Peyrusse, O.; Klein, L.

    2002-01-01

    Time-resolved K-shell x-ray spectra are recorded from sub-100 nm aluminum foils irradiated by 150-fs laser pulses at relativistic intensities of Iλ 2 =2x10 18 W μm 2 /cm 2 . The thermal penetration depth is greater than the foil thickness in these targets so that uniform heating takes place at constant density before hydrodynamic motion occurs. The high-contrast, high-intensity laser pulse, broad spectral band, and short time resolution utilized in this experiment permit a simplified interpretation of the dynamical evolution of the radiating matter. The observed spectrum displays two distinct phases. At early time, ≤500 fs after detecting target emission, a broad quasicontinuous spectral feature with strong satellite emission from multiply excited levels is seen. At a later time, the He-like resonance line emission is dominant. The time-integrated data is in accord with previous studies with time resolution greater than 1 ps. The early time satellite emission is shown to be a signature of an initial large area, high density, low-temperature plasma created in the foil by fast electrons accelerated by the intense radiation field in the laser spot. We conclude that, because of this early time phenomenon and contrary to previous predictions, a short, high-intensity laser pulse incident on a thin foil does not create a uniform hot and dense plasma. The heating mechanism has been studied as a function of foil thickness, laser pulse length, and intensity. In addition, the spectra are found to be in broad agreement with a hydrodynamic expansion code postprocessed by a collisional-radiative model based on superconfiguration average rates and on the unresolved transition array formalism

  8. Real-time monitoring of airborne beryllium, at OSHA limit levels, by time-resolved laser-induced breakdown spectroscopy

    International Nuclear Information System (INIS)

    Radziemski, L.J.; Loree, T.R.; Cremers, D.A.

    1982-01-01

    Real-time detection of beryllium particulate is being investigated by the new technique of laser-induced breakdown spectroscopy. For beryllium detection we monitor the 313.1-nm feature of once ionized beryllium (Be II). Numerous publications describe the technique, our beryllium results, and other applications. Here we summarize the important points and describe our experiments with beryllium

  9. Time-resolved study of a pulsed dc discharge using quantum cascade laser absorption spectroscopy : NO and gas temperature kinetics

    NARCIS (Netherlands)

    Welzel, S.; Gatilova, L.; Röpcke, J.; Rousseau, A.

    2007-01-01

    In a pulsed dc discharge of an Ar–N2 mixture containing 0.91% of NO the kinetics of the destruction of NO has been studied under static and flowing conditions, i.e. in a closed and open discharge tube (p = 266 Pa). For this purpose quantum cascade laser absorption spectroscopy (QCLAS) in the

  10. Time-resolved X-ray absorption spectroscopy for laser-ablated silicon particles in xenon gas

    International Nuclear Information System (INIS)

    Makimura, Tetsuya; Sakuramoto, Tamaki; Murakami, Kouichi

    1996-01-01

    We developed a laboratory-scale in situ apparatus for soft X-ray absorption spectroscopy with a time resolution of 10 ns and a space resolution of 100 μm. Utilizing this spectrometer, we have investigated the dynamics of silicon atoms formed by laser ablation in xenon gas. It was found that 4d-electrons in the xenon atoms are excited through collision with electrons in the laser-generated silicon plasma. (author)

  11. Time-Resolved Fourier Transform Emission Spectroscopy of He/CH4 in a Positive Column Discharge

    Czech Academy of Sciences Publication Activity Database

    Civiš, Svatopluk; Kubelík, Petr; Ferus, Martin

    2012-01-01

    Roč. 116, č. 12 (2012), s. 3137-3147 ISSN 1089-5639 R&D Projects: GA AV ČR IAA400400705; GA AV ČR IAAX00100903; GA ČR GAP208/10/2302 Institutional research plan: CEZ:AV0Z40400503; CEZ:AV0Z10100523 Keywords : infrared-laser spectroscopy * high-temperature pyrolysis * amorphous-carbon films Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.771, year: 2012

  12. Charge carrier mobility in poly[methyl(phenyl)silylene] studied by time-resolved terahertz spectroscopy and molecular modeling

    Czech Academy of Sciences Publication Activity Database

    Němec, Hynek; Kratochvílová, Irena; Kužel, Petr; Šebera, Jakub; Kochalska, Anna; Nožár, Juraj; Nešpůrek, Stanislav

    2011-01-01

    Roč. 13, č. 7 (2011), s. 2850-2856 ISSN 1463-9076 R&D Projects: GA ČR(CZ) GP202/09/P099; GA ČR GA203/08/1594; GA AV ČR KAN401770651; GA MŠk LC512; GA ČR(CZ) GAP304/10/1951 Institutional research plan: CEZ:AV0Z10100520; CEZ:AV0Z40500505 Keywords : molecular electronics * THz spectroscopy * charge carrier mobility Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 3.573, year: 2011

  13. Time resolved measurement of laser-ablated particles by LAPXAS (Laser Plasma Soft X-ray Absorption Spectroscopy)

    International Nuclear Information System (INIS)

    Miyashita, Atsumi; Yoda, Osamu; Murakami, Kouichi

    1999-01-01

    The time- and spatially-resolved properties of laser ablated carbon, boron and silicon particles were measured by LAPXAS (Laser Plasma Soft X-ray Absorption Spectroscopy). The maximum speed of positively charged ions is higher than those of neutral atoms and negatively charged ions. The spatial distributions of the laser-ablated particles in the localized rare gas environment were measured. In helium gas environment, by the helium cloud generated on the top of ablation plume depressed the ablation plume. There is no formation of silicon clusters till 15 μs after laser ablation in the argon gas environment. (author)

  14. Time-resolved photoemission spectroscopy of electronic cooling and localization in CH3NH3PbI3 crystals

    Science.gov (United States)

    Chen, Zhesheng; Lee, Min-i.; Zhang, Zailan; Diab, Hiba; Garrot, Damien; Lédée, Ferdinand; Fertey, Pierre; Papalazarou, Evangelos; Marsi, Marino; Ponseca, Carlito; Deleporte, Emmanuelle; Tejeda, Antonio; Perfetti, Luca

    2017-09-01

    We measure the surface of CH3NH3PbI3 single crystals by making use of two-photon photoemission spectroscopy. Our method monitors the electronic distribution of photoexcited electrons, explicitly discriminating the initial thermalization from slower dynamical processes. The reported results disclose the fast-dissipation channels of hot carriers (0.25 ps), set an upper bound to the surface-induced recombination velocity (PbI3 samples is consistent with the progressive reduction of photoconversion efficiency in operating devices. Minimizing the density of shallow traps and solving the aging problem may boost the macroscopic efficiency of solar cells to the theoretical limit.

  15. Excitation dynamics of dye doped tris(8-hydroxy quinoline) aluminum films studied using time-resolved photoelectron spectroscopy

    International Nuclear Information System (INIS)

    Read, K.; Karlsson, H. S.; Murnane, M. M.; Kapteyn, H. C.; Haight, R.

    2001-01-01

    In this work, we use excite-probe photoelectron spectroscopy to study the decay of electronic excitation in tris(8-hydroxy quinoline) aluminum (Alq) doped with the organic dye 4-dicyanomethylene-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran (DCM). Ultrashort laser pulses are used to photoexcite electrons into unoccupied molecular orbitals, and the ensuing decay rate is directly observed using photoelectron spectroscopy. Decay of the electronic excitation is studied as a function of DCM doping percentage and excitation intensity. The decay rate is seen to increase with both doping percentage and excitation intensity. These data are explained using a model including Foerster transfer, stimulated emission, concentration quenching, and bimolecular singlet - singlet exciton annihilation. In this model, we find that it is necessary to include a very fast (faster than predicted in standard Foerster transfer theory) excitation transfer of a fraction of the excitation from the Alq to the DCM, where that fraction corresponds to the approximate nearest-neighbor population. [copyright] 2001 American Institute of Physics

  16. Review of the theoretical description of time-resolved angle-resolved photoemission spectroscopy in electron-phonon mediated superconductors

    Energy Technology Data Exchange (ETDEWEB)

    Kemper, A.F. [Department of Physics, North Carolina State University, Raleigh, NC (United States); Sentef, M.A. [Max Planck Institute for the Structure and Dynamics of Matter, Center for Free Electron Laser Science, Hamburg (Germany); Moritz, B. [Stanford Institute for Materials and Energy Sciences (SIMES), SLAC National Accelerator Laboratory, Menlo Park, CA (United States); Devereaux, T.P. [Stanford Institute for Materials and Energy Sciences (SIMES), SLAC National Accelerator Laboratory, Menlo Park, CA (United States); Geballe Laboratory for Advanced Materials, Stanford University, Stanford, CA (United States); Freericks, J.K. [Department of Physics, Georgetown University, Washington, DC (United States)

    2017-09-15

    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 focus on exact results emanating from sum rules and approximate numerical results which describe rules of thumb for relaxation processes. In addition, in the superconducting state, we describe how Anderson-Higgs oscillations can be excited due to the nonlinear coupling with the electric field and describe mechanisms where pumping the system enhances superconductivity. (copyright 2017 by WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  17. Mapping of calf muscle oxygenation and haemoglobin content during dynamic plantar flexion exercise by multi-channel time-resolved near-infrared spectroscopy

    International Nuclear Information System (INIS)

    Torricelli, Alessandro; Quaresima, Valentina; Pifferi, Antonio; Biscotti, Giovanni; Spinelli, Lorenzo; Taroni, Paola; Ferrari, Marco; Cubeddu, Rinaldo

    2004-01-01

    A compact and fast multi-channel time-resolved near-infrared spectroscopy system for tissue oximetry was developed. It employs semiconductor laser and fibre optics for delivery of optical signals. Photons are collected by eight 1 mm fibres and detected by a multianode photomultiplier. A time-correlated single photon counting board is used for the parallel acquisition of time-resolved reflectance curves. Estimate of the reduced scattering coefficient is achieved by fitting with a standard model of diffusion theory, while the modified Lambert-Beer law is used to assess the absorption coefficient. In vivo measurements were performed on five healthy volunteers to monitor spatial changes in calf muscle (medial and lateral gastrocnemius; MG, LG) oxygen saturation (SmO 2 ) and total haemoglobin concentration (tHb) during dynamic plantar flexion exercise performed at 50% of the maximal voluntary contraction. At rest SmO 2 was 73.0 ± 0.9 and 70.5 ± 1.7% in MG and LG, respectively (P = 0.045). At the end of the exercise, SmO 2 decreased (69.1 ± 1.8 and 63.8 ± 2.1% in MG and LG, respectively; P 2 and tHb

  18. Investigations of lateral and vertical compositional gradients in Cu(In,Ga)Se{sub 2} by highly spatially, spectrally and time resolved cathodoluminescence spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Mueller, Mathias; Ribbe, Stefan; Hempel, Thomas; Bertram, Frank; Christen, Juergen [Institute for Experimental Physics, Otto-von-Guericke-University, Magdeburg (Germany); Witte, Wolfram; Hariskos, Dimitrios [Zentrum fuer Sonnenenergie- und Wasserstoff-Forschung Baden-Wuerttemberg (ZSW), Stuttgart (Germany)

    2011-07-01

    Luminescence properties of Cu(In,Ga)Se{sub 2} (CIGS) layers with different thicknesses were investigated by means of highly spatially, spectrally and time resolved cathodoluminescence (CL) spectroscopy at low temperature (T=5 K). A polycrystalline CIGS thin film with a thickness of 2.4 {mu}m was grown using an in-line co-evaporation process with a final Cu-poor composition on top of a sputtered Mo layer on a soda lime glass substrate. The layer thickness was then reduced by highly controlled bromine methanol etching. The typical grainy (d{sub average}=3 {mu}m) structure of the untouched sample develops thin longish structures under the influence of the etchant. Integral CL spectra of the samples are dominated by donor-acceptor pair (DAP) luminescence. The peak energies of these spectra are ranging from 1.13 eV to 1.22 eV with decreasing layer thickness. The lateral distribution of the luminescence is inhomogeneous regarding the intensity as well as the peak energy. Time resolved CL shows a strong dependence of the initial lifetime from the emission energy.

  19. Isolated Gramicidin Peptides Probed by IR Spectroscopy

    Czech Academy of Sciences Publication Activity Database

    Rijs, A. M.; Kabeláč, Martin; Abo-Riziq, A.; Hobza, Pavel; de Vries, M. S.

    2011-01-01

    Roč. 12, č. 10 (2011), s. 1816-1821 ISSN 1439-4235 R&D Projects: GA MŠk LC512; GA AV ČR IAA400550808 Institutional research plan: CEZ:AV0Z40550506 Keywords : density functional calculations * gramicidin * IR spectroscopy * protein folding Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.412, year: 2011

  20. Time-Resolved Quantum Cascade Laser Absorption Spectroscopy of Pulsed Plasma Assisted Chemical Vapor Deposition Processes Containing BCl3

    Science.gov (United States)

    Lang, Norbert; Hempel, Frank; Strämke, Siegfried; Röpcke, Jürgen

    2011-08-01

    In situ measurements are reported giving insight into the plasma chemical conversion of the precursor BCl3 in industrial applications of boriding plasmas. For the online monitoring of its ground state concentration, quantum cascade laser absorption spectroscopy (QCLAS) in the mid-infrared spectral range was applied in a plasma assisted chemical vapor deposition (PACVD) reactor. A compact quantum cascade laser measurement and control system (Q-MACS) was developed to allow a flexible and completely dust-sealed optical coupling to the reactor chamber of an industrial plasma surface modification system. The process under the study was a pulsed DC plasma with periodically injected BCl3 at 200 Pa. A synchronization of the Q-MACS with the process control unit enabled an insight into individual process cycles with a sensitivity of 10-6 cm-1·Hz-1/2. Different fragmentation rates of the precursor were found during an individual process cycle. The detected BCl3 concentrations were in the order of 1014 molecules·cm-3. The reported results of in situ monitoring with QCLAS demonstrate the potential for effective optimization procedures in industrial PACVD processes.

  1. Effects of aging on working memory performance and prefrontal cortex activity:A time-resolved spectroscopy study

    Institute of Scientific and Technical Information of China (English)

    Jie Shi; Wenjing Zhou; Tongchao Geng; Huancong Zuo; Masahiro Tanida; Kaoru Sakatani

    2016-01-01

    Objective:This study aimed to employ time‐resolved spectroscopy (TRS) to explore age‐related differences in prefrontal cortex (PFC) activity while subjects performed a working memory task. Methods:We employed TRS to measure PFC activity in ten healthy younger and ten healthy older subjects while they performed a working memory (WM) task. All subjects performed the Sternberg test (ST) in which the memory‐set size varied between one and six digits. Using TRS, we recorded changes in cerebral blood oxygenation as a measure of changes in PFC activity during the task. In order to identify left/right asymmetry of PFC activity during the working memory task, we calculated the laterality score, i.e.,Δoxy‐Hb (rightΔoxy‐Hb—leftΔoxy‐Hb);positive values indicate greater activity in the right PFC, while negative values indicate greater activity in the left PFC. Results:During the ST, statistical analyses showed no significant differences between the younger and older groups in accuracy for low memory‐load and high memory‐load. In high memory‐load tasks, however, older subjects were slower than younger subjects (P Conclusions: The present results are consistent with the hemispheric asymmetry reduction in older adults (HAROLD) model;working memory tasks cause asymmetrical PFC activation in younger adults, while older adults tend to show reduced hemispheric lateralization.

  2. Effects of aging on working memory performance and prefrontal cortex activity: A time-resolved spectroscopy study

    Institute of Scientific and Technical Information of China (English)

    Jie Shi; Wenjing Zhou; Tongchao Geng; Huancong Zuo; Masahiro Tanida; Kaoru Sakatani

    2016-01-01

    Objective:This study aimed to employ time‐resolved spectroscopy(TRS)to explore age‐related differences in prefrontal cortex(PFC)activity while subjects performed a working memory task.Methods:We employed TRS to measure PFC activity in ten healthy younger and ten healthy older subjects while they performed a working memory(WM)task.All subjects performed the Sternberg test(ST)in which the memory‐set size varied between one and six digits.Using TRS,we recorded changes in cerebral blood oxygenation as a measure of changes in PFC activity during the task.In order to identify left/right asymmetry of PFC activity during the working memory task,we calculated the laterality score,i.e.,Δoxy‐Hb(rightΔoxy‐Hb—leftΔoxy‐Hb);positive values indicate greater activity in the right PFC,while negative values indicate greater activity in the left PFC.Results:During the ST,statistical analyses showed no significant differences between the younger and older groups in accuracy for low memory‐load and high memory‐load.In high memory‐load tasks,however,older subjects were slower than younger subjects(P<0.05).We found that the younger group showed right lateral responses with a stronger right than left activation in the frontal pole,whereas the older group showed bilateral responses(P<0.05).Conclusions:The present results are consistent with the hemispheric asymmetry reduction in older adults(HAROLD)model;working memory tasks cause asymmetrical PFC activation in younger adults,while older adults tend to show reduced hemispheric lateralization.

  3. Photodissociation of CH3CHO at 248 nm by time-resolved Fourier-transform infrared emission spectroscopy: Verification of roaming and triple fragmentation

    Science.gov (United States)

    Hung, Kai-Chan; Tsai, Po-Yu; Li, Hou-Kuan; Lin, King-Chuen

    2014-02-01

    By using time-resolved Fourier-transform infrared emission spectroscopy, the HCO fragment dissociated from acetaldehyde (CH3CHO) at 248 nm is found to partially decompose to H and CO. The fragment yields are enhanced by the Ar addition that facilitates the collision-induced internal conversion. The channels to CH2CO + H2 and CH3CO + H are not detected significantly. The rotational population distribution of CO, after removing the Ar collision effect, shows a bimodal feature comprising both low- and high-rotational (J) components, sharing a fraction of 19% and 81%, respectively, for the vibrational state v = 1. The low-J component is ascribed to both roaming pathway and triple fragmentation. They are determined to have a branching ratio of 0.06, respectively, relative to the whole v = 1 population. The CO roaming is accompanied by a highly vibrational population of CH4 that yields a vibrational bimodality.

  4. Static and time-resolved mid-infrared spectroscopy of Hg0.95Cd0.05Cr2Se4 spinel.

    Science.gov (United States)

    Barsaume, S; Telegin, A V; Sukhorukov, Yu P; Stavrias, N; Fedorov, V A; Menshchikova, T K; Kimel, A V

    2017-08-16

    Static and time-resolved mid-infrared spectroscopy of ferromagnetic single crystal Hg 0.95 Cd 0.05 Cr 2 Se 4 was performed below the absorption edge, in order to reveal the origin of the electronic transitions contributing to the magneto-optical properties of this material. The mid-infrared spectroscopy reveals a strong absorption peak around 0.236 eV which formerly was assigned to a transition within the selenide-chromium complexes ([Formula: see text] Se -Cr 2+ ). To reveal the sensitivity of the transition to the magnetic order, we performed the studies in a temperature range across the Curie temperature and magnetic fields across the value at which the saturation of ferromagnetic magnetization occurs. Despite the fact that the Curie temperature of this ferromagnetic semiconductor is around 107 K, the intensity of the mid-infrared transition reduces substantially increasing the temperature, so that already at 70 K the absorption peak is hardly visible. Such a dramatic decrease of the oscillator strength is observed simultaneously with the strong red-shift of the absorption edge in the magnetic semiconductor. Employing a time-resolved pump-and-probe technique enabled us to determine the lifetime of the electrons in the excited state of this optical transition. In the temperature range from 7 K to 80 K, the lifetime changes from 3 ps to 6 ps. This behavior agrees with the phenomenon of giant oscillator strength described earlier for weakly bound excitons in nonmagnetic semiconductors.

  5. Novel lanthanide doped micro- and mesoporous solids. Characterization of ion-host-interactions, species distribution and luminescence properties using time-resolved luminescence spectroscopy

    International Nuclear Information System (INIS)

    Gessner, Andre

    2010-12-01

    In this work lanthanide-doped microporous zeolites, microporous-mesoporous hybrid materials and mesoporous silicates were investigated regarding their luminescence properties and the ion-host-interactions using time-resolved luminescence spectroscopy. Thereby, time-resolved emission spectra (TRES) provide information in the wavelength and time domain. For the analysis of the TRES a broad set of analytic methods was applied and thus a corresponding ''toolbox'' developed. Fitting of the luminescence decays was performed with a discrete number of exponentials and supported by luminescence decay times distributions. Time-resolved area normalized emission spectra (TRANES), an advancement of TRES, could be used for the determination of the number of emissive lanthanide species in porous materials for the first time. Calculation of the decay-associated spectra (DAS) allowed the correlation of spectral information with luminescence decay times and thus delivered the luminescence spectra of the different europium species. For europium(III) we could use in addition the time-dependent asymmetry ratio and spectral evolution of the 5 D 0 - 7 F 0 -transition with time to obtain further information about the distribution of the lanthanide ions in the host material. Luminescence decay times and spectra allowed conclusions on the number of OH-oscillators in and the symmetry of the first coordination sphere. For the microporous and microporous-mesoporous materials were found different lanthanide species, which were characterized by the above mentioned methods. These lanthanide species can be found on different positions in the host material. One position is located deep in the pore system. Here, lanthanide ions are hardly accessible for water and mainly coordinated by framework oxygens. This results in long luminescence decay times and distorted coordination spheres. The second position can be found near or on the outer surface or in the mesopores. Lanthanide ions located here, are

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

    Science.gov (United States)

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

    2010-01-14

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

  7. Validation of a high-power, time-resolved, near-infrared spectroscopy system for measurement of superficial and deep muscle deoxygenation during exercise.

    Science.gov (United States)

    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.

  8. Study on the interaction of phthalate esters to human serum albumin by steady-state and time-resolved fluorescence and circular dichroism spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Xie, Xiaoyun [National Key Laboratory of Organic Chemistry, Lanzhou University, Lanzhou 730000 (China); College of Earth and Environmental Sciences, Lanzhou University, Lanzhou 730000 (China); Wang, Zhaowei [College of Earth and Environmental Sciences, Lanzhou University, Lanzhou 730000 (China); Zhou, Ximin; Wang, Xiaoru [National Key Laboratory of Organic Chemistry, Lanzhou University, Lanzhou 730000 (China); Chen, Xingguo, E-mail: chenxg@lzu.edu.cn [National Key Laboratory of Organic Chemistry, Lanzhou University, Lanzhou 730000 (China); Department of Chemistry, Lanzhou University, Lanzhou 730000 (China)

    2011-09-15

    Highlights: {center_dot} Molecular docking revealed PAEs to be located in the hydrophobic pocket of HSA. {center_dot} HSA-DMP had one class of binding sites while HSA-BBP and HSA-DEHP had two types. {center_dot} Hydrophobic and hydrogen interactions dominated in the association of HSA-PAEs. {center_dot} The lifetime of Trp residue of HSA decreased after the addition of PAEs. {center_dot} The presences of PAEs could alter the second structure of HSA. - Abstract: Phthalate esters (PAEs) are globally pervasive contaminants that are considered to be endocrine disruptor chemicals and toxic environmental priority pollutants. In this paper, the interactions between PAEs and human serum albumin (HSA) were examined by molecular modelling, steady state and time-resolved fluorescence, ultraviolet-visible spectroscopy (UV-vis) and circular dichroism spectroscopy (CD). The association constants between PAEs and HSA were determined using the Stern-Volmer and Scatchard equations. The binding of dimethyl phthalate (DMP) to HSA has a single class of binding site and its binding constants (K) are 4.08 x 10{sup 3}, 3.97 x 10{sup 3}, 3.45 x 10{sup 3}, and 3.20 x 10{sup 3} L mol{sup -1} at 289, 296, 303, and 310 K, respectively. The Stern-Volmer and Scatchard plots both had two regression curves for HSA-butylbenzyl phthalate (BBP) and HSA-di-2-ethylhexyl phthalate (DEHP), which indicated that these bindings were via two types of binding sites: the numbers of binding site for the first type were lower than for the second type. The binding constants of the first type binding site were higher than those of the second type binding site at corresponding temperatures, the results suggesting that the first type of binding site had high affinity and the second binding site involved other sites with lower binding affinity and selectivity. The thermodynamic parameters of the binding reactions ({Delta}G{sup o}, {Delta}H{sup o} and {Delta}S{sup o}) were measured, and they indicated the presences

  9. Infrared multiphoton dissociation of acrolein. Time-resolved observation of CO ( v = 1) IR emission at 4.7 μm

    Science.gov (United States)

    Chowdhury, P. K.; Rama Rao, K. V. S.; Mittal, J. P.

    1994-02-01

    In contrast to the photochemistry of electronically excited acrolein producing vinyl and formyl radicals via CC bond rupture, multiphoton vibrationally excited molecules undergo concerted dissociation generating CO and ethylene. Vibrational excitation in the CO product is detected immediately following the CO 2 laser pulse by observing IR emission at 4.7 μm. The decay of the IR emission was studied as a function of acrolein pressure. A vibrational-vibrational relaxation rate constant of CO ( v=1) by acrolein is found to be 1240 ± 200 Torr -1 s -1.

  10. Probing the influence of X-rays on aqueous copper solutions using time-resolved in situ combined video/X-ray absorption near-edge/ultraviolet-visible spectroscopy

    NARCIS (Netherlands)

    Mesu, J. Gerbrand; Beale, Andrew M.; de Groot, Frank M. F.; Weckhuysen, Bert M.

    2006-01-01

    Time-resolved in situ video monitoring and ultraviolet-visible spectroscopy in combination with X-ray absorption near-edge spectroscopy (XANES) have been used for the first time in a combined manner to study the effect of synchrotron radiation on a series of homogeneous aqueous copper solutions in a

  11. Spectral characterization of crude oil using fluorescence (synchronous and time-resolved) and NIR (Near Infrared Spectroscopy); Caracterizacao espectral do petroleo utilizando fluorescencia (sincronizada e resolvida no tempo) e NIR (Near Infrared Spectroscopy)

    Energy Technology Data Exchange (ETDEWEB)

    Falla Sotelo, F.; Araujo Pantoja, P.; Lopez-Gejo, J.; Le Roux, G.A.C.; Nascimento, C.A.O. [Universidade de Sao Paulo (USP), SP (Brazil). Dept. de Engenharia Quimica. Lab. de Simulacao e Controle de Processos; Quina, F.H. [Universidade de Sao Paulo (USP), SP (Brazil). Inst. de Quimica. Centro de Capacitacao e Pesquisa em Meio Ambiente (CEPEMA)

    2008-07-01

    The objective of the present work is to evaluate the performance of two spectroscopic techniques employed in the crude oil characterization: NIR spectroscopy and fluorescence spectroscopy (Synchronous fluorescence - SF and Time Resolved Fluorescence - TRF) for the development of correlation models between spectral profiles of crude oil samples and both physical properties (viscosity and API density) and physico-chemical properties (SARA analysis: Saturated, Aromatic, Resins and Asphaltenes). The better results for viscosity and density were obtained using NIR whose prediction capacity was good (1.5 cP and 0.5 deg API, respectively). For SARA analysis, fluorescence spectroscopy revealed its potential in the model calibration showing good results (R2 coefficients greater than 0.85). TRF spectroscopy had better performance than SF spectroscopy. (author)

  12. Photodissociation of gaseous CH3COSH at 248 nm by time-resolved Fourier-transform infrared emission spectroscopy: Observation of three dissociation channels

    International Nuclear Information System (INIS)

    Hu, En-Lan; Tsai, Po-Yu; Fan, He; Lin, King-Chuen

    2013-01-01

    Upon one-photon excitation at 248 nm, gaseous CH 3 C(O)SH is dissociated following three pathways with the products of (1) OCS + CH 4 , (2) CH 3 SH + CO, and (3) CH 2 CO + H 2 S that are detected using time-resolved Fourier-transform infrared emission spectroscopy. The excited state 1 (n O , π * CO ) has a radiative lifetime of 249 ± 11 ns long enough to allow for Ar collisions that induce internal conversion and enhance the fragment yields. The rate constant of collision-induced internal conversion is estimated to be 1.1 × 10 −10 cm 3 molecule −1 s −1 . Among the primary dissociation products, a fraction of the CH 2 CO moiety may undergo further decomposition to CH 2 + CO, of which CH 2 is confirmed by reaction with O 2 producing CO 2 , CO, OH, and H 2 CO. Such a secondary decomposition was not observed previously in the Ar matrix-isolated experiments. The high-resolution spectra of CO are analyzed to determine the ro-vibrational energy deposition of 8.7 ± 0.7 kcal/mol, while the remaining primary products with smaller rotational constants are recognized but cannot be spectrally resolved. The CO fragment detected is mainly ascribed to the primary production. A prior distribution method is applied to predict the vibrational distribution of CO that is consistent with the experimental findings.

  13. Solid-phase nano-extraction and laser-excited time-resolved Shpol'skii spectroscopy for the analysis of polycyclic aromatic hydrocarbons in drinking water samples.

    Science.gov (United States)

    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.

  14. Chemical sensitivity of InP/In0.48Ga0.52P surface quantum dots studied by time-resolved photoluminescence spectroscopy

    International Nuclear Information System (INIS)

    De Angelis, Roberta; Casalboni, Mauro; De Matteis, Fabio; Hatami, Fariba; Masselink, William T.; Zhang, Hong; Prosposito, Paolo

    2015-01-01

    InP/InGaP surface quantum dots represent an attractive material for optical chemical sensors since they show a remarkable near infra-red emission at room temperature, whose intensity increases rapidly and reversibly depending on the composition of the environmental atmosphere. We show here their emission properties by time resolved photoluminescence spectroscopy investigation. Photoluminescence transients with and without chemical solvent vapours (methanol, clorophorm, acetone and water) were fitted with a 3-exponential decay law with times of about 0.5 ns, 2 ns and 7 ns. The measurements revealed a weak effect on clorophorm, acetone and water, while the initial decay time of InP surface quantum dots increases (up to 15%) upon methanol vapour exposure, indicating that the organic molecules efficiently saturate QD non-radiative surface states. - Highlights: • InP SQDs emission depends on the presence of solvent vapours in the atmosphere. • TR photoluminescence transients were fitted with a 3-exponential decay law. • The initial decay time increases (up to 15%) upon methanol vapour exposure. • Organic molecules efficiently saturate QD non-radiative surface states.

  15. Development of a method for the in situ measurement of polycyclic aromatic hydrocarbons with time resolved laser fluorescence spectroscopy. Final report

    International Nuclear Information System (INIS)

    Jaeger, E.; Weissbach, A.; Koenig, F.; Paul, T.

    1994-01-01

    A method was developed for the detection of polycyclic aromatic hydrocarbons (PAH) in water on the basis of time resolved laser fluorescence spectroscopy. The detection of the sum of PAH in ground- and surfacewater is possible with high sensitivity and selectivity. The fluorescence of other substances like chlorophyll or dissolved organic matter is suppressed by a special choice of spectral and temporal windows. The method works without any sample preparation and gives the results in a very short time. On the basis of this method a first device was built with a sensitivity of 0,1 μg/1 PAH in water. The measuring time was less than one minute. The on site use of this prototype is possible because of the use of a battery driven nitrogen laser together with a notebook computer for system control The application of fiberoptic cables up to 30 meter length makes it possible to use the system for screening and monitoring of polluted areas both in existing wells and without any well by using geological probe techniques. (orig.) [de

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

    Science.gov (United States)

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

    2018-06-01

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

  17. Excited state non-adiabatic dynamics of the smallest polyene, trans 1,3-butadiene. I. Time-resolved photoelectron-photoion coincidence spectroscopy

    Science.gov (United States)

    Boguslavskiy, Andrey E.; Schalk, Oliver; Gador, Niklas; Glover, William J.; Mori, Toshifumi; Schultz, Thomas; Schuurman, Michael S.; Martínez, Todd J.; Stolow, Albert

    2018-04-01

    The ultrafast excited state dynamics of the smallest polyene, trans-1,3-butadiene, were studied by femtosecond time-resolved photoelectron-photoion coincidence (TRPEPICO) spectroscopy. The evolution of the excited state wavepacket, created by pumping the bright 1Bu (ππ*) electronic state at its origin of 216 nm, is projected via one- and two-photon ionization at 267 nm onto several ionization continua. The results are interpreted in terms of Koopmans' correlations and Franck-Condon factors for the excited and cationic states involved. The known predissociative character of the cation excited states is utilized to assign photoelectron bands to specific continua using TRPEPICO spectroscopy. This permits us to report the direct observation of the famously elusive S1(21Ag) dark electronic state during the internal conversion of trans 1,3-butadiene. Our phenomenological analysis permits the spectroscopic determination of several important time constants. We report the overall decay lifetimes of the 11Bu and 21Ag states and observe the re-appearance of the hot ground state molecule. We argue that the apparent dephasing time of the S2(11Bu) state, which leads to the extreme breadth of the absorption spectrum, is principally due to large amplitude torsional motion on the 1Bu surface in conjunction with strong non-adiabatic couplings via conical intersections, whereupon nuclear wavepacket revivals to the initial Franck-Condon region become effectively impossible. In Paper II [W. J. Glover et al., J. Chem. Phys. 148, 164303 (2018)], ab initio multiple spawning is used for on-the-fly computations of the excited state non-adiabatic wavepacket dynamics and their associated TRPEPICO observables, allowing for direct comparisons of experiment with theory.

  18. Photo-Induced Spin-State Conversion in Solvated Transition Metal Complexes Probed via Time-Resolved Soft X-ray Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Huse, Nils; Kim, Tae Kyu; Jamula, Lindsey; McCusker, James K.; de Groot, Frank M. F.; Schoenlein, Robert W.

    2010-04-30

    Solution-phase photoinduced low-spin to high-spin conversion in the FeII polypyridyl complex [Fe(tren(py)3)]2+ (where tren(py)3 is tris(2-pyridylmethyliminoethyl)amine) has been studied via picosecond soft X-ray spectroscopy. Following 1A1 --> 1MLCT (metal-to-ligand charge transfer) excitation at 560 nm, changes in the iron L2- and L3-edges were observed concomitant with formation of the transient high-spin 5T2 state. Charge-transfer multiplet calculations coupled with data acquired on low-spin and high-spin model complexes revealed a reduction in ligand field splitting of 1 eV in the high-spin state relative to the singlet ground state. A significant reduction in orbital overlap between the central Fe-3d and the ligand N-2p orbitals was directly observed, consistent with the expected ca. 0.2 Angstrom increase in Fe-N bond length upon formation of the high-spin state. The overall occupancy of the Fe-3d orbitals remains constant upon spin crossover, suggesting that the reduction in sigma-donation is compensated by significant attenuation of pi-back-bonding in the metal-ligand interactions. These results demonstrate the feasibility and unique potential of time-resolved soft X-ray absorption spectroscopy to study ultrafast reactions in the liquid phase by directly probing the valence orbitals of first-row metals as well as lighter elements during the course of photochemical transformations.

  19. IR Cards: Inquiry-Based Introduction to Infrared Spectroscopy

    Science.gov (United States)

    Bennett, Jacqueline; Forster, Tabetha

    2010-01-01

    As infrared spectroscopy (IR) is frequently used in undergraduate organic chemistry courses, an inductive introduction to IR spectroscopy that uses index cards printed with spectra, structures, and chemical names is described. Groups of students are given an alphabetized deck of these "IR cards" to sort into functional groups. The students then…

  20. Subpicosecond oxygen trapping in the heme pocket of the oxygen sensor FixL observed by time-resolved resonance Raman spectroscopy.

    Science.gov (United States)

    Kruglik, Sergei G; Jasaitis, Audrius; Hola, Klara; Yamashita, Taku; Liebl, Ursula; Martin, Jean-Louis; Vos, Marten H

    2007-05-01

    Dissociation of oxygen from the heme domain of the bacterial oxygen sensor protein FixL constitutes the first step in hypoxia-induced signaling. In the present study, the photodissociation of the heme-O2 bond was used to synchronize this event, and time-resolved resonance Raman (TR(3)) spectroscopy with subpicosecond time resolution was implemented to characterize the heme configuration of the primary photoproduct. TR(3) measurements on heme-oxycomplexes are highly challenging and have not yet been reported. Whereas in all other known six-coordinated heme protein complexes with diatomic ligands, including the oxymyoglobin reported here, heme iron out-of-plane motion (doming) occurs faster than 1 ps after iron-ligand bond breaking; surprisingly, no sizeable doming is observed in the oxycomplex of the Bradyrhizobium japonicum FixL sensor domain (FixLH). This assessment is deduced from the absence of the iron-histidine band around 217 cm(-1) as early as 0.5 ps. We suggest that efficient ultrafast oxygen rebinding to the heme occurs on the femtosecond time scale, thus hindering heme doming. Comparing WT oxy-FixLH, mutant proteins FixLH-R220H and FixLH-R220Q, the respective carbonmonoxy-complexes, and oxymyoglobin, we show that a hydrogen bond of the terminal oxygen atom with the residue in position 220 is responsible for the observed behavior; in WT FixL this residue is arginine, crucially implicated in signal transmission. We propose that the rigid O2 configuration imposed by this residue, in combination with the hydrophobic and constrained properties of the distal cavity, keep dissociated oxygen in place. These results uncover the origin of the "oxygen cage" properties of this oxygen sensor protein.

  1. Study of the Bulk Charge Carrier Dynamics in Anatase and Rutile TiO2 Single Crystals by Femtosecond Time Resolved Spectroscopy

    KAUST Repository

    Maity, Partha

    2018-04-02

    Understanding of the fundamentals behind charge carriers of photo-catalytic materials are still illusive hindering progress in our quest for renewable energy. TiO2 anatase and rutile are the most understood phases in photo-catalysis and serve as the best model for fundamental studies. Their ultrafast charge carrier dynamics especially on TiO2 anatase single crystal (the most active phase) are unresolved. Here femtosecond time resolved spectroscopy (TRS) was carried out to explore the dynamics of photo-excited charge carriers’ recombination in anatase single crystal, for the first time using pump fluence effects, and compares it to that of the rutile single crystal. A significant difference in charge carrier recombination rates between both crystals is observed. We found that the time constants for carrier recombination are two orders of magnitude slower for anatase (101) when compared to those of rutile (110). Moreover, bulk defects introduced by reduction of the samples via annealing in ultra-high vacuum resulted in faster recombination rates for both polymorphs. Both states (fresh and reduced) probed by pump fluence dependence measurements revealed that the major recombination channel in fresh and reduced anatase and reduced rutile is the first-order Shockley–Reed mediated. However, for fresh rutile, third-body Auger recombination was observed, attributed to the presence of higher density of intrinsic charge carriers. At all excitation wavelengths and fluence investigated, anatase (101) single crystal show longer charge carrier lifetime when compared to rutile (110) single. This may explain the superiority of the anatase phase for the electron transfer H+ reduction to molecular hydrogen.

  2. Reaction dynamics of O({sup 1}D) + HCOOD/DCOOH investigated with time-resolved Fourier-transform infrared emission spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Shang-Chen; Putikam, Raghunath; Lin, M. C., E-mail: chemmcl@emory.edu, E-mail: tsuchis@sepia.plala.or.jp, E-mail: yplee@mail.nctu.edu.tw; Tsuchiya, Soji, E-mail: chemmcl@emory.edu, E-mail: tsuchis@sepia.plala.or.jp, E-mail: yplee@mail.nctu.edu.tw [Department of Applied Chemistry and Institute of Molecular Science, National Chiao Tung University, Hsinchu 30010, Taiwan (China); Nghia, N. T. [School of Chemical Engineering - Hanoi University of Science and Technology, Hanoi (Viet Nam); Nguyen, Hue M. T. [Center for Computational Science and Faculty of Chemistry, Hanoi National University of Education, Hanoi (Viet Nam); Lee, Yuan-Pern, E-mail: chemmcl@emory.edu, E-mail: tsuchis@sepia.plala.or.jp, E-mail: yplee@mail.nctu.edu.tw [Department of Applied Chemistry and Institute of Molecular Science, National Chiao Tung University, Hsinchu 30010, Taiwan (China); Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 10617, Taiwan (China)

    2014-10-21

    We investigated the reaction dynamics of O({sup 1}D) towards hydrogen atoms of two types in HCOOH. The reaction was initiated on irradiation of a flowing mixture of O{sub 3} and HCOOD or DCOOH at 248 nm. The relative vibration-rotational populations of OH and OD (1 ≦ v ≦ 4, J ≤ 15) states were determined from time-resolved IR emission recorded with a step-scan Fourier-transform spectrometer. In the reaction of O({sup 1}D) + HCOOD, the rotational distribution of product OH is nearly Boltzmann, whereas that of OD is bimodal. The product ratio [OH]/[OD] is 0.16 ± 0.05. In the reaction of O({sup 1}D) + DCOOH, the rotational distribution of product OH is bimodal, but the observed OD lines are too weak to provide reliable intensities. The three observed OH/OD channels agree with three major channels of production predicted with quantum-chemical calculations. In the case of O({sup 1}D) + HCOOD, two intermediates HOC(O)OD and HC(O)OOD are produced in the initial C−H and O−D insertion, respectively. The former undergoes further decomposition of the newly formed OH or the original OD, whereas the latter produces OD via direct decomposition. Decomposition of HOC(O)OD produced OH and OD with similar vibrational excitation, indicating efficient intramolecular vibrational relaxation, IVR. Decomposition of HC(O)OOD produced OD with greater rotational excitation. The predicted [OH]/[OD] ratio is 0.20 for O({sup 1}D) + HCOOD and 4.08 for O({sup 1}D) + DCOOH; the former agrees satisfactorily with experiments. We also observed the v{sub 3} emission from the product CO{sub 2}. This emission band is deconvoluted into two components corresponding to internal energies E = 317 and 96 kJ mol{sup −1} of CO{sub 2}, predicted to be produced via direct dehydration of HOC(O)OH and secondary decomposition of HC(O)O that was produced via decomposition of HC(O)OOH, respectively.

  3. Time-resolved studies

    International Nuclear Information System (INIS)

    Mills, D.M.

    1992-01-01

    When new or more powerful probes become available that offer both shorter data-collection times and the opportunity to apply innovative approaches to established techniques, it is natural that investigators consider the feasibility of exploring the kinetics of time-evolving systems. This stimulating area of research not only can lead to insights into the metastable or excited states that a system may populate on its way to a ground state, but can also lead to a better understanding of that final state. Synchrotron radiation, with its unique properties, offers just such a tool to extend X-ray measurements from the static to the time-resolved regime. The most straight-forward application of synchrotron radiation to the study of transient phenomena is directly through the possibility of decreased data-collection times via the enormous increase in flux over that of a laboratory X-ray system. Even further increases in intensity can be obtained through the use of novel X-ray optical devices. Widebandpass monochromators, e.g., that utilize the continuous spectral distribution of synchrotron radiation, can increase flux on the sample several orders of magnitude over conventional X-ray optical systems thereby allowing a further shortening of the data-collection time. Another approach that uses the continuous spectral nature of synchrotron radiation to decrease data-collection times is the open-quote parallel data collectionclose quotes method. Using this technique, intensities as a function of X-ray energy are recorded simultaneously for all energies rather than sequentially recording data at each energy, allowing for a dramatic decrease in the data-collection time

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

    OpenAIRE

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

    1997-01-01

    Time-resolved vibrational spectra are used to elucidate the structural changes in the retinal chromophore within the K-590 intermediate that precedes the formation of the L-550 intermediate in the room-temperature (RT) bacteriorhodopsin (BR) photocycle. Measured by picosecond time-resolved coherent anti-Stokes Raman scattering (PTR/CARS), these vibrational data are recorded within the 750 cm-1 to 1720 cm-1 spectral region and with time delays of 50-260 ns after the RT/BR photocycle is optical...

  5. [Time resolved plasma spectroscopy of imploded gas-filled microballoons: The next generation]. Final technical report, 17 April 1995--30 September 1997

    International Nuclear Information System (INIS)

    Hooper, C.F. Jr.

    1998-03-01

    This report is comprised of three documents which deal with plasma spectroscopy of laser-produced plasmas. In Appendix A the authors present a discussion of plasma line broadening with emphasis on the effects of accounting for ion-dynamic corrections. For two decades, high power lasers have been used to implode microballoons filled with gases such as neon, argon, deuterium, or mixtures of deuterium and argon. These implosions have generated high-temperature (∼ 1 keV) and high density (∼ 10 23 /cc--10 25 /cc) plasmas. As a result of these experiments, the authors are able to observe the radiative properties of highly charged ions in the presence of a variety of strongly coupled plasmas. Spectral radiation observed from these experiments is frequently in the x-ray region and the radiative properties are greatly influenced by plasma effects. In section 2 of this paper the authors discuss the theoretical techniques employed to interpret these spectra and describe two sets of implosion experiments. In section 3 they list some conclusions. Appendix B presents more research related to ion-dynamic corrections. The authors examine the combined effects of ion dynamics and opacity on line profiles used in the analysis of hot dense plasmas. Specifically, they have calculated Stark broadened line profiles for both resonance and satellite lines in highly stripped Ar ions, both in the quasi-static ion approximation, and including the effects of ion dynamics. Using the results of an NLTE kinetics code, combined with an escape factor formalism to account for the effects of radiative transfer, they have calculated the relative intensities of these lines, as well as the effects of opacity on their profiles. This model spectra is used in the analysis of experimental data. In a series of experiments performed at the Laboratory for Laser Energetics plastic microballoons filled with DD and doped with Ar were imploded using the Omega laser system. Here, the authors use time-resolved K

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

    Science.gov (United States)

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

    2014-12-24

    Thermal stability of charged LiNixMnyCozO2 (NMC, with x + y + z = 1, x:y:z = 4:3:3 (NMC433), 5:3:2 (NMC532), 6:2:2 (NMC622), and 8:1:1 (NMC811)) cathode materials is systematically studied using combined in situ time-resolved X-ray diffraction and mass spectroscopy (TR-XRD/MS) techniques upon heating up to 600 °C. The TR-XRD/MS results indicate that the content of Ni, Co, and Mn significantly affects both the structural changes and the oxygen release features during heating: the more Ni and less Co and Mn, the lower the onset temperature of the phase transition (i.e., thermal decomposition) and the larger amount of oxygen release. Interestingly, the NMC532 seems to be the optimized composition to maintain a reasonably good thermal stability, comparable to the low-nickel-content materials (e.g., NMC333 and NMC433), while having a high capacity close to the high-nickel-content materials (e.g., NMC811 and NMC622). The origin of the thermal decomposition of NMC cathode materials was elucidated by the changes in the oxidation states of each transition metal (TM) cations (i.e., Ni, Co, and Mn) and their site preferences during thermal decomposition. It is revealed that Mn ions mainly occupy the 3a octahedral sites of a layered structure (R3̅m) but Co ions prefer to migrate to the 8a tetrahedral sites of a spinel structure (Fd3̅m) during the thermal decomposition. Such element-dependent cation migration plays a very important role in the thermal stability of NMC cathode materials. The reasonably good thermal stability and high capacity characteristics of the NMC532 composition is originated from the well-balanced ratio of nickel content to manganese and cobalt contents. This systematic study provides insight into the rational design of NMC-based cathode materials with a desired balance between thermal stability and high energy density.

  7. Processes of the excitation energy migration and transfer in Ce3+-doped alkali gadolinium phosphates studied with time-resolved photoluminescence spectroscopy technique

    International Nuclear Information System (INIS)

    Stryganyuk, G.; Shalapska, T.; Voloshinovskii, A.; Gektin, A.; Krasnikov, A.; Zazubovich, S.

    2011-01-01

    Spectral-kinetic characteristics of Gd 3+ and Ce 3+ luminescence from a series of Ce 3+ -doped alkali gadolinium phosphates of MGdP 4 O 12 type (M=Li, Na, Cs) have been studied within 4.2-300 K temperature range using time-resolved luminescence spectroscopy techniques. The processes of energy migration along the Gd 3+ sub-lattice and energy transfer between the Gd 3+ and Ce 3+ ions have been investigated. Peculiarities of these processes have been compared for MGdP 4 O 12 phosphate hosts with different alkali metal ions. A contribution of different levels from the 6 P j multiplet of the lowest Gd 3+ excited state into the energy migration and transfer processes has been clarified. The phonon-assisted occupation of high-energy 6 P 5/2,3/2 levels by Gd 3+ in the excited 6 P j state has been revealed as a shift of Gd 3+6 P j → 8 S 7/2 emission into the short-wavelength spectral range upon the temperature increase. The relaxation of excited Gd 3+ via phonon-assisted population of Gd 3+6 P 5/2 level (next higher one to the lowest excited 6 P 7/2 ) is supposed to be responsible for the rise in probability of energy migration within the Gd 3+ sub-lattice initiating the Gd 3+ →Ce 3+ energy transfer at T 3+ →Ce 3+ energy transfer at T>150 K is explained by the increase in probability of Gd 3+ relaxation into the highest 6 P 3/2 level of the 6 P j multiplet. An efficient reversed Ce 3+ →Gd 3+ energy transfer has been revealed for the studied phosphates at 4.2 K. - Highlights: →We investigate the Gd 3+ -Ce 3+ energy transfer in alkali gadolinium phosphates. → Thermal population of Gd 3+6 P 5/2 level improves migration along the Gd sub-lattice. → Increasing overlap of Gd 3+ and Ce 3+ states enhances the Gd 3+ -Ce 3+ energy transfer. → In LiGdP 4 O 12 :Ce and NaGdP 4 O 12 :Ce an efficient Ce 3+ -Gd 3+ transfer occurs at 4-300 K. → An effective reverse Gd 3+ -Ce 3+ energy transfer becomes possible at T>150 K.

  8. Structural differences in the two agonist binding sites of the Torpedo nicotinic acetylcholine receptor revealed by time-resolved fluorescence spectroscopy

    DEFF Research Database (Denmark)

    Martinez, K. L.; Corringer, P. J.; Edelstein, S. J.

    2000-01-01

    The nicotinic acetylcholine receptor (nAChR) from Torpedo marmorata carries two nonequivalent agonist binding sites at the αδ and αγ subunit interfaces. These sites have been characterized by time-resolved fluorescence with the partial nicotinic agonist dansyl-C6-choline (Dnscho). When bound...

  9. Time-resolved absorption measurements on OMEGA

    International Nuclear Information System (INIS)

    Jaanimagi, P.A.; DaSilva, L.; Delettrez, J.; Gregory, G.G.; Richardson, M.C.

    1986-01-01

    Time-resolved measurements of the incident laser light that is scattered and/or refracted from targets irradiated by the 24 uv-beam OMEGA laser at LLE, have provided some interesting features related to time-resolved absorption. The decrease in laser absorption characteristic of irradiating a target that implodes during the laser pulse has been observed. The increase in absorption expected as the critical density surface moves from a low to a high Z material in the target has also been noted. The detailed interpretation of these results is made through comparisons with simulation using the code LILAC, as well as with streak data from time-resolved x-ray imaging and spectroscopy. In addition, time and space-resolved imaging of the scattered light yields information on laser irradiation uniformity conditions on the target. The report consists of viewgraphs

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

    Energy Technology Data Exchange (ETDEWEB)

    Ogawa, Manami; Yamamoto, Susumu; Nakamura, Fumitaka; Yukawa, Ryu; Fukushima, Akiko; Harasawa, Ayumi; Kakizaki, Akito; Matsuda, Iwao [Institute for Solid State Physics, University of Tokyo, 5-1-5 Kashiwanoha, Chiba 277-8581 (Japan); Kousa, Yuka; Kondoh, Hiroshi [Department of Chemistry, Keio University, Yokohama 223-8522 (Japan); Tanaka, Yoshihito [RIKEN/SPring-8 Center, 1-1-1, Kouto, Sayo-cho, Sayo-gun, Hyogo 679-5148 (Japan)

    2012-02-15

    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.

  11. Photoelectron spectroscopy at a free-electron laser. Investigation of space-charge effects in angle-resolved and core-level spectroscopy and realizaton of a time-resolved core-level photoemission experiment

    International Nuclear Information System (INIS)

    Marczynski-Buehlow, Martin

    2012-01-01

    The free-electron laser (FEL) in Hamburg (FLASH) is a very interesting light source with which to perform photoelectron spectroscopy (PES) experiments. Its special characteristics include highly intense photon pulses (up to 100 J/pulse), a photon energy range of 30 eV to 1500 eV, transverse coherence as well as pulse durations of some ten femtoseconds. Especially in terms of time-resolved PES (TRPES), the deeper lying core levels can be reached with photon energies up to 1500 eV with acceptable intensity now and, therefore, element-specific, time-resolved core-level PES (XPS) is feasible at FLASH. During the work of this thesis various experimental setups were constructed in order to realize angle-resolved (ARPES), core-level (XPS) as well as time-resolved PES experiments at the plane grating monochromator beamline PG2 at FLASH. Existing as well as newly developed systems for online monitoring of FEL pulse intensities and generating spatial and temporal overlap of FEL and optical laser pulses for time-resolved experiments are successfully integrated into the experimental setup for PES. In order to understand space-charge effects (SCEs) in PES and, therefore, being able to handle those effects in future experiments using highly intense and pulsed photon sources, the origin of energetic broadenings and shifts in photoelectron spectra are studied by means of a molecular dynamic N-body simulation using a modified Treecode Algorithm for sufficiently fast and accurate calculations. It turned out that the most influencing parameter is the ''linear electron density'' - the ratio of the number of photoelectrons to the diameter of the illuminated spot on the sample. Furthermore, the simulations could reproduce the observations described in the literature fairly well. Some rules of thumb for XPS and ARPES measurements could be deduced from the simulations. Experimentally, SCEs are investigated by means of ARPES as well as XPS measurements as a function of FEL pulse

  12. Photoelectron spectroscopy at a free-electron laser. Investigation of space-charge effects in angle-resolved and core-level spectroscopy and realizaton of a time-resolved core-level photoemission experiment

    Energy Technology Data Exchange (ETDEWEB)

    Marczynski-Buehlow, Martin

    2012-01-30

    The free-electron laser (FEL) in Hamburg (FLASH) is a very interesting light source with which to perform photoelectron spectroscopy (PES) experiments. Its special characteristics include highly intense photon pulses (up to 100 J/pulse), a photon energy range of 30 eV to 1500 eV, transverse coherence as well as pulse durations of some ten femtoseconds. Especially in terms of time-resolved PES (TRPES), the deeper lying core levels can be reached with photon energies up to 1500 eV with acceptable intensity now and, therefore, element-specific, time-resolved core-level PES (XPS) is feasible at FLASH. During the work of this thesis various experimental setups were constructed in order to realize angle-resolved (ARPES), core-level (XPS) as well as time-resolved PES experiments at the plane grating monochromator beamline PG2 at FLASH. Existing as well as newly developed systems for online monitoring of FEL pulse intensities and generating spatial and temporal overlap of FEL and optical laser pulses for time-resolved experiments are successfully integrated into the experimental setup for PES. In order to understand space-charge effects (SCEs) in PES and, therefore, being able to handle those effects in future experiments using highly intense and pulsed photon sources, the origin of energetic broadenings and shifts in photoelectron spectra are studied by means of a molecular dynamic N-body simulation using a modified Treecode Algorithm for sufficiently fast and accurate calculations. It turned out that the most influencing parameter is the ''linear electron density'' - the ratio of the number of photoelectrons to the diameter of the illuminated spot on the sample. Furthermore, the simulations could reproduce the observations described in the literature fairly well. Some rules of thumb for XPS and ARPES measurements could be deduced from the simulations. Experimentally, SCEs are investigated by means of ARPES as well as XPS measurements as a function of

  13. Type I photosensitized reactions of oxopurines. Kinetics and thermodynamics of the reaction with triplet benzophenone by time-resolved photoacoustic spectroscopy

    Science.gov (United States)

    Murgida, Daniel H.; Erra Balsells, Rosa; Crippa, Pier Raimondo; Viappiani, Cristiano

    1998-09-01

    Benzophenone photosensitized reactions of caffeine, theophylline and theobromine were investigated in acetonitrile by time-resolved laser-induced photoacoustics. In the three cases global quenching rate constants of triplet benzophenone were measured as a function of temperature and it was observed that this is a non-activated process. Besides, for theobromine and theophylline heats for NH hydrogen abstraction reactions were determined. In agreement with semiempirical calculation predictions, hydrogen abstraction is thermodynamically more favorable and faster for theophylline (Δ H=-265 kJ mol -1, kr=9.6×10 8 M -1 s -1) than for theobromine (Δ H=-168 kJ mol -1, kr=3.7×10 8 M -1 s -1).

  14. Linearly Polarized IR Spectroscopy Theory and Applications for Structural Analysis

    CERN Document Server

    Kolev, Tsonko

    2011-01-01

    A technique that is useful in the study of pharmaceutical products and biological molecules, polarization IR spectroscopy has undergone continuous development since it first emerged almost 100 years ago. Capturing the state of the science as it exists today, "Linearly Polarized IR Spectroscopy: Theory and Applications for Structural Analysis" demonstrates how the technique can be properly utilized to obtain important information about the structure and spectral properties of oriented compounds. The book starts with the theoretical basis of linear-dichroic infrared (IR-LD) spectroscop

  15. The dependence of the ultrafast relaxation kinetics of the S2 and S1 states in β-carotene homologs and lycopene on conjugation length studied by femtosecond time-resolved absorption and Kerr-gate fluorescence spectroscopies

    Science.gov (United States)

    Kosumi, Daisuke; Fujiwara, Masazumi; Fujii, Ritsuko; Cogdell, Richard J.; Hashimoto, Hideki; Yoshizawa, Masayuki

    2009-06-01

    The ultrafast relaxation kinetics of all-trans-β-carotene homologs with varying numbers of conjugated double bonds n(n =7-15) and lycopene (n =11) has been investigated using femtosecond time-resolved absorption and Kerr-gate fluorescence spectroscopies, both carried out under identical excitation conditions. The nonradiative relaxation rates of the optically allowed S2(1Bu+1) state were precisely determined by the time-resolved fluorescence. The kinetics of the optically forbidden S1(2Ag-1) state were observed by the time-resolved absorption measurements. The dependence of the S1 relaxation rates upon the conjugation length is adequately described by application of the energy gap law. In contrast to this, the nonradiative relaxation rates of S2 have a minimum at n =9 and show a reverse energy gap law dependence for values of n above 11. This anomalous behavior of the S2 relaxation rates can be explained by the presence of an intermediate state (here called the Sx state) located between the S2 and S1 states at large values of n (such as n =11). The presence of such an intermediate state would then result in the following sequential relaxation pathway S2→Sx→S1→S0. A model based on conical intersections between the potential energy curves of these excited singlet states can readily explain the measured relationships between the decay rates and the energy gaps.

  16. Time resolved techniques: An overview

    International Nuclear Information System (INIS)

    Larson, B.C.; Tischler, J.Z.

    1990-06-01

    Synchrotron sources provide exceptional opportunities for carrying out time-resolved x-ray diffraction investigations. The high intensity, high angular resolution, and continuously tunable energy spectrum of synchrotron x-ray beams lend themselves directly to carrying out sophisticated time-resolved x-ray scattering measurements on a wide range of materials and phenomena. When these attributes are coupled with the pulsed time-structure of synchrotron sources, entirely new time-resolved scattering possibilities are opened. Synchrotron beams typically consist of sub-nanosecond pulses of x-rays separated in time by a few tens of nanoseconds to a few hundred nanoseconds so that these beams appear as continuous x-ray sources for investigations of phenomena on time scales ranging from hours down to microseconds. Studies requiring time-resolution ranging from microseconds to fractions of a nanosecond can be carried out in a triggering mode by stimulating the phenomena under investigation in coincidence with the x-ray pulses. Time resolution on the picosecond scale can, in principle, be achieved through the use of streak camera techniques in which the time structure of the individual x-ray pulses are viewed as quasi-continuous sources with ∼100--200 picoseconds duration. Techniques for carrying out time-resolved scattering measurements on time scales varying from picoseconds to kiloseconds at present and proposed synchrotron sources are discussed and examples of time-resolved studies are cited. 17 refs., 8 figs

  17. Internal energy of HCl upon photolysis of 2-chloropropene at 193 nm investigated with time-resolved Fourier-transform spectroscopy and quasiclassical trajectories

    International Nuclear Information System (INIS)

    Chang, C.-M.; Huang, Y.-H.; Liu, S.-Y.; Lee, Y.-P.; Pombar-Perez, Marta; Martinez-Nunez, Emilio; Vazquez, Saulo A.

    2008-01-01

    Following photodissociation of 2-chloropropene (H 2 CCClCH 3 ) at 193 nm, vibration-rotationally resolved emission spectra of HCl (υ≤6) in the spectral region of 1900-2900 cm -1 were recorded with a step-scan time-resolved Fourier-transform spectrometer. All vibrational levels show a small low-J component corresponding to ∼400 K and a major high-J component corresponding to 7100-18 700 K with average rotational energy of 39± 3 11 kJ mol -1 . The vibrational population of HCl is inverted at υ=2, and the average vibrational energy is 86±5 kJ mol -1 . Two possible channels of molecular elimination producing HCl+propyne or HCl+allene cannot be distinguished positively based on the observed internal energy distribution of HCl. The observed rotational distributions fit qualitatively with the distributions of both channels obtained with quasiclassical trajectories (QCTs), but the QCT calculations predict negligible populations for states at small J. The observed vibrational distribution agrees satisfactorily with the total QCT distribution obtained as a weighted sum of contributions from both four-center elimination channels. Internal energy distributions of HCl from 2-chloropropene and vinyl chloride are compared.

  18. Quantitative study of energy-transfer mechanism in Eu,O-codoped GaN by time-resolved photoluminescence spectroscopy

    Science.gov (United States)

    Inaba, Tomohiro; Kojima, Takanori; Yamashita, Genki; Matsubara, Eiichi; Mitchell, Brandon; Miyagawa, Reina; Eryu, Osamu; Tatebayashi, Jun; Ashida, Masaaki; Fujiwara, Yasufumi

    2018-04-01

    In order to investigate the excitation processes in Eu,O-codoped GaN (GaN:Eu,O), the time-resolved photoluminescence signal including the rising part is analyzed. A rate equation is developed based upon a model for the excitation processes in GaN:Eu to fit the experimental data. The non-radiative recombination rate of the trap state in the GaN host, the energy transfer rate between the Eu3+ ions and the GaN host, the radiative transition probability of Eu3+ ion, as well as the ratio of the number of luminescent sites (OMVPE 4α and OMVPE 4β), are simultaneously determined. It is revealed and quantified that radiative transition probability of the Eu ion is the bottleneck for the enhancement of light output from GaN:Eu. We also evaluate the effect of the growth conditions on the luminescent efficiency of GaN:Eu quantitatively, and find the correlation between emission intensity of GaN:Eu and the fitting parameters introduced in our model.

  19. 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.

    Science.gov (United States)

    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.

  20. A study of relaxation mechanisms in the A{sup 2}{Sigma}{sup +} state of nitric oxide by time resolved double resonant polarization spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Stampanoni-Panariello, A; Bombach, R; Hemmerling, B; Hubschmid, W [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

    1997-06-01

    Double resonant polarization labeling spectroscopy is applied to detect nitric oxide in flames and to characterize rotational energy transfer and orientation changing collisions in its first excited electronic state. (author) 4 figs., 3 refs.

  1. Time resolved infrared spectroscopy of femtosecond proton dynamics in the liquid phase; Spectroscopie infrarouge resolue en temps pour l'etude de la dynamique femtoseconde du proton en phase liquide

    Energy Technology Data Exchange (ETDEWEB)

    Amir, W

    2003-12-15

    This work of thesis aims to understand the strong mobility of protons in water. Water is fundamental to life and mediates many chemical and biological processes. However this liquid is poorly understood at the molecular level. The richness of interdisciplinary sciences allows us to study the properties which make it so unique. The technique used for this study was the femtosecond time resolved vibrational spectroscopy. Several experiments were carried out to characterize the femtosecond proton dynamics in water. The visualization of the rotation of water molecules obtained by anisotropy measurements will be presented. This experiment is carried out in isotopic water HDO/D{sub 2}O for reasons of experimental and theoretical suitability. However this is not water. Pure water H{sub 2}O was also studied without thermal effects across vibrations modes. An intermolecular energy resonant transfer was observed. Finally the localized structure of the proton in water (called Eigen form) was clearly experimentally observed. This molecule is implicated in the abnormal mobility of the proton in water (Grotthuss mechanism). (author)

  2. Vibrational spectrum of the K-590 intermediate in the bacteriorhodopsin photocycle at room temperature: picosecond time-resolved resonance coherent anti-Raman spectroscopy

    Science.gov (United States)

    Ujj, L.; Jäger, F.; Popp, A.; Atkinson, G. H.

    1996-12-01

    The vibrational spectrum of the K-590 intermediate, thought to contribute significantly to the energy storage and transduction mechanism in the bacteriorhodopsin (BR) photocycle, is measured at room temperature using picosecond time-resolved resonance coherent anti-Stokes Raman scattering (PTR/CARS). The room-temperature BR photocycle is initiated by the 3 ps, 570 nm excitation of the ground-state species, BR-570, prepared in both H 2O and D 2O suspensions of BR. PTR/CARS data, recorded 50 ps after BR-570 excitation, at which time only BR-570 and K-590 are present, have an excellent S/N which provides a significantly more detailed view of the K-590 vibrational degrees of freedom than previously available. Two picosecond (6 ps FWHM) laser pulses, ω1 (633.4 nm) and ωS (675-700 nm), are used to record PTR/CARS data via electronic resonance enhancement in both BR-570 and K-590, each of which contains a distinct retinal structure (assigned as 13- rans, 15- anti, 13- cis, respectively). To obtain the vibrational spectrum of K-590 separately, the PTR/CARS spectra from the mixture of isomeric retinals is quantitatively analyzed in terms of third-order susceptibility ( η(3)) relationships. PTR/CARS spectra of K-590 recorded from both H 2O and D 2O suspensions of BR are compared with the analogous vibrational data obtained via spontaneous resonance Raman (RR) scattering at both low (77 K) and room temperature. Analyses of these vibrational spectra identify temperature-dependent effects and changes assignable to the substitution of deuterium at the Schiff-base nitrogen not previously reported.

  3. Time-resolved quantitative phosphoproteomics

    DEFF Research Database (Denmark)

    Verano-Braga, Thiago; Schwämmle, Veit; Sylvester, Marc

    2012-01-01

    proteins involved in the Ang-(1-7) signaling, we performed a mass spectrometry-based time-resolved quantitative phosphoproteome study of human aortic endothelial cells (HAEC) treated with Ang-(1-7). We identified 1288 unique phosphosites on 699 different proteins with 99% certainty of correct peptide...

  4. Time-resolved FTIR emission spectroscopy of Cu in the 1800-3800 cm(-1) region: transitions involving f and g states and oscillator strengths

    Czech Academy of Sciences Publication Activity Database

    Civiš, Svatopluk; Matulková, Irena; Cihelka, Jaroslav; Kubelík, Petr; Kawaguchi, K.; Chernov, V. E.

    2011-01-01

    Roč. 44, č. 2 (2011), 025002 ISSN 0953-4075 R&D Projects: GA AV ČR IAA400400705; GA AV ČR KAN100500652 Institutional research plan: CEZ:AV0Z40400503 Keywords : metal poor stars * atomic data * FTIR emission spectroscopy Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.875, year: 2011

  5. Time-resolved Fourier-transform infrared emission spectroscopy of Au in the 1800-4000-cm(-1) region: Rydberg transitions

    Czech Academy of Sciences Publication Activity Database

    Civiš, Svatopluk; Matulková, Irena; Cihelka, Jaroslav

    2010-01-01

    Roč. 81, č. 1 (2010), 012510 ISSN 1050-2947 R&D Projects: GA AV ČR IAA400400705; GA AV ČR KAN100500652 Institutional research plan: CEZ:AV0Z40400503 Keywords : spectroscopy * Rydberg transitions * theoretical chemistry Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.861, year: 2010

  6. Time-resolved Fourier-transform infrared emission spectroscopy of Ag in the (1300-3600)-cm(-1) region: Transitions involving f and g states and oscillator strengths

    Czech Academy of Sciences Publication Activity Database

    Civiš, Svatopluk; Matulková, Irena; Cihelka, Jaroslav; Kubelík, Petr

    2010-01-01

    Roč. 82, č. 2 (2010), 022502 ISSN 1050-2947 R&D Projects: GA AV ČR IAA400400705; GA AV ČR KAN100500652 Institutional research plan: CEZ:AV0Z40400503 Keywords : spectroscopy * transitions * oscillator strengths Subject RIV: CF - Physical ; The oretical Chemistry Impact factor: 2.861, year: 2010

  7. Time-resolved luminescence from feldspars: New insight into fading

    DEFF Research Database (Denmark)

    Tsukamoto, S.; Denby, P.M.; Murray, A.S.

    2006-01-01

    Time-resolved infrared optically stimulated luminescence (IR-OSL) signals of K- and Na-feldspar samples extracted from sediments were measured in UV, blue and red detection windows, using a fast photon counter and pulsed IR stimulation (lambda = 875 nm). We observe that the relative contribution ...

  8. Charge transport in TiO.sub.2./sub. films with complex percolation pathways investigated by time-resolved terahertz spectroscopy

    Czech Academy of Sciences Publication Activity Database

    Němec, Hynek; Zajac, Vít; Rychetský, Ivan; Fattakhova-Rohlfing, D.; Mandlmeier, B.; Bein, T.; Mics, Zoltan; Kužel, Petr

    2013-01-01

    Roč. 3, č. 3 (2013), s. 302-313 ISSN 2156-342X R&D Projects: GA ČR GAP204/12/0232; GA ČR GA13-12386S Grant - others:AVČR(CZ) M100101218 Institutional support: RVO:68378271 Keywords : terahertz spectroscopy * charge transport * TiO 2 nanoparticles Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 4.342, year: 2013

  9. Time-resolved terahertz spectroscopy reveals the influence of charged sensitizing quantum dots on the electron dynamics in ZnO

    Czech Academy of Sciences Publication Activity Database

    Bamini, S.N.; Němec, Hynek; Žídek, Karel; Abdellah, M.; Al-Marri, M.J.; Chábera, P.; Ponseca, C.; Zheng, K.; Pullerits, T.

    2017-01-01

    Roč. 19, č. 8 (2017), s. 6006-6012 ISSN 1463-9076 R&D Projects: GA ČR GA17-03662S Institutional support: RVO:68378271 ; RVO:61389021 Keywords : sensitized semiconductors * ultrafast dynamics * terahertz spectroscopy Subject RIV: BM - Solid Matter Physics ; Magnetism OBOR OECD: Condensed matter physics (including formerly solid state physics , supercond.) Impact factor: 4.123, year: 2016

  10. Characterization of Hydrogen Bonds by IR Spectroscopy

    Directory of Open Access Journals (Sweden)

    Vojta, D.

    2012-05-01

    Full Text Available In the identification and quantification of hydrogen bond, as one of the most abundant non-covalent interactions in phenomena like self-assembly and molecular recognition, IR spectrosopy has been employed as the most sensitive method. The performance of the high dilution method enables determination of the stability constant of hydrogen-bonded complex as one of the most important thermodynamic quantities used in their characterization. However, the alleged experimental simplicity of the mentioned method is loaded with errors originating not only from researcher intervention but also independent from it. The second source of error is particularly emphasized and elaborated in this paper, which is designed as the recipe for the successful characterization of hydrogen bonds. Besides the enumeration of all steps in the determination of hydrogen-bonded stability constants, the reader can be acquainted with the most important ex perimental conditions that should be fulfilled in order to minimize the naturally occurring errors in this type of investigation. In the spectral analysis, the application of both uni- and multivariate approach has been discussed. Some computer packages, considering the latter, are mentioned, described, and recommended. KUI -10/2012Received August 1, 2011Accepted October 24, 2011

  11. Femtosecond time-resolved optical and Raman spectroscopy of photoinduced spin crossover: temporal resolution of low-to-high spin optical switching.

    Science.gov (United States)

    Smeigh, Amanda L; Creelman, Mark; Mathies, Richard A; McCusker, James K

    2008-10-29

    A combination of femtosecond electronic absorption and stimulated Raman spectroscopies has been employed to determine the kinetics associated with low-spin to high-spin conversion following charge-transfer excitation of a FeII spin-crossover system in solution. A time constant of tau = 190 +/- 50 fs for the formation of the 5T2 ligand-field state was assigned based on the establishment of two isosbestic points in the ultraviolet in conjunction with changes in ligand stretching frequencies and Raman scattering amplitudes; additional dynamics observed in both the electronic and vibrational spectra further indicate that vibrational relaxation in the high-spin state occurs with a time constant of ca. 10 ps. The results set an important precedent for extremely rapid, formally forbidden (DeltaS = 2) nonradiative relaxation as well as defining the time scale for intramolecular optical switching between two electronic states possessing vastly different spectroscopic, geometric, and magnetic properties.

  12. Time-resolved measurement of emission profiles in pulsed radiofrequency glow discharge optical emission spectroscopy: Investigation of the pre-peak

    International Nuclear Information System (INIS)

    Alberts, D.; Horvath, P.; Nelis, Th.; Pereiro, R.; Bordel, N.; Michler, J.; Sanz-Medel, A.

    2010-01-01

    Radiofrequency glow discharge coupled to optical emission spectroscopy has been used in pulsed mode in order to perform a detailed study of the measured temporal emission profiles for a wide range of copper transitions. Special attention has been paid to the early emission peak (or so-called pre-peak), observed at the beginning of the emission pulse profile. The effects of the important pulse parameters such as frequency, duty cycle, pulse width and power-off time, have been studied upon the Cu pulse emission profiles. The influence of discharge parameters, such as pressure and power, was studied as well. Results have shown that the intensity observed in the pre-peak can be 10 times as large as the plateau value for resonant lines and up to 5 times in case of transitions to the metastable levels. Increasing pressure or power increased the pre-peak intensity while its appearance in time changed. The pre-peak decreased when the discharge off-time was shorter than 100 μs. According to such results, the presence of the pre-peak could be probably due to the lack of self-absorption during the first 50 μs, and not to the ignition of the plasma. Under the selected operation conditions, the use of the pre-peak emission as analytical signals increases the linearity of calibration curves for resonant lines subjected to self-absorption at high concentrations.

  13. Time-resolved measurement of emission profiles in pulsed radiofrequency glow discharge optical emission spectroscopy: Investigation of the pre-peak

    Energy Technology Data Exchange (ETDEWEB)

    Alberts, D. [Department of Physical and Analytical Chemistry, Faculty of Chemistry, University of Oviedo, Julian Claveria 8, 33006 Oviedo (Spain); Horvath, P. [Swiss Federal Laboratories for Materials Testing and Research (EMPA), Feuerwerkerstrasse 39, 3602 Thun (Switzerland); Nelis, Th. [LAPLACE, Universite Paul Sabatier, 118 rte de Narbonne, Bat3R2, 31062 Toulouse Cedex (France); CU Jean Francois Champollion, Place de Verdun 81012 Albi Cedex 9 (France); Pereiro, R. [Department of Physical and Analytical Chemistry, Faculty of Chemistry, University of Oviedo, Julian Claveria 8, 33006 Oviedo (Spain); Bordel, N. [Department of Physics, Faculty of Science, University of Oviedo, Calvo Sotelo, 33007 Oviedo (Spain); Michler, J. [Swiss Federal Laboratories for Materials Testing and Research (EMPA), Feuerwerkerstrasse 39, 3602 Thun (Switzerland); Sanz-Medel, A., E-mail: asm@uniovi.e [Department of Physical and Analytical Chemistry, Faculty of Chemistry, University of Oviedo, Julian Claveria 8, 33006 Oviedo (Spain)

    2010-07-15

    Radiofrequency glow discharge coupled to optical emission spectroscopy has been used in pulsed mode in order to perform a detailed study of the measured temporal emission profiles for a wide range of copper transitions. Special attention has been paid to the early emission peak (or so-called pre-peak), observed at the beginning of the emission pulse profile. The effects of the important pulse parameters such as frequency, duty cycle, pulse width and power-off time, have been studied upon the Cu pulse emission profiles. The influence of discharge parameters, such as pressure and power, was studied as well. Results have shown that the intensity observed in the pre-peak can be 10 times as large as the plateau value for resonant lines and up to 5 times in case of transitions to the metastable levels. Increasing pressure or power increased the pre-peak intensity while its appearance in time changed. The pre-peak decreased when the discharge off-time was shorter than 100 {mu}s. According to such results, the presence of the pre-peak could be probably due to the lack of self-absorption during the first 50 {mu}s, and not to the ignition of the plasma. Under the selected operation conditions, the use of the pre-peak emission as analytical signals increases the linearity of calibration curves for resonant lines subjected to self-absorption at high concentrations.

  14. 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.

    Science.gov (United States)

    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.

  15. Laser Spark Formamide Decomposition Studied by FT-IR Spectroscopy

    Czech Academy of Sciences Publication Activity Database

    Ferus, Martin; Kubelík, Petr; Civiš, Svatopluk

    2011-01-01

    Roč. 115, č. 44 (2011), s. 12132-12141 ISSN 1089-5639 R&D Projects: GA AV ČR IAA400400705; GA AV ČR IAAX00100903; GA ČR GAP208/10/2302 Institutional research plan: CEZ:AV0Z40400503 Keywords : FT-IR spectroscopy * high-power laser * induced dielectric-breakdown Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.946, year: 2011

  16. Uptake Of Trivalent Actinides (Cm(III)) And Lanthanides (Eu(III)) By Cement-Type Minerals: A Wet Chemistry And Time-Resolved Laser Fluorescence Spectroscopy (TRLFS) Study

    Energy Technology Data Exchange (ETDEWEB)

    Tits, J.; Stumpf, T; Wieland, E.; Fanghaenel, T

    2003-03-01

    The interaction of the two chemical homologues Cm (III) and Eu(III) with calcium silicate hydrates at pH 13.3 has been investigated in batch-type sorption studies using Eu(III), and complemented with time-resolved laser fluorescence spectroscopy using Cm(III). The sorption data for Eu(III) reveal fast sorption kinetics, and a strong uptake by CSH phases, with distribution ratios of 6({+-}3)*105 L kg-1. Three different types of sorbed Cm(III) species have been identified: a non-fluorescing species, which was identified as Cm cluster present either as surface precipitate or as Cm(III) colloid in solution, and two sorbed fluorescing species. The sorbed fluorescing species have characteristic emission spectra (main peak maxima at 618.9 nm and 620.9 nm) and fluorescence emission lifetimes (289 {+-} 11 ms and 1482{+-} 200 ms). From the fluorescence lifetimes, it appears that the two fluorescing Cm(III) species have, respectively, one to two or no water molecules left in their first coordination sphere, suggesting that these species are incorporated into the CSH structure. A structural model for Cm(III) and Eu(III) incorporation into CSH phases is proposed based on the substitution of Ca at two different types of sites in the CSH structure. (author)

  17. Complexation of Cm(III) and Eu(III) with 2,6-bis(5-(2,2-dimethylpropyl)-1H-pyrazol-3-yl)pyridine and 2-bromohexanoic acid studied by time-resolved laser fluorescence spectroscopy

    International Nuclear Information System (INIS)

    Bremer, A.; Panak, P.J.; Heidelberg Univ.; Geist, A.

    2013-01-01

    The complexation of Cm(III) and Eu(III) with 2,6-bis(5-(2,2-dimethylpropyl)-1H-pyrazol-3-yl)pyridine (C5-BPP) and 2-bromohexanoic acid as lipophilic anion has been investigated by time-resolved laser fluorescence spectroscopy. Upon increasing ligand concentration three different Cm(III)-C5-BPP species with emission bands at 604.1 nm, 607.9 nm and 611.4 nm, respectively, are found and attributed to complexes with one, two and three C5-BPP molecules in the inner coordination sphere. Comparison with results of TRLFS experiments without 2-bromohexanoic acid shows that the C5-BPP ligand is able to completely displace the lipophilic anion from the inner coordination sphere, forming [Cm(C5-BPP) 3 ] 3+ complexes. This complex is also found in the organic phase of an extraction experiment performed with Cm(III), demonstrating that the lipophilic anion required for the extraction is not directly coordinated to the metal ion in the species formed during extraction. In case of Eu(III) the number of different species formed cannot be determined accurately. Nevertheless, the formation of the complex [EU(C5-BPP) 3 ] 3+ in the presence of 2-bromohexanoic acid is confirmed. (orig.)

  18. Direct Detection of a Chemical Equilibrium between a Localized Singlet Diradical and Its σ-Bonded Species by Time-Resolved UV/Vis and IR Spectroscopy.

    Science.gov (United States)

    Yoshidomi, Shohei; Mishima, Megumi; Seyama, Shin; Abe, Manabu; Fujiwara, Yoshihisa; Ishibashi, Taka-Aki

    2017-03-06

    Localized singlet diradicals are key intermediates in bond homolyses. The singlet diradicals are energetically much less stable than the σ-bonded species. In general, only one-way reactions from diradicals to σ-bonded species are observed. In this study, a thermal equilibrium between a singlet 1,2-diazacyclopentane-3,5-diyl diradical and the corresponding σ-bonded species was directly observed. The singlet diradical was more stable than the σ-bonded species. The solvent effect clarified key features, such as the zwitterionic character of the singlet diradical. The effect of the nitrogen atoms is discussed in detail. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Analysis of co-eluted isomers of high-molecular weight polycyclic aromatic hydrocarbons in high performance liquid chromatography fractions via solid-phase nanoextraction and time-resolved Shpol'skii spectroscopy.

    Science.gov (United States)

    Wilson, Walter B; Campiglia, Andres D

    2011-09-28

    We present an accurate method for the determination of isomers of high-molecular weight polycyclic aromatic hydrocarbons co-eluted in HPLC fractions. The feasibility of this approach is demonstrated with two isomers of molecular weight 302 with identical mass fragmentation patterns, namely dibenzo[a,i]pyrene and naphtho[2,3-a]pyrene. Qualitative and quantitative analysis is carried out via laser-excited time-resolved Shpol'skii spectroscopy at liquid helium temperature. Unambiguous identification of co-eluted isomers is based on their characteristic 4.2 K line-narrowed spectra in n-octane as well as their fluorescence lifetimes. Pre-concentration of HPLC fractions prior to spectroscopic analysis is performed with the aid of gold nanoparticles via an environmentally friendly procedure. In addition to the two co-eluted isomers, the analytical figures of merit of the entire procedure were evaluated with dibenzo[a,l]pyrene, dibenzo[a,h]pyrene and dibenzo[a,e]pyrene. The analytical recoveries from drinking water samples varied between 98.2±5.5 (dibenzo[a,l]pyrene) and 102.7±3.2% (dibenzo[a,i]pyrene). The limits of detection ranged from 51.1 ng L(-1) (naphtho[2,3-a]pyrene) to 154 ng L(-1) (dibenzo[a,e]pyrene). The excellent analytical figures of merit associated to its HPLC compatibility makes this approach an attractive alternative for the analysis of co-eluted isomers with identical mass spectra. Copyright © 2011 Elsevier B.V. All rights reserved.

  20. Time Resolved Broadband Terahertz Relaxation Dynamics of Electron in Water

    DEFF Research Database (Denmark)

    Wang, Tianwu; Iwaszczuk, Krzysztof; Cooke, David G.

    We investigated the transient response of the solvated electron in water ejected by photodetachment from potassium ferrocyanide using time resolved terahertz spectroscopy (TSTS). Ultrabroadband THz transients are generated and detected by a two-color femtosecond-induced air plasma and air biased...

  1. Study of the deuterated albumin by FT-IR spectroscopy

    International Nuclear Information System (INIS)

    Stoenescu, Daniela; Sahini, V.E.

    2000-01-01

    The albumin is a protein from the soluble or corpuscular protein class, which exists in cells, in dissolved state or in form of a hydrated gel. Proteins are essential constituents beside water, inorganic salts, lipids, carbon hydrates, vitamins, enzymes. The albumin is also a protein soluble in water and in diluted electrolyte solutions (acids, bases and salts). The investigation of the vibration isotopic effect has a great importance both for the diatomic molecules and for the polyatomic molecules. This paper is the first from a series of works which are intended to study the physico-chemical properties of the deuterated albumin and of the albumin solutions in heavy water by an isotopic exchange method. To put in evidence H-D exchange, the FT-IR spectroscopy is used when the deuterated albumin has different layer thickness. It is also of interest to elucidate the isotopic exchange between the hydrogen and oxygen atoms in bovine serum albumin macromolecules. (authors)

  2. Differentiation of Leishmania species by FT-IR spectroscopy

    Science.gov (United States)

    Aguiar, Josafá C.; Mittmann, Josane; Ferreira, Isabelle; Ferreira-Strixino, Juliana; Raniero, Leandro

    2015-05-01

    Leishmaniasis is a parasitic infectious disease caused by protozoa that belong to the genus Leishmania. It is transmitted by the bite of an infected female Sand fly. The disease is endemic in 88 countries Desjeux (2001) [1] (16 developed countries and 72 developing countries) on four continents. In Brazil, epidemiological data show the disease is present in all Brazilian regions, with the highest incidences in the North and Northeast. There are several methods used to diagnose leishmaniasis, but these procedures have many limitations, are time consuming, have low sensitivity, and are expensive. In this context, Fourier Transform Infrared Spectroscopy (FT-IR) analysis has the potential to provide rapid results and may be adapted for a clinical test with high sensitivity and specificity. In this work, FT-IR was used as a tool to investigate the promastigotes of Leishmaniaamazonensis, Leishmaniachagasi, and Leishmaniamajor species. The spectra were analyzed by cluster analysis and deconvolution procedure base on spectra second derivatives. Results: cluster analysis found four specific regions that are able to identify the Leishmania species. The dendrogram representation clearly indicates the heterogeneity among Leishmania species. The band deconvolution done by the curve fitting in these regions quantitatively differentiated the polysaccharides, amide III, phospholipids, proteins, and nucleic acids. L. chagasi and L. major showed a greater biochemistry similarity and have three bands that were not registered in L. amazonensis. The L. amazonensis presented three specific bands that were not recorded in the other two species. It is evident that the FT-IR method is an indispensable tool to discriminate these parasites. The high sensitivity and specificity of this technique opens up the possibilities for further studies about characterization of other microorganisms.

  3. Using Fourier transform IR spectroscopy to analyze biological materials

    Science.gov (United States)

    Baker, Matthew J; Trevisan, Júlio; Bassan, Paul; Bhargava, Rohit; Butler, Holly J; Dorling, Konrad M; Fielden, Peter R; Fogarty, Simon W; Fullwood, Nigel J; Heys, Kelly A; Hughes, Caryn; Lasch, Peter; Martin-Hirsch, Pierre L; Obinaju, Blessing; Sockalingum, Ganesh D; Sulé-Suso, Josep; Strong, Rebecca J; Walsh, Michael J; Wood, Bayden R; Gardner, Peter; Martin, Francis L

    2015-01-01

    IR spectroscopy is an excellent method for biological analyses. It enables the nonperturbative, label-free extraction of biochemical information and images toward diagnosis and the assessment of cell functionality. Although not strictly microscopy in the conventional sense, it allows the construction of images of tissue or cell architecture by the passing of spectral data through a variety of computational algorithms. Because such images are constructed from fingerprint spectra, the notion is that they can be an objective reflection of the underlying health status of the analyzed sample. One of the major difficulties in the field has been determining a consensus on spectral pre-processing and data analysis. This manuscript brings together as coauthors some of the leaders in this field to allow the standardization of methods and procedures for adapting a multistage approach to a methodology that can be applied to a variety of cell biological questions or used within a clinical setting for disease screening or diagnosis. We describe a protocol for collecting IR spectra and images from biological samples (e.g., fixed cytology and tissue sections, live cells or biofluids) that assesses the instrumental options available, appropriate sample preparation, different sampling modes as well as important advances in spectral data acquisition. After acquisition, data processing consists of a sequence of steps including quality control, spectral pre-processing, feature extraction and classification of the supervised or unsupervised type. A typical experiment can be completed and analyzed within hours. Example results are presented on the use of IR spectra combined with multivariate data processing. PMID:24992094

  4. IR Spectroscopy of Ethylene Glycol Solutions of Dimethylsulfoxide

    Science.gov (United States)

    Kononova, E. G.; Rodnikova, M. N.; Solonina, I. A.; Sirotkin, D. A.

    2018-07-01

    Features of ethylene glycol (EG) solutions of dimethylsulfoxide (DMSO) with low and moderate concentrations (from 2 to 50 mol % of DMSO) are studied by IR spectroscopy on a Bruker Tensor 37 FT-IR spectrometer in the wavenumber range of 400 to 4000 cm-1. The main monitored bands are the S=O stretching vibration band of DMSO (1057 cm-1) and the C-O (1086 and 1041 cm-1) and O-H (3350 cm-1) stretching vibration bands of EG. The obtained data show complex DMSO · 2EG to be present in all solutions with the studied concentrations due to formation of H-bonds between the S=O group of DMSO and the OH group of EG. In the concentration range of 6 to 25 mol % DMSO, the OH stretching vibration of EG is found to be broadened (by up to 70 cm-1), suggesting the strengthening of hydrogen bonds in the spatial network of the system due to the solvophobic effect of DMSO molecules and the formation of DMSO · 2EG. Starting from 25 mol % DMSO, narrowing of the OH stretching vibration is noted, and the bands of free DMSO appear along with the DMSO · 2EG complex, suggesting microseparation in the investigated system. At 50 mol % DMSO, the amounts of free and bound species in the system became comparable.

  5. Time-resolved photoelectron spectrometry of a dephasing process in pyrazine

    International Nuclear Information System (INIS)

    Pavlov, R.L.; Pavlov, L.I.; Delchev, Ya.I.; Pavlova, S.I.

    2001-01-01

    The first femtosecond time-resolved photoelectron imaging (PEI) is presented. The method is characterized by photoionization of NO and further applied to ultrafast dephasing in pyrazine. Intermediate case behaviour in radiationless transition is clearly observed in time-resolved photoelectron kinetic energy distribution. Femtosecond PEI is with much improved efficiency than conventional photoelectron spectroscopies. It is anticipated that the unifield approach of time-resolved photoelectron and photoion imaging opens the possibility of observing photon-induced dynamics in real time

  6. Kinetics and branching ratios of the reactions NH2+NO2->N2O+H2O and NH2+NO2->H2NO+NO studied by pulse radiolysis combined with time-resolved infrared diode laser spectroscopy

    DEFF Research Database (Denmark)

    Meunier, H.; Pagsberg, Palle Bjørn; Sillesen, A.

    1996-01-01

    studied by monitoring the decay of NH2 and the simultaneous formation of N2O and NO by time-resolved infrared diode laser spectroscopy. The decay rate of NH2 was studied as a function of NO2 concentration to obtain an overall rate constant k(NH2 + NO2) = (1.35 +/- 0.15) X 10(-11) molecule(-1) cm(3) s(-1...

  7. Time Resolved X-Ray Scattering of molecules in Solution

    DEFF Research Database (Denmark)

    Brandt van Driel, Tim

    The dissertation describes the use of Time-Resolved X-ray Diffuse Scattering (TR-XDS) to study photo-induced structural changes in molecules in solution. The application of the technique is exemplified with experiments on two bimetallic molecules. The main focus is on the data-flow and process......)42+ obtained at European Synchrotron Radiation Facility (ESRF) are presented to exemplify TR-XDS at synchrotrons. Similarly, measurements on Ir2(dimen)42+ are used to show the XFEL data-flow and how it deviates from the prior. A method to identify and account for systematic fluctuations...

  8. Chemical profiling and adulteration screening of Aquilariae Lignum Resinatum by Fourier transform infrared (FT-IR) spectroscopy and two-dimensional correlation infrared (2D-IR) spectroscopy

    Science.gov (United States)

    Qu, Lei; Chen, Jian-bo; Zhang, Gui-Jun; Sun, Su-qin; Zheng, Jing

    2017-03-01

    As a kind of expensive perfume and valuable herb, Aquilariae Lignum Resinatum (ALR) is often adulterated for economic motivations. In this research, Fourier transform infrared (FT-IR) spectroscopy is employed to establish a simple and quick method for the adulteration screening of ALR. First, the principal chemical constituents of ALR are characterized by FT-IR spectroscopy at room temperature and two-dimensional correlation infrared (2D-IR) spectroscopy with thermal perturbation. Besides the common cellulose and lignin compounds, a certain amount of resin is the characteristic constituent of ALR. Synchronous and asynchronous 2D-IR spectra indicate that the resin (an unstable secondary metabolite) is more sensitive than cellulose and lignin (stable structural constituents) to the thermal perturbation. Using a certified ALR sample as the reference, the infrared spectral correlation threshold is determined by 30 authentic samples and 6 adulterated samples. The spectral correlation coefficient of an authentic ALR sample to the standard reference should be not less than 0.9886 (p = 0.01). Three commercial adulterated ALR samples are identified by the correlation threshold. Further interpretation of the infrared spectra of the adulterated samples indicates the common adulterating methods - counterfeiting with other kind of wood, adding ingredient such as sand to increase the weight, and adding the cheap resin such as rosin to increase the content of resin compounds. Results of this research prove that FT-IR spectroscopy can be used as a simple and accurate quality control method of ALR.

  9. Decomposition of time-resolved tomographic PIV

    NARCIS (Netherlands)

    Schmid, P.J.; Violato, D.; Scarano, F.

    2012-01-01

    An experimental study has been conducted on a transitional water jet at a Reynolds number of Re = 5,000. Flow fields have been obtained by means of time-resolved tomographic particle image velocimetry capturing all relevant spatial and temporal scales. The measured threedimensional flow fields have

  10. IL 6: 2D-IR spectroscopy: chemistry and biophysics in real time

    International Nuclear Information System (INIS)

    Bredenbeck, Jens

    2010-01-01

    Pulsed multidimensional experiments, daily business in the field of NMR spectroscopy, have been demonstrated only relatively recently in IR spectroscopy. Similar as nuclear spins in multidimensional NMR, molecular vibrations are employed in multidimensional IR experiments as probes of molecular structure and dynamics, albeit with femtosecond time resolution. Different types of multidimensional IR experiments have been implemented, resembling basic NMR experiments such as NOESY, COSY and EXSY. In contrast to one-dimensional linear spectroscopy, such multidimensional experiments reveal couplings and correlations of vibrations, which are closely linked to molecular structure and its change in time. The use of mixed IR/VIS pulse sequences further extends the potential of multidimensional IR spectroscopy, enabling studies of ultrafast non-equilibrium processes as well as surface specific, highly sensitive experiments. A UV/VIS pulse preceding the IR pulse sequence can be used to prepare the system under study in a non-equilibrium state. 2D-IR snapshots of the evolving non-equilibrium system are then taken, for example during a photochemical reaction or during the photo-cycle of a light sensitive protein. Preparing the system in a non-equilibrium state by UV/Vis excitation during the IR pulse sequence allows for correlating states of reactant and product of the light triggered process via their 2D-IR cross peaks - a technique that has been used to map the connectivity between different binding sites of a ligand as it migrates through a protein. Introduction of a non-resonant VIS pulse at the end of the IR part of the experiment allows to selectively up-convert the infrared signal of interfacial molecules to the visible spectral range by sum frequency generation. In this way, femtosecond interfacial 2D-IR spectroscopy can be implemented, achieving sub-monolayer sensitivity. (author)

  11. Characterization of Momordica charantia Ussing FT-IR Spectroscopy

    Directory of Open Access Journals (Sweden)

    Attila Keseru

    2016-11-01

    In this paper, because earlier claim shows that the plant used as stomachic, carminative, tonic, antipyretic, antidiabetic, in rheumatoid arthritis and gout, the present investigation was carried to characterized a principal components of plant using FT-IR technique

  12. Nanomechanical IR spectroscopy for fast analysis of liquid-dispersed engineered nanomaterials

    OpenAIRE

    Andersen, Alina Joukainen; Yamada, Shoko; Ek, Pramod Kumar; Andresen, Thomas Lars; Boisen, Anja; Schmid, Silvan

    2016-01-01

    The proliferated use of engineered nanomaterials (ENMs), e.g. in nanomedicine, calls for novel techniques allowing for fast and sensitive analysis of minute samples. Here we present nanomechanical IR spectroscopy (NAM-IR) for chemical analysis of picograms of ENMs. ENMs are nebulized directly from dispersion and efficiently collected on nanomechanical string resonators through a non-diffusion limited sampling method. Even very small amounts of sample can convert absorbed IR light into a measu...

  13. IR-IR Conformation Specific Spectroscopy of Na+(Glucose) Adducts

    Science.gov (United States)

    Voss, Jonathan M.; Kregel, Steven J.; Fischer, Kaitlyn C.; Garand, Etienne

    2018-01-01

    We report an IR-IR double resonance study of the structural landscape present in the Na+(glucose) complex. Our experimental approach involves minimal modifications to a typical IR predissociation setup, and can be carried out via ion-dip or isomer-burning methods, providing additional flexibility to suit different experimental needs. In the current study, the single-laser IR predissociation spectrum of Na+(glucose), which clearly indicates contributions from multiple structures, was experimentally disentangled to reveal the presence of three α-conformers and five β-conformers. Comparisons with calculations show that these eight conformations correspond to the lowest energy gas-phase structures with distinctive Na+ coordination. [Figure not available: see fulltext.

  14. Fibre-Optic IR-Spectroscopy for Biomedical Diagnostics

    OpenAIRE

    Bindig, Uwe; Gersonde, Ingo; Meinke, Martina; Becker, Yukiyo; Müller, Gerhard

    2003-01-01

    The use of microscopy is a valuable means of gaining vital information for medical diagnostics. Due to a number of recent technological developments advances have been made in IR microscopy and in particular, rapid detection methods. Microscopic examination methods usually involve sampling followed by a method of sample purification or preparation. The advantages of the IR analytical method are that it is based on a direct, non‒destructive measurement of sample material and that the resulting...

  15. Nanomechanical IR spectroscopy for fast analysis of liquid-dispersed engineered nanomaterials

    DEFF Research Database (Denmark)

    Andersen, Alina Joukainen; Yamada, Shoko; Ek, Pramod Kumar

    2016-01-01

    The proliferated use of engineered nanomaterials (ENMs), e.g. in nanomedicine, calls for novel techniques allowing for fast and sensitive analysis of minute samples. Here we present nanomechanical IR spectroscopy (NAM-IR) for chemical analysis of picograms of ENMs. ENMs are nebulized directly from...

  16. Nanomechanical IR Spectroscopy for the fast analysis of picogram samples of engineered nanomaterials

    DEFF Research Database (Denmark)

    Andersen, Alina Joukainen; Ek, Pramod Kumar; Andresen, Thomas Lars

    2014-01-01

    The proliferation of engineered nanomaterials (ENMs), e.g. in nanomedicine, demands for novel sensitive techniques allowing for the analysis of minute samples. We present nanoelectromechanical system-based IR spectroscopy (NEMS-IR) of picograms of polymeric micelles. The micelles are nebulized...

  17. IR spectroscopy at the ITO-organic interface

    Energy Technology Data Exchange (ETDEWEB)

    Alt, Milan [Karlsruher Institut fuer Technologie, Karlsruhe (Germany); Shazada, Ahmad [Max-Planck Institut fuer Polymerforschung, Mainz (Germany); Tamanai, Akemi; Trollmann, Jens; Glaser, Tobias; Beck, Sebastian; Tengeler, Sven; Pucci, Annemarie [Kirchhoff-Institut fuer Physik, Heidelberg (Germany)

    2012-07-01

    Thin films of P3HT have been prepared by spin coating and electrooxidative polymerization on platinum- and ITO-coated substrates. Additionally, P3HT-films on silicon substrates have been prepared by spin coating only. The measured IR spectra of the spin coated films allowed for an elaboration of a detailed optical model for P3HT, which has been used to simulate IR reflection-absorption spectra on ITO and Pt substrates. Comparison of simulated spectra with measurements revealed no substrate influence on the IR spectra for the spincoated films. In case of spincoated P3HT-films on ITO-substrate, the obtained IR spectra correspond to simulation data very well up to 6000 wavenumbers. In the electropolymerized P3HT films we have identified residuals of the electrolyte ionic liquid, acting as dopand for P3HT. While IR spectra of the electropolymerized P3HT films on Pt substrate could be explained reasonably well as a superposition of chemically doped P3HT and the ionic electrolyte, the IR spectra of electropolymerized P3HT films on ITO substrates showed strongly deposition-time dependent deviations. These were most likely related to varying properties of the ITO surface between reference and sample measurement due to an interaction of ITO and the electrolyte at the film-substrate interface.

  18. Discrimination of Chinese Sauce liquor using FT-IR and two-dimensional correlation IR spectroscopy

    Science.gov (United States)

    Sun, Su-Qin; Li, Chang-Wen; Wei, Ji-Ping; Zhou, Qun; Noda, Isao

    2006-11-01

    We applied the three-step IR macro-fingerprint identification method to obtain the IR characteristic fingerprints of so-called Chinese Sauce liquor (Moutai liquor and Kinsly liquor) and a counterfeit Moutai. These fingerprints can be used for the identification and discrimination of similar liquor products. The comparison of their conventional IR spectra, as the first step of identification, shows that the primary difference in Sauce liquor is the intensity of characteristic peaks at 1592 and 1225 cm -1. The comparison of the second derivative IR spectra, as the second step of identification, shows that the characteristic absorption in 1400-1800 cm -1 is substantially different. The comparison of 2D-IR correlation spectra, as the third and final step of identification, can discriminate the liquors from another direction. Furthermore, the method was successfully applied to the discrimination of a counterfeit Moutai from the genuine Sauce liquor. The success of the three-step IR macro-fingerprint identification to provide a rapid and effective method for the identification of Chinese liquor suggests the potential extension of this technique to the identification and discrimination of other wine and spirits, as well.

  19. Deflection evaluation using time-resolved radiography

    International Nuclear Information System (INIS)

    Fry, D.A.; Lucero, J.P.

    1990-01-01

    Time-resolved radiography is the creation of an x-ray image for which both the start-exposure and stop-exposure times are known with respect to the event under study. The combination of image and timing are used to derive information about the event. The authors have applied time-resolved radiography to evaluate motions of explosive-driven events. In the particular application discussed in this paper, the author's intent is to measure maximum deflections of the components involved. Exposures are made during the time just before to just after the event of interest occurs. A smear or blur of motion out to its furthest extent is recorded on the image. Comparison of the dynamic images with static images allows deflection measurements to be made

  20. Supercontinuum based mid-IR imaging spectroscopy for cancer detection

    DEFF Research Database (Denmark)

    Bang, Ole; Møller, Uffe Visbech; Kubat, Irnis

    2014-01-01

    -power laser diodes, quantum cascade lasers and synchrotron radiation, have precluded mid-IR applications where the spatial coherence, broad bandwidth, high brightness and portability of a supercontinuum laser are all required. In an international collaboration in the EU project MINERVA [minerva...

  1. Stationary and time resolved PL spectroscopy for analysis of ultrafst photoreactions in MALDI and solar cell samples; Stationaere und zeitaufgeloeste Photolumineszenz-Spektroskopie zur Analyse ultraschneller Photoreaktionen in MALDI- und Solarzellenproben

    Energy Technology Data Exchange (ETDEWEB)

    Hoyer, Theo

    2009-02-12

    Stationary and time resolved measurements of photoluminescence (PL) were performed to analyse ultrafast photoreactions in solid MALDI (Matrix-Assisted Laser Desorption/Ionization) and solar cell samples. The investigation of pure cinnamic acid samples resulted in a first-time observation of a PL signature which is controlled by a photodimerisation on a ps- and fs-time scale. Other matrix compounds showed clear evidence of ultrafast photoinduced crystal reactions as well. In analyte/matrix mixtures consisting of angiotensin II and alpha-cyano-4-hydroxycinnamic acid or sinapinic acid, an additional effective PL quenching of matrix monomers was identified. This clearly indicates the existence of a further ultrafast photoreaction which strongly competes with the photodimerisation. The additional reaction is assumed to be a photoisomerisation of matrix monomers and to occur in the immediate vicinity of the analyte molecules. PL measurements on solar cell samples were performed with a P3HT/PCBM-mixture. The results show that within 150 fs about 50% of the P3HT-excitations relax via spontaneous charge transfer to PCBM molecules in this mixture.

  2. Chemical profiling and adulteration screening of Aquilariae Lignum Resinatum by Fourier transform infrared (FT-IR) spectroscopy and two-dimensional correlation infrared (2D-IR) spectroscopy.

    Science.gov (United States)

    Qu, Lei; Chen, Jian-Bo; Zhang, Gui-Jun; Sun, Su-Qin; Zheng, Jing

    2017-03-05

    As a kind of expensive perfume and valuable herb, Aquilariae Lignum Resinatum (ALR) is often adulterated for economic motivations. In this research, Fourier transform infrared (FT-IR) spectroscopy is employed to establish a simple and quick method for the adulteration screening of ALR. First, the principal chemical constituents of ALR are characterized by FT-IR spectroscopy at room temperature and two-dimensional correlation infrared (2D-IR) spectroscopy with thermal perturbation. Besides the common cellulose and lignin compounds, a certain amount of resin is the characteristic constituent of ALR. Synchronous and asynchronous 2D-IR spectra indicate that the resin (an unstable secondary metabolite) is more sensitive than cellulose and lignin (stable structural constituents) to the thermal perturbation. Using a certified ALR sample as the reference, the infrared spectral correlation threshold is determined by 30 authentic samples and 6 adulterated samples. The spectral correlation coefficient of an authentic ALR sample to the standard reference should be not less than 0.9886 (p=0.01). Three commercial adulterated ALR samples are identified by the correlation threshold. Further interpretation of the infrared spectra of the adulterated samples indicates the common adulterating methods - counterfeiting with other kind of wood, adding ingredient such as sand to increase the weight, and adding the cheap resin such as rosin to increase the content of resin compounds. Results of this research prove that FT-IR spectroscopy can be used as a simple and accurate quality control method of ALR. Copyright © 2016 Elsevier B.V. All rights reserved.

  3. FT-IR spectroscopy of lipoproteins—A comparative study

    Science.gov (United States)

    Krilov, Dubravka; Balarin, Maja; Kosović, Marin; Gamulin, Ozren; Brnjas-Kraljević, Jasminka

    2009-08-01

    FT-IR spectra, in the frequency region 4000-600 cm -1, of four major lipoprotein classes: very low density lipoprotein (VLDL), low density lipoprotein (LDL) and two subclasses of high density lipoproteins (HDL 2 and HDL 3) were analyzed to obtain their detailed spectral characterization. Information about the protein domain of particle was obtained from the analysis of amide I band. The procedure of decomposition and curve fitting of this band confirms the data already known about the secondary structure of two different apolipoproteins: apo A-I in HDL 2 and HDL 3 and apo B-100 in LDL and VLDL. For information about the lipid composition and packing of the particular lipoprotein the well expressed lipid bands in the spectra were analyzed. Characterization of spectral details in the FT-IR spectrum of natural lipoprotein is necessary to study the influence of external compounds on its structure.

  4. Time-resolved studies. Ch. 9

    International Nuclear Information System (INIS)

    Mills, Dennis M.; Argonne National Lab., IL

    1991-01-01

    Synchrotron radiation, with its unique properties, offers a tool to extend X-ray measurements from the static to the time-resolved regime. The most straight-forward application of synchrotron radiation to the study of transient phenomena is directly through the possibility of decreased data-collection times via the enormous increase in flux over that of a laboratory X-ray system. Even further increases in intensity can be obtained through the use of novel X-ray optical devices. Wide-bandpass monochromators, e.g., that utilize the continuous spectral distribution of synchrotron radiation, can increase flux on the sample several orders of magnitude over conventional X-ray optical systems thereby allowing a further shortening of the data-collection time. Another approach that uses the continuous spectral nature of synchrotron radiation to decrease data-collection times is the 'parallel data collection' method. Using this technique, intensities as a function of X-ray energy are recorded simultaneously for all energies rather than sequentially recording data at each energy, allowing for a dramatic decrease in data-collection time. Perhaps the most exciting advances in time-resolved X-ray studies will be made by those methods that exploit the pulsed nature of the radiation emitted from storage rings. Pulsed techniques have had an enormous impact in the study of the temporal evolution of transient phenomena. The extension from continuous to modulated sources for use in time-resolved work has been carried over in a host of fields that use both pulsed particle and pulsed electro-magnetic beams. In this chapter the new experimental techniques are reviewed and illustrated with some experiments. (author). 98 refs.; 20 figs.; 5 tabs

  5. Time-resolved x-ray diagnostics

    International Nuclear Information System (INIS)

    Lyons, P.B.

    1981-01-01

    Techniques for time-resolved x-ray diagnostics will be reviewed with emphasis on systems utilizing x-ray diodes or scintillators. System design concerns for high-bandwidth (> 1 GHz) diagnostics will be emphasized. The limitations of a coaxial cable system and a technique for equalizing to improve bandwidth of such a system will be reviewed. Characteristics of new multi-GHz amplifiers will be presented. An example of a complete operational system on the Los Alamos Helios laser will be presented which has a bandwidth near 3 GHz over 38 m of coax. The system includes the cable, an amplifier, an oscilloscope, and a digital camera readout

  6. Space and time resolved spectroscopy of laser-produced plasmas: A study of density-sensitive x-ray transitions in helium-like and neon-like ions

    International Nuclear Information System (INIS)

    Young, Bruce Kai Fong.

    1988-09-01

    The determination of level populations and detailed population mechanisms in dense plasmas has become an increasingly important problem in atomic physics. In this work, the density variation of line intensities and level populations in aluminum K-shell and molybdenum and silver L-shell emission spectra have been measured from high-powered, laser-produced plasmas. For each case, the density dependence of the observed line emission is due to the effect of high frequency electron-ion collisions on metastable levels. The density dependent line intensities vary greatly in laser-produced plasmas and can be used to extract detailed information concerning the population kinetics and level populations of the ions. The laser-plasmas had to be fully characterized in order to clearly compare the observed density dependence with atomic theory predictions. This has been achieved through the combined use of new diagnostic instruments and microdot targets which provided simultaneously space, time, and spectrally resolved data. The plasma temperatures were determined from the slope of the hydrogen-like recombination continuum. The time resolved electron density profiles were measured using multiple frame holographic interferometry. Thus, the density dependence of K-shell spectral lines could be clearly examined, independent of assumptions concerning the dynamics of the plasma. In aluminum, the electron density dependence of various helium-like line intensity ratios were measured. Standard collisional radiative equilibrium models fail to account for the observed density dependence measured for the ''He/sub α//IC'' ratio. Instead, a quasi-steady state atomic model based on a purely recombining plasma is shown to accurately predict the measured density dependence. This same recombining plasma calculation successfully models the density dependence of the high-n ''He/sub γ//He/sub β/'' and ''He/sub δ//He/sub β/'' helium-like resonance line intensity ratios

  7. Space and time resolved spectroscopy of laser-produced plasmas: A study of density-sensitive x-ray transitions in helium-like and neon-like ions

    Energy Technology Data Exchange (ETDEWEB)

    Young, Bruce Kai Fong

    1988-09-01

    The determination of level populations and detailed population mechanisms in dense plasmas has become an increasingly important problem in atomic physics. In this work, the density variation of line intensities and level populations in aluminum K-shell and molybdenum and silver L-shell emission spectra have been measured from high-powered, laser-produced plasmas. For each case, the density dependence of the observed line emission is due to the effect of high frequency electron-ion collisions on metastable levels. The density dependent line intensities vary greatly in laser-produced plasmas and can be used to extract detailed information concerning the population kinetics and level populations of the ions. The laser-plasmas had to be fully characterized in order to clearly compare the observed density dependence with atomic theory predictions. This has been achieved through the combined use of new diagnostic instruments and microdot targets which provided simultaneously space, time, and spectrally resolved data. The plasma temperatures were determined from the slope of the hydrogen-like recombination continuum. The time resolved electron density profiles were measured using multiple frame holographic interferometry. Thus, the density dependence of K-shell spectral lines could be clearly examined, independent of assumptions concerning the dynamics of the plasma. In aluminum, the electron density dependence of various helium-like line intensity ratios were measured. Standard collisional radiative equilibrium models fail to account for the observed density dependence measured for the ''He/sub ..cap alpha..//IC'' ratio. Instead, a quasi-steady state atomic model based on a purely recombining plasma is shown to accurately predict the measured density dependence. This same recombining plasma calculation successfully models the density dependence of the high-n ''He/sub ..gamma..//He/sub ..beta../'' and ''He/sub delta

  8. Femtosecond Time-resolved Optical Polarigraphy (FTOP)

    International Nuclear Information System (INIS)

    Aoshima, S.; Fujimoto, M.; Hosoda, M.; Tsuchiya, Y.

    2000-01-01

    A novel time-resolved imaging technique named FTOP (Femtosecond Time-resolved Optical Polarigraphy) for visualizing the ultrafast propagation dynamics of intense light pulses in a medium has been proposed and demonstrated. Femtosecond snapshot images can be created with a high spatial resolution by imaging only the polarization components of the probe pulse; these polarization components change due to the instantaneous birefringence induced by the pump pulse in the medium. Ultrafast temporal changes in the two-dimensional spatial distribution of the optical pulse intensity were clearly visualized in consecutive images by changing the delay between the pump and probe. We observe that several filaments appear and then come together before the vacuum focus due to nonlinear effects in air. We also prove that filamentation dynamics such as the formation position and the propagation behavior are complex and are strongly affected by the pump energy. The results collected clearly show that this method FTOP succeeds for the first time in directly visualizing the ultrafast dynamics of the self-modulated nonlinear propagation of light. (author)

  9. Time Resolved Deposition Measurements in NSTX

    International Nuclear Information System (INIS)

    Skinner, C.H.; Kugel, H.; Roquemore, A.L.; Hogan, J.; Wampler, W.R.

    2004-01-01

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

  10. Photothermal IR spectroscopy with perforated membrane micromechanical resonators

    DEFF Research Database (Denmark)

    Kurek, Maksymilian

    -IR method. In order to overcome them, string resonators were replaced by membranes. A reliable sampling technique was maintained by adding perforation to membranes and thereby essentially getting membrane porous filters. Membranes gave also access to fully integrated magnetic transduction that allowed...... for significant shrinkage and simplification of the system. An analytical model of a locally heated membrane was developed and confirmed through FEM simulations. Then, low stress silicon nitride perforated membranes were fabricated and characterized using two different experimental setups that employed optical...

  11. Study on Angelica and its different extracts by Fourier transform infrared spectroscopy and two-dimensional correlation IR spectroscopy

    Science.gov (United States)

    Liu, Hong-xia; Sun, Su-qin; Lv, Guang-hua; Chan, Kelvin K. C.

    2006-05-01

    In order to develop a rapid and effective analysis method for studying integrally the main constituents in the medicinal materials and their extracts, discriminating the extracts from different extraction process, comparing the categories of chemical constituents in the different extracts and monitoring the qualities of medicinal materials, we applied Fourier transform infrared spectroscopy (FT-IR) associated with second derivative infrared spectroscopy and two-dimensional correlation infrared spectroscopy (2D-IR) to study the main constituents in traditional Chinese medicine Angelica and its different extracts (extracted by petroleum ether, ethanol and water in turn). The findings indicated that FT-IR spectrum can provide many holistic variation rules of chemical constituents. Use of the macroscopical fingerprint characters of FT-IR and 2D-IR spectrum can not only identify the main chemical constituents in medicinal materials and their different extracts, but also compare the components differences among the similar samples. This analytical method is highly rapid, effective, visual and accurate for pharmaceutical research.

  12. Anisotropy in Bone Demineralization Revealed by Polarized Far-IR Spectroscopy

    Directory of Open Access Journals (Sweden)

    Roman Schuetz

    2015-04-01

    Full Text Available Bone material is composed of an organic matrix of collagen fibers and apatite nanoparticles. Previously, vibrational spectroscopy techniques such as infrared (IR and Raman spectroscopy have proved to be particularly useful for characterizing the two constituent organic and inorganic phases of bone. In this work, we tested the potential use of high intensity synchrotron-based far-IR radiation (50–500 cm−1 to gain new insights into structure and chemical composition of bovine fibrolamellar bone. The results from our study can be summarized in the following four points: (I compared to far-IR spectra obtained from synthetic hydroxyapatite powder, those from fibrolamellar bone showed similar peak positions, but very different peak widths; (II during stepwise demineralization of the bone samples, there was no significant change neither to far-IR peak width nor position, demonstrating that mineral dissolution occurred in a uniform manner; (III application of external loading on fully demineralized bone had no significant effect on the obtained spectra, while dehydration of samples resulted in clear differences. (IV using linear dichroism, we showed that the anisotropic structure of fibrolamellar bone is also reflected in anisotropic far-IR absorbance properties of both the organic and inorganic phases. Far-IR spectroscopy thus provides a novel way to functionally characterize bone structure and chemistry, and with further technological improvements, has the potential to become a useful clinical diagnostic tool to better assess quality of collagen-based tissues.

  13. Time-resolved brightness measurements by streaking

    Science.gov (United States)

    Torrance, Joshua S.; Speirs, Rory W.; McCulloch, Andrew J.; Scholten, Robert E.

    2018-03-01

    Brightness is a key figure of merit for charged particle beams, and time-resolved brightness measurements can elucidate the processes involved in beam creation and manipulation. Here we report on a simple, robust, and widely applicable method for the measurement of beam brightness with temporal resolution by streaking one-dimensional pepperpots, and demonstrate the technique to characterize electron bunches produced from a cold-atom electron source. We demonstrate brightness measurements with 145 ps temporal resolution and a minimum resolvable emittance of 40 nm rad. This technique provides an efficient method of exploring source parameters and will prove useful for examining the efficacy of techniques to counter space-charge expansion, a critical hurdle to achieving single-shot imaging of atomic scale targets.

  14. Time-resolved measurements of luminescence

    Energy Technology Data Exchange (ETDEWEB)

    Collier, Bradley B. [Department of Biomedical Engineering, 408 Mechanical Engineering Office Building, Spence Street, Texas A and M University, College Station, TX 77843 (United States); McShane, Michael J., E-mail: mcshane@tamu.edu [Department of Biomedical Engineering, 408 Mechanical Engineering Office Building, Spence Street, Texas A and M University, College Station, TX 77843 (United States); Materials Science and Engineering Program, 408 Mechanical Engineering Office Building, Spence Street, Texas A and M University, College Station, TX 77843 (United States)

    2013-12-15

    Luminescence sensing and imaging has become more widespread in recent years in a variety of industries including the biomedical and environmental fields. Measurements of luminescence lifetime hold inherent advantages over intensity-based response measurements, and advances in both technology and methods have enabled their use in a broader spectrum of applications including real-time medical diagnostics. This review will focus on recent advances in analytical methods, particularly calculation techniques, including time- and frequency-domain lifetime approaches as well as other time-resolved measurements of luminescence. -- Highlights: • Developments in technology have led to widespread use of luminescence lifetime. • Growing interest for sensing and imaging applications. • Recent advances in approaches to lifetime calculations are reviewed. • Advantages and disadvantages of various methods are weighed. • Other methods for measurement of luminescence lifetime also described.

  15. Time-resolved measurements of luminescence

    International Nuclear Information System (INIS)

    Collier, Bradley B.; McShane, Michael J.

    2013-01-01

    Luminescence sensing and imaging has become more widespread in recent years in a variety of industries including the biomedical and environmental fields. Measurements of luminescence lifetime hold inherent advantages over intensity-based response measurements, and advances in both technology and methods have enabled their use in a broader spectrum of applications including real-time medical diagnostics. This review will focus on recent advances in analytical methods, particularly calculation techniques, including time- and frequency-domain lifetime approaches as well as other time-resolved measurements of luminescence. -- Highlights: • Developments in technology have led to widespread use of luminescence lifetime. • Growing interest for sensing and imaging applications. • Recent advances in approaches to lifetime calculations are reviewed. • Advantages and disadvantages of various methods are weighed. • Other methods for measurement of luminescence lifetime also described

  16. Time - resolved thermography at Tokamak T-10

    International Nuclear Information System (INIS)

    Grunow, C.; Guenther, K.; Lingertat, J.; Chicherov, V.M.; Evstigneev, S.A.; Zvonkov, S.N.

    1987-01-01

    Thermographic experiments were performed at T-10 tokamak to investigate the thermic coupling of plasma and the limiter. The limiter is an internal equipment of the vacuum vessel of tokamak-type fusion devices and the interaction of plasma with limiter results a high thermal load of limiter for short time. In according to improve the limiter design the temperature distribution on the limiter surface was measured by a time-resolved thermographic method. Typical isotherms and temperature increment curves are presented. This measurement can be used as a systematic plasma diagnostic method because the limiter is installed in the tokamak whereas special additional probes often disturb the plasma discharge. (D.Gy.) 3 refs.; 7 figs

  17. Monitoring coal conversion processes by IR-spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Hobert, H.; Kempe, J.; Stephanowitz, H. (Friedrich-Schiller-Universitaet, Jena (German Democratic Republic))

    1990-01-01

    Explains application of infrared spectroscopy combined with multivariate data analysis by an on-line computer system for assessing coal quality and suitability of brown coal for conversion processes. Coal samples were pelletized under addition of KBr and analyzed using an IRF 180 Fourier transform spectrometer in the spectral range of 400 to 2,000 cm{sup -1}. Components of spectra are presented; the oil yield from coal hydrogenation is calculated by regression analysis. Covariance spectra of carbon, organic hydrogen and sulfur are shown. It is concluded that the field of application for the method includes industrial coal liquefaction, gasification as well as briquetting and coking. 8 refs.

  18. Time resolved FTIR study of the catalytic CO oxidation under periodic variation of the reactant concentration

    Energy Technology Data Exchange (ETDEWEB)

    Kritzenberger, J; Wokaun, A [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

    1997-06-01

    Oxidation of CO over palladium/zirconia catalyst obtained from an amorphous Pd{sub 25}Zr{sub 75} precursor was investigated by time resolved FTIR spectroscopy. Sine wave shaped modulation of the reactant concentration, i.e. variation of CO or O{sub 2} partial pressure, was used to induce variations of the IR signals of product (CO{sub 2}) and unconverted reactant (CO), which were detected in a multi-pass absorption cell. The phase shift {phi} between external perturbation and variation of the CO{sub 2} signal was examined in dependence on temperature (100{sup o}C{<=}T{<=}350{sup o}C) and modulation frequency (1.39x10{sup -4}Hz{<=}{omega}{<=}6.67x10{sup -2}Hz). From the phase shift values, a simple Eley-Rideal mechanism is excluded, and the rate limiting step of the Langmuir-Hinshelwood mechanism for the CO oxidation may be identified. Adsorption and possible surface movement of CO to the actual reaction site determine the rate of the CO oxidation on the palladium/zirconia catalyst used in our study. The introduction of an external perturbation is a first step towards the application of two-dimensional infrared spectroscopy to heterogeneous catalyzed reactions. (author) 3 figs., 4 refs.

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

    Science.gov (United States)

    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.

  20. Quantitative analysis of time-resolved infrared stimulated luminescence in feldspars

    DEFF Research Database (Denmark)

    Pagonis, Vasilis; Ankjærgaard, Christina; Jain, Mayank

    2016-01-01

    Time-resolved infrared-stimulated luminescence (TR-IRSL) from feldspar samples is of importance in the field of luminescence dating, since it provides information on the luminescence mechanism in these materials. In this paper we present new analytical equations which can be used to analyze TR-IR...

  1. The study of the curing of the polyurethane coating by method of IR spectroscopy

    Directory of Open Access Journals (Sweden)

    N. A. Korshunova

    2016-12-01

    Full Text Available The results of the study of the curing process of polyurethane compositions with participation of two different catalysts by the method of IR spectroscopy are given. The time dependences of curing of polyurethane coatings from concentrations of catalysts were determined, on the basis of which the most effective catalyst was selected.

  2. Monitoring lipase-catalyzed interesterification for bulky fats modification with FT-IR/NIR spectroscopy

    DEFF Research Database (Denmark)

    Chang, Tinghong; Lai, Xuxin; Zhang, Hong

    2005-01-01

    This work demonstrates the application of FT-IR and FT-NIR spectroscopy to monitor the enzymatic interesterification process for bulky fat modification. The reaction was conducted between palm stearin and coconut oil (70/30, w/w) with the catalysis of Lipozyme TL IM at 70°C in a batch reactor...

  3. Structure Determination of Unknown Organic Liquids Using NMR and IR Spectroscopy: A General Chemistry Laboratory

    Science.gov (United States)

    Pavel, John T.; Hyde, Erin C.; Bruch, Martha D.

    2012-01-01

    This experiment introduced general chemistry students to the basic concepts of organic structures and to the power of spectroscopic methods for structure determination. Students employed a combination of IR and NMR spectroscopy to perform de novo structure determination of unknown alcohols, without being provided with a list of possible…

  4. Chapter 1.1 Crystallinity of Nanocellulose Materials by Near-IR FT-Raman Spectroscopy

    Science.gov (United States)

    Umesh P. Agarwal; Richard S. Reiner; Sally A. Ralph

    2013-01-01

    Considering that crystallinity is one of the important properties that influence the end use of cellulose nanomaterials, it is important that the former be measured accurately. Recently, a new method based on near-IR FTRaman spectroscopy was proposed to determine cellulose I crystallinity. It was reported that in the Raman spectrum of cellulose materials, the...

  5. Solid Acid-Catalyzed Cellulose Hydrolysis Monitored by In Situ ATR-IR Spectroscopy

    NARCIS (Netherlands)

    Zakzeski, J.; Grisel, R.J.H.; Smit, A.T.; Weckhuysen, B.M.

    2012-01-01

    The solid acid-catalyzed hydrolysis of cellulose was studied under elevated temperatures and autogenous pressures using in situ ATR-IR spectroscopy. Standards of cellulose and pure reaction products, which include glucose, fructose, hydroxymethylfurfural (HMF), levulinic acid (LA), formic acid, and

  6. Time resolved ion beam induced charge collection

    International Nuclear Information System (INIS)

    Sexton W, Frederick; Walsh S, David; Doyle L, Barney; Dodd E, Paul

    2000-01-01

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

  7. Enzyme reactions and their time resolved measurements

    International Nuclear Information System (INIS)

    Hajdu, Janos

    1990-01-01

    This paper discusses experimental strategies in data collection with the Laue method and summarises recent results using synchrotron radiation. Then, an assessment is made of the progress towards time resolved studies with protein crystals and the problems that remain. The paper consists of three parts which respectively describe some aspects of Laue diffraction, recent examples of structural results from Laue diffraction, and kinetic Laue crystallography. In the first part, characteristics of Laue diffraction is discussed first, focusing on the harmonics problems, spatials problem, wavelength normalization, low resolution hole, data completeness, and uneven coverage of reciprocal space. Then, capture of the symmetry unique reflection set is discussed focusing on the effect of wavelength range on the number of reciprocal lattice points occupying diffracting positions, effect of crystal to film distance and the film area and shape on the number of reflections captured, and effect of crystal symmetry on the number of unique reflections within the number of reflections captured. The second part addresses the determination of the structure of turkey egg white lysozyme, and calcium binding in tomato bushy stunt virus. The third part describes the initiation of reactions in enzyme crystals, picosecond Laue diffraction at high energy storage rings, and detectors. (N.K.)

  8. Time resolved ion beam induced charge collection

    Energy Technology Data Exchange (ETDEWEB)

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

    2000-04-01

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

  9. Preliminary study of corrosion mechanisms of actinides alloys: calibration of FT-IR spectroscopy

    International Nuclear Information System (INIS)

    Magnien, Veronique; Cadignan, Marx; Faivret, Olivier; Rosa, Gaelle

    2008-01-01

    In situ analyzes of gaseous atmospheres could be performed by FT-IR spectroscopy in order to study the corrosion reactions of actinides. Nevertheless experimental conditions and the nature of studied species have a strong effect on IR absorption laws. Thus a prior calibration of our set-up is required to obtain an accurate estimation of gas concentration. For this purpose, the behavior of several air pure gases has been investigated according to their concentration from IR spectra. Reproducible results revealed subsequent increases of the most significant peak areas with gas pressure and small deviations from Beer Lambert's law. This preliminary work allowed to determine precise absorption laws for each studied pure gas in our in situ experimental conditions. Besides our FT-IR set-up was well suitable to quantitative analysis of gaseous atmosphere during corrosion reactions. Finally the effect of foreign gas will be investigated through more complex air mixtures to obtain a complete calibration network. (authors)

  10. Interrogating the vibrational relaxation of highly excited polyatomics with time-resolved diode laser spectroscopy: C6H6, C6D6, and C6F6+CO2

    International Nuclear Information System (INIS)

    Sedlacek, A.J.; Weston, R.E. Jr.; Flynn, G.W.

    1991-01-01

    The vibrational relaxation of highly excited ground state benzene, benzene d 6 , and hexafluorobenzene by CO 2 has been investigated with high resolution diode laser spectroscopy. The vibrationally hot polyatomics are formed by single photon 248 nm excitation to the S 1 state followed by rapid radiationless transitions. It has been found that in all cases less than 1% of the energy initially present in the polyatomics is deposited into the high frequency mode of CO 2 (ν 3 ). An investigation of the CO 2 (00 0 1) nascent rotational distribution under single collision conditions reveals that very little rotational excitation accompanies vibrational energy transfer to the ν 3 mode. The CO 2 (ν 3 ) rotational states can be described by temperatures, T rot , as follows: C 6 H 6 , T rot =360±30 K; C 6 D 6 , T rot =350±35 K and C 6 F 6 , T rot =340±23 K. An estimate of left-angle ΔE right-angle ν3 , the mean energy transferred to the CO 2 ν 3 mode per collision, suggests that as the availability of low frequency modes in the excited molecule increases, less energy is deposited into the high frequency mode of CO 2 . Finally, evidence is presented suggesting that even at moderate laser fluences, the two-photon ionization of benzene can lead to substantial CO 2 ν 3 excitation via electron+CO 2 inelastic collisions

  11. Preliminary Discrimination of Cheese Adulteration by FT-IR Spectroscopy

    Directory of Open Access Journals (Sweden)

    Lucian Cuibus

    2014-11-01

    Full Text Available The present work describes a preliminary study to compare some traditional Romanian cheeses and adulterated cheeses using Attenuated Total Reflectance-Fourier transform infrared spectroscopy (ATR-FTIR. For PLS model calibration (6 concentration levels and validation (5 concentration levels sets were prepared from commercial Dalia Cheese from different manufacturers by spiking it with palm oil at concentrations ranging 2-50 % and 5-40 %, respectively. Fifteen Dalia Cheese were evaluated as external set. The spectra of each sample, after homogenization, were acquired in triplicate using a FTIR Shimatsu Prestige 21 Spectrophotometer, with a horizontal diamond ATR accessory in the MIR region 4000-600 cm-1. Statistical methods as PLS were applied using MVC1 routines written for Matlab R2010a. As first step the optimal condition for PLS model were obtained using cross-validation on the Calibration set. Spectral region in 3873-652 cm-1, and 3 PLS-factors were stated as the best conditions and showed an R2 value of 0.9338 and a relative error in the calibration of 17.2%. Then validation set was evaluated, obtaining good recovery rates (108% and acceptable dispersion of the data (20%. The curve of actual vs. predicted values shows slope near to 1 and origin close to 0, with an R2 of 0.9695. When the external sample set was evaluated, samples F19, F21, F22 and F24, showed detectable levels of palm fats. The results proved that FTIR-PLS is a reliable non-destructive technique for a rapid quantification the level of adulteration in cheese.  The spectroscopic methods could assist the quality control authority, traders and the producers to discriminate the adulterated cheeses with palm oil.

  12. Probing Gas Adsorption in Zeolites by Variable-Temperature IR Spectroscopy: An Overview of Current Research.

    Science.gov (United States)

    Garrone, Edoardo; Delgado, Montserrat R; Bonelli, Barbara; Arean, Carlos O

    2017-09-15

    The current state of the art in the application of variable-temperature IR (VTIR) spectroscopy to the study of (i) adsorption sites in zeolites, including dual cation sites; (ii) the structure of adsorption complexes and (iii) gas-solid interaction energy is reviewed. The main focus is placed on the potential use of zeolites for gas separation, purification and transport, but possible extension to the field of heterogeneous catalysis is also envisaged. A critical comparison with classical IR spectroscopy and adsorption calorimetry shows that the main merits of VTIR spectroscopy are (i) its ability to provide simultaneously the spectroscopic signature of the adsorption complex and the standard enthalpy change involved in the adsorption process; and (ii) the enhanced potential of VTIR to be site specific in favorable cases.

  13. Remote Thermal IR Spectroscopy of our Solar System

    Science.gov (United States)

    Kostiuk, Theodor; Hewagama, Tilak; Goldstein, Jeffrey; Livengood, Timothy; Fast, Kelly

    1999-01-01

    Indirect methods to detect extrasolar planets have been successful in identifying a number of stars with companion planets. No direct detection of an extrasolar planet has yet been reported. Spectroscopy in the thermal infrared region provides a potentially powerful approach to detection and characterization of planets and planetary systems. We can use knowledge of our own solar system, its planets and their atmospheres to model spectral characteristics of planets around other stars. Spectra derived from modeling our own solar system seen from an extrasolar perspective can be used to constrain detection strategies, identification of planetary class (terrestrial vs. gaseous) and retrieval of chemical, thermal and dynamical information. Emission from planets in our solar system peaks in the thermal infrared region, approximately 10 - 30 microns, substantially displaced from the maximum of the much brighter solar emission in the visible near 0.5 microns. This fact provides a relatively good contrast ratio to discriminate between stellar (solar) and planetary emission and optimize the delectability of planetary spectra. Important molecular constituents in planetary atmospheres have rotational-vibrational spectra in the thermal infrared region. Spectra from these molecules have been well characterized in the laboratory and studied in the atmospheres of solar system planets from ground-based and space platforms. The best example of such measurements are the studies with Fourier transform spectrometers, the Infrared Interferometer Spectrometers (IRIS), from spacecraft: Earth observed from NIMBUS 8, Mars observed from Mariner 9, and the outer planets observed from Voyager spacecraft. An Earth-like planet is characterized by atmospheric spectra of ozone, carbon dioxide, and water. Terrestrial planets have oxidizing atmospheres which are easily distinguished from reducing atmospheres of gaseous giant planets which lack oxygen-bearing species and are characterized by spectra

  14. The discrimination of 72 nitrate, chlorate and perchlorate salts using IR and Raman spectroscopy

    Science.gov (United States)

    Zapata, Félix; García-Ruiz, Carmen

    2018-01-01

    Inorganic oxidizing energetic salts including nitrates, chlorates and perchlorates are widely used in the manufacture of not only licit pyrotechnic compositions, but also illicit homemade explosive mixtures. Their identification in forensic laboratories is usually accomplished by either capillary electrophoresis or ion chromatography, with the disadvantage of dissociating the salt into its ions. On the contrary, vibrational spectroscopy, including IR and Raman, enables the non-invasive identification of the salt, i.e. avoiding its dissociation. This study focuses on the discrimination of all nitrate, chlorate and perchlorate salts that are commercially available, using both Raman and IR spectroscopy, with the aim of testing whether every salt can be unequivocally identified. Besides the visual spectra comparison by assigning every band with the corresponding molecular vibrational mode, a statistical analysis based on Pearson correlation was performed to ensure an objective identification, either using Raman, IR or both. Positively, 25 salts (out of 72) were unequivocally identified using Raman, 30 salts when using IR and 44 when combining both techniques. Negatively, some salts were undistinguishable even using both techniques demonstrating there are some salts that provide very similar Raman and IR spectra.

  15. Rapid identification of Pterocarpus santalinus and Dalbergia louvelii by FTIR and 2D correlation IR spectroscopy

    Science.gov (United States)

    Zhang, Fang-Da; Xu, Chang-Hua; Li, Ming-Yu; Huang, An-Min; Sun, Su-Qin

    2014-07-01

    Since Pterocarpus santalinus and Dalbergia louvelii, which are of precious Rosewood, are very similar in their appearance and anatomy characteristics, cheaper Hongmu D. louvelii is often illegally used to impersonate valuable P. santalinus, especially in Chinese furniture manufacture. In order to develop a rapid and effective method for easy confused wood furniture differentiation, we applied tri-step identification method, i.e., conventional infrared spectroscopy (FT-IR), second derivative infrared (SD-IR) spectroscopy and two-dimensional correlation infrared (2DCOS-IR) spectroscopy to investigate P. santalinus and D. louvelii furniture. According to FT-IR and SD-IR spectra, it has been found two unconditional stable difference at 848 cm-1 and 700 cm-1 and relative stable differences at 1735 cm-1, 1623 cm-1, 1614 cm-1, 1602 cm-1, 1509 cm-1, 1456 cm-1, 1200 cm-1, 1158 cm-1, 1055 cm-1, 1034 cm-1 and 895 cm-1 between D. louvelii and P. santalinus IR spectra. The stable discrepancy indicates that the category of extractives is different between the two species. Besides, the relative stable differences imply that the content of holocellulose in P. santalinus is more than that of D. louvelii, whereas the quantity of extractives in D. louvelii is higher. Furthermore, evident differences have been observed in their 2DCOS-IR spectra of 1550-1415 cm-1 and 1325-1030 cm-1. P. santalinus has two strong auto-peaks at 1459 cm-1 and 1467 cm-1, three mid-strong auto-peaks at 1518 cm-1, 1089 cm-1 and 1100 cm-1 and five weak auto-peaks at 1432 cm-1, 1437 cm-1, 1046 cm-1, 1056 cm-1 and 1307 cm-1 while D. louvelii has four strong auto-peaks at 1465 cm-1, 1523 cm-1, 1084 cm-1 and 1100 cm-1, four mid-strong auto-peaks at 1430 cm-1, 1499 cm-1, 1505 cm-1 and 1056 cm-1 and two auto-peaks at 1540 cm-1 and 1284 cm-1. This study has proved that FT-IR integrated with 2DCOS-IR could be applicable for precious wood furniture authentication in a direct, rapid and holistic manner.

  16. Detection of metanil yellow contamination in turmeric using FT-Raman and FT-IR spectroscopy

    Science.gov (United States)

    Dhakal, Sagar; Chao, Kuanglin; Qin, Jianwei; Kim, Moon; Schmidt, Walter; Chan, Dian

    2016-05-01

    Turmeric is well known for its medicinal value and is often used in Asian cuisine. Economically motivated contamination of turmeric by chemicals such as metanil yellow has been repeatedly reported. Although traditional technologies can detect such contaminants in food, high operational costs and operational complexities have limited their use to the laboratory. This study used Fourier Transform Raman Spectroscopy (FT-Raman) and Fourier Transform - Infrared Spectroscopy (FT-IR) to identify metanil yellow contamination in turmeric powder. Mixtures of metanil yellow in turmeric were prepared at concentrations of 30%, 25%, 20%, 15%, 10%, 5%, 1% and 0.01% (w/w). The FT-Raman and FT-IR spectral signal of pure turmeric powder, pure metanil yellow powder and the 8 sample mixtures were obtained and analyzed independently to identify metanil yellow contamination in turmeric. The results show that FT-Raman spectroscopy and FT-IR spectroscopy can detect metanil yellow mixed with turmeric at concentrations as low as 1% and 5%, respectively, and may be useful for non-destructive detection of adulterated turmeric powder.

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

    Science.gov (United States)

    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

  18. Combined IR-Raman vs vibrational sum-frequency heterospectral correlation spectroscopy

    Science.gov (United States)

    Roy, Sandra; Beutier, Clémentine; Hore, Dennis K.

    2018-06-01

    Vibrational sum-frequency generation spectroscopy is a valuable probe of surface structure, particularly when the same molecules are present in one of the adjacent bulk solid or solution phases. As a result of the non-centrosymmetric requirement of SFG, the signal generated is a marker of the extent to which the molecules are ordered in an arrangement that breaks the up-down symmetry at the surface. In cases where the accompanying changes in the bulk are of interest in understanding and interpreting the surface structure, simultaneous analysis of the bulk IR absorption or bulk Raman scattering is helpful, and may be used in heterospectral surface-bulk two-dimensional correlation. We demonstrate that, in such cases, generating a new type of bulk spectrum that combines the IR and Raman amplitudes is a better candidate than the individual IR and Raman spectra for the purpose of correlation with the SFG signal.

  19. GHz Yb:KYW oscillators in time-resolved spectroscopy

    Science.gov (United States)

    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.

  20. Assessment of Azithromycin in Pharmaceutical Formulation by Fourier-transform Infrared (FT-IR Transmission Spectroscopy

    Directory of Open Access Journals (Sweden)

    Muhammad Ali Mallah

    2011-12-01

    Full Text Available A simple, rapid and economical method for azithromycin quantification in solid tablet and capsule formulations has been developed by applying Fourier-transform Infrared (FT-IR transmission spectroscopy for regular quality monitoring. The newly developed method avoids the sample preparation, except grinding for pellet formation and does not involve consumption of any solvent as it absolutely eliminates the need of extraction. KBr pellets were employed for the appraisal of azithromycin while acquiring spectra of standards as well as samples on FT-IR. By selecting the FT-IR carbonyl band (C=O in the region 1,744–1,709 cm−1 the calibration model was developed based on simple Beer’s law. The excellent regression coefficient (R2 0.999 was accomplished for calibration set having standard error of calibration equal to 0.01 mg. The current work exposes that transmission FT-IR spectroscopy can definitely be applied to determine the exact amount of azithromycin to control the processing and quality of solid formulations with reduced cost and short analysis time.

  1. Characterization by Fourier transform infrared spectroscopy (FT-IR) and 2D IR correlation spectroscopy of a carbosilane dendrimer with peripheral ammonium groups

    Energy Technology Data Exchange (ETDEWEB)

    Popescu, Maria-Cristina, E-mail: cpopescu@icmpp.ro [' Petru Poni' Institute of Macromolecular Chemistry (Romania); Gomez, Rafael; Mata, Fco Javier de la; Rasines, Beatriz [Universidad de Alcala, Departamento de Quimica Inorganica (Spain); Simionescu, Bogdan C. [' Petru Poni' Institute of Macromolecular Chemistry (Romania)

    2013-06-15

    Fourier transform infrared spectroscopy and 2D correlation spectroscopy were used to study the microstructural changes occurring on heating of a new carbosilane dendrimer with peripheral ammonium groups. Temperature-dependent spectral variations in the 3,010-2,710, 1,530-1,170, and 1,170-625 cm{sup -1} regions were monitored during the heating process. The dependence, on temperature, of integral absorptions and position of spectral bands was established and the spectral modifications associated with molecular conformation rearrangements, allowing molecular shape changes, were found. Before 180 Degree-Sign C, the studied carbosilane dendrimer proved to be stable, while at higher temperatures it oxidizes and Si-O groups appear. 2D IR correlation spectroscopy gives new information about the effect of temperature on the structure and dynamics of the system. Synchronous and asynchronous spectra indicate that, at low temperature, conformational changes of CH{sub 3} and CH{sub 3}-N{sup +} groups take place first. With increasing temperature, the intensity variation of the CH{sub 2}, C-N, Si-C and C-C groups from the dendritic core is faster than that of the terminal units. This indicates that, with increasing temperature, the segments of the dendritic core obtain enough energy to change their conformation more easily as compared to the terminal units, due to their internal flexibility.

  2. Characterization by Fourier transform infrared spectroscopy (FT-IR) and 2D IR correlation spectroscopy of a carbosilane dendrimer with peripheral ammonium groups

    International Nuclear Information System (INIS)

    Popescu, Maria-Cristina; Gómez, Rafael; Mata, Fco Javier de la; Rasines, Beatriz; Simionescu, Bogdan C.

    2013-01-01

    Fourier transform infrared spectroscopy and 2D correlation spectroscopy were used to study the microstructural changes occurring on heating of a new carbosilane dendrimer with peripheral ammonium groups. Temperature-dependent spectral variations in the 3,010–2,710, 1,530–1,170, and 1,170–625 cm −1 regions were monitored during the heating process. The dependence, on temperature, of integral absorptions and position of spectral bands was established and the spectral modifications associated with molecular conformation rearrangements, allowing molecular shape changes, were found. Before 180 °C, the studied carbosilane dendrimer proved to be stable, while at higher temperatures it oxidizes and Si–O groups appear. 2D IR correlation spectroscopy gives new information about the effect of temperature on the structure and dynamics of the system. Synchronous and asynchronous spectra indicate that, at low temperature, conformational changes of CH 3 and CH 3 –N + groups take place first. With increasing temperature, the intensity variation of the CH 2 , C–N, Si–C and C–C groups from the dendritic core is faster than that of the terminal units. This indicates that, with increasing temperature, the segments of the dendritic core obtain enough energy to change their conformation more easily as compared to the terminal units, due to their internal flexibility.

  3. Molecular orientation in aligned electrospun polyimide nanofibers by polarized FT-IR spectroscopy.

    Science.gov (United States)

    Yang, Haoqi; Jiang, Shaohua; Fang, Hong; Hu, Xiaowu; Duan, Gaigai; Hou, Haoqing

    2018-07-05

    Quantitative explanation on the improved mechanical properties of aligned electrospun polyimide (PI) nanofibers as the increased imidization temperatures is highly required. In this work, polarized FT-IR spectroscopy is applied to solve this problem. Based on the polarized FT-IR spectroscopy and the molecular model in the fibers, the length of the repeat unit of PI molecule, the angle between the fiber axis and the symmetric stretching direction of carbonyl group on the imide ring, and the angle between the PI molecular axis and fiber axis are all investigated. The Mark-Howink equation is used to calculate the number-average molar mass of PI molecules. The orientation states of PI molecules in the electrospun nanofibers are studied from the number-average molar mass of PI molecules and the average fiber diameter. Quantitative analysis of the orientation factor of PI molecules in the electrospun nanofibers is performed by polarized FT-IR spectroscopy. Copyright © 2018 Elsevier B.V. All rights reserved.

  4. Time-Resolved Synchronous Fluorescence for Biomedical Diagnosis

    Science.gov (United States)

    Zhang, Xiaofeng; Fales, Andrew; Vo-Dinh, Tuan

    2015-01-01

    This article presents our most recent advances in synchronous fluorescence (SF) methodology for biomedical diagnostics. The SF method is characterized by simultaneously scanning both the excitation and emission wavelengths while keeping a constant wavelength interval between them. Compared to conventional fluorescence spectroscopy, the SF method simplifies the emission spectrum while enabling greater selectivity, and has been successfully used to detect subtle differences in the fluorescence emission signatures of biochemical species in cells and tissues. The SF method can be used in imaging to analyze dysplastic cells in vitro and tissue in vivo. Based on the SF method, here we demonstrate the feasibility of a time-resolved synchronous fluorescence (TRSF) method, which incorporates the intrinsic fluorescent decay characteristics of the fluorophores. Our prototype TRSF system has clearly shown its advantage in spectro-temporal separation of the fluorophores that were otherwise difficult to spectrally separate in SF spectroscopy. We envision that our previously-tested SF imaging and the newly-developed TRSF methods will combine their proven diagnostic potentials in cancer diagnosis to further improve the efficacy of SF-based biomedical diagnostics. PMID:26404289

  5. Application of Fourier transform infrared (FT-IR) spectroscopy in determination of microalgal compositions.

    Science.gov (United States)

    Meng, Yingying; Yao, Changhong; Xue, Song; Yang, Haibo

    2014-01-01

    Fourier transform infrared spectroscopy (FT-IR) was applied in algal strain screening and monitoring cell composition dynamics in a marine microalga Isochrysis zhangjiangensis during algal cultivation. The content of lipid, carbohydrate and protein of samples determined by traditional methods had validated the accuracy of FT-IR method. For algal screening, the band absorption ratios of lipid/amide I and carbo/amide I from FT-IR measurements allowed for the selection of Isochrysis sp. and Tetraselmis subcordiformis as the most potential lipid and carbohydrate producers, respectively. The cell composition dynamics of I. zhangjiangensis measured by FT-IR revealed the diversion of carbon allocation from protein to carbohydrate and neutral lipid when nitrogen-replete cells were subjected to nitrogen limitation. The carbo/amide I band absorption ratio had also been demonstrated to depict physiological status under nutrient stress in T. subcordiformis. FT-IR serves as a tool for the simultaneous measurement of lipid, carbohydrate, and protein content in cell. Copyright © 2013 Elsevier Ltd. All rights reserved.

  6. Advances in high-order harmonic generation sources for time-resolved investigations

    Energy Technology Data Exchange (ETDEWEB)

    Reduzzi, Maurizio [Dipartimento di Fisica, Politecnico di Milano, Piazza Leonardo da Vinci 32, 20133 Milano (Italy); Institute of Photonics and Nanotechnologies, CNR-IFN, Piazza Leonardo da Vinci 32, 20133 Milano (Italy); Carpeggiani, Paolo [Dipartimento di Fisica, Politecnico di Milano, Piazza Leonardo da Vinci 32, 20133 Milano (Italy); Kühn, Sergei [ELI-ALPS, ELI-Hu Kft., Dugonics ter 13, H-6720 Szeged (Hungary); Calegari, Francesca [Institute of Photonics and Nanotechnologies, CNR-IFN, Piazza Leonardo da Vinci 32, 20133 Milano (Italy); Nisoli, Mauro; Stagira, Salvatore [Dipartimento di Fisica, Politecnico di Milano, Piazza Leonardo da Vinci 32, 20133 Milano (Italy); Institute of Photonics and Nanotechnologies, CNR-IFN, Piazza Leonardo da Vinci 32, 20133 Milano (Italy); Vozzi, Caterina [Institute of Photonics and Nanotechnologies, CNR-IFN, Piazza Leonardo da Vinci 32, 20133 Milano (Italy); Dombi, Peter [ELI-ALPS, ELI-Hu Kft., Dugonics ter 13, H-6720 Szeged (Hungary); Wigner Research Center for Physics, 1121 Budapest (Hungary); Kahaly, Subhendu [ELI-ALPS, ELI-Hu Kft., Dugonics ter 13, H-6720 Szeged (Hungary); Tzallas, Paris; Charalambidis, Dimitris [ELI-ALPS, ELI-Hu Kft., Dugonics ter 13, H-6720 Szeged (Hungary); Foundation for Research and Technology – Hellas, Institute of Electronic Structure and Lasers, P.O. Box 1527, GR-711 10 Heraklion, Crete (Greece); Varju, Katalin [ELI-ALPS, ELI-Hu Kft., Dugonics ter 13, H-6720 Szeged (Hungary); Department of Optics and Quantum Electronics, University of Szeged, Dóm tér 9, 6720 Szeged (Hungary); Osvay, Karoly [ELI-ALPS, ELI-Hu Kft., Dugonics ter 13, H-6720 Szeged (Hungary); and others

    2015-10-15

    We review the main research directions ongoing in the development of extreme ultraviolet sources based on high-harmonic generation for the synthesization and application of trains and isolated attosecond pulses to time-resolved spectroscopy. A few experimental and theoretical works will be discussed in connection to well-established attosecond techniques. In this context, we present the unique possibilities offered for time-resolved investigations on the attosecond timescale by the new Extreme Light Infrastructure Attosecond Light Pulse Source, which is currently under construction.

  7. Advances in high-order harmonic generation sources for time-resolved investigations

    International Nuclear Information System (INIS)

    Reduzzi, Maurizio; Carpeggiani, Paolo; Kühn, Sergei; Calegari, Francesca; Nisoli, Mauro; Stagira, Salvatore; Vozzi, Caterina; Dombi, Peter; Kahaly, Subhendu; Tzallas, Paris; Charalambidis, Dimitris; Varju, Katalin; Osvay, Karoly

    2015-01-01

    We review the main research directions ongoing in the development of extreme ultraviolet sources based on high-harmonic generation for the synthesization and application of trains and isolated attosecond pulses to time-resolved spectroscopy. A few experimental and theoretical works will be discussed in connection to well-established attosecond techniques. In this context, we present the unique possibilities offered for time-resolved investigations on the attosecond timescale by the new Extreme Light Infrastructure Attosecond Light Pulse Source, which is currently under construction.

  8. Identification and characterization of salmonella serotypes using DNA spectral characteristics by fourier transform infrared (FT-IR) spectroscopy

    Science.gov (United States)

    Analysis of DNA samples of Salmonella serotypes (Salmonella Typhimurium, Salmonella Enteritidis, Salmonella Infantis, Salmonella Heidelberg and Salmonella Kentucky) were performed using Fourier transform infrared spectroscopy (FT-IR) spectrometer by placing directly in contact with a diamond attenua...

  9. Time-resolved Femtosecond Photon Echo Probes Bimodal Solvent Dynamics

    NARCIS (Netherlands)

    Pshenichnikov, M.S; Duppen, K.; Wiersma, D. A.

    1995-01-01

    We report on time-resolved femtosecond photon echo experiments of a dye molecule in a polar solution. The photon echo is time resolved by mixing the echo with a femtosecond gate pulse in a nonlinear crystal. It is shown that the temporal profile of the photon echo allows separation of the

  10. Mid IR-fiber spectroscopy in the 2-17μm range

    Science.gov (United States)

    Artyushenko, Viatcheslav G.; Bocharnikov, A.; Colquhoun, Gary; Leach, Clive A.; Lobachov, Vladimir; Pirogova, Lyudmila; Sakharova, Tatjana; Savitskij, Dmitrij; Ezhevskaya, Tatjana; Bublikov, Alexandr

    2007-10-01

    The latest development in IR-fibre optics enables us to expand the spectral range of process spectroscopy from 2μm out to 17μm (5000 to 600cm-1) i.e. into the most informative "finger-print" part of the spectrum. Mid-IR wavelength ranges from 2 to 6-10μm may be covered by Chalcogenide IR-glass CIR-fibres while Polycrystalline PIR-fibres made of Silver Halides solid solutions transmit 4-17 μm wavelength radiation. PIR-fibre immersion ATR probes and Transmission/Reflection probes had been manufactured and successfully tested with different FTIR spectrometers in the field of remote spectroscopy for forensic substances identification, chemical reaction control, and monitoring of exhaust or exhalation gases. Using these techniques no sample preparation is necessary for fibre probes to measure evanescent, reflection and transmission spectra, in situ and in real time. QCL spectrometer may be used as a portable device for multispectral gas analysis at 1ppb level of detectivity for various applications in environmental pollution monitoring.

  11. Collaborative Student Laboratory Exercise Using FT-IR Spectroscopy for the Kinetics Study of a Biotin Analogue

    Science.gov (United States)

    Leong, Jhaque; Ackroyd, Nathan C.; Ho, Karen

    2014-01-01

    The synthesis of N-methoxycarbonyl-2-imidazolidone, an analogue of biotin, was conducted by organic chemistry students and confirmed using FT-IR and H NMR. Spectroscopy students used FT-IR to measure the rate of hydrolysis of the product and determined the rate constant for the reaction using the integrated rate law. From the magnitude of the rate…

  12. Quantitative analysis of time-resolved infrared stimulated luminescence in feldspars

    DEFF Research Database (Denmark)

    Pagonis, Vasilis; Ankjærgaard, Christina; Jain, Mayank

    2016-01-01

    Time-resolved infrared-stimulated luminescence (TR-IRSL) from feldspar samples is of importance in the field of luminescence dating, since it provides information on the luminescence mechanism in these materials. In this paper we present new analytical equations which can be used to analyze TR-IR....... The equations are applied to experimental TR-IRSL data of natural feldspars, and good agreement is found between experimental and modeling results....

  13. Rapid identification of Chinese Sauce liquor from different fermentation positions with FT-IR spectroscopy

    Science.gov (United States)

    Li, Changwen; Wei, Jiping; Zhou, Qun; Sun, Suqin

    2008-07-01

    FT-IR and two-dimensional correlation spectroscopy (2D-IR) technology were applied to discriminate Chinese Sauce liquor from different fermentation positions (top, middle and bottom of fermentation cellar) for the first time. The liquors at top, middle and bottom of fermentation cellar, possessed the characteristic peaks at 1731 cm -1, 1733 cm -1 and 1602 cm -1, respectively. In the 2D correlation infrared spectra, the differences were amplified. A strong auto-peak at 1725 cm -1 showed in the 2D spectra of the Top Liquor, which indicated that the liquor might contain some ester compounds. Different from Top Liquor, three auto-peaks at 1695, 1590 and 1480 cm -1 were identified in 2D spectra of Middle Liquor, which were the characteristic absorption of acid, lactate. In 2D spectra of Bottom Liquor, two auto-peaks at 1570 and 1485 cm -1 indicated that lactate was the major component. As a result, FT-IR and 2D-IR correlation spectra technology provided a rapid and effective method for the quality analysis of the Sauce liquor.

  14. Attenuated total reflectance-FT-IR spectroscopy for gunshot residue analysis: potential for ammunition determination.

    Science.gov (United States)

    Bueno, Justin; Sikirzhytski, Vitali; Lednev, Igor K

    2013-08-06

    The ability to link a suspect to a particular shooting incident is a principal task for many forensic investigators. Here, we attempt to achieve this goal by analysis of gunshot residue (GSR) through the use of attenuated total reflectance (ATR) Fourier transform infrared spectroscopy (FT-IR) combined with statistical analysis. The firearm discharge process is analogous to a complex chemical process. Therefore, the products of this process (GSR) will vary based upon numerous factors, including the specific combination of the firearm and ammunition which was discharged. Differentiation of FT-IR data, collected from GSR particles originating from three different firearm-ammunition combinations (0.38 in., 0.40 in., and 9 mm calibers), was achieved using projection to latent structures discriminant analysis (PLS-DA). The technique was cross (leave-one-out), both internally and externally, validated. External validation was achieved via assignment (caliber identification) of unknown FT-IR spectra from unknown GSR particles. The results demonstrate great potential for ATR-FT-IR spectroscopic analysis of GSR for forensic purposes.

  15. Catalysis of GTP hydrolysis by small GTPases at atomic detail by integration of X-ray crystallography, experimental, and theoretical IR spectroscopy.

    Science.gov (United States)

    Rudack, Till; Jenrich, Sarah; Brucker, Sven; Vetter, Ingrid R; Gerwert, Klaus; Kötting, Carsten

    2015-10-02

    Small GTPases regulate key processes in cells. Malfunction of their GTPase reaction by mutations is involved in severe diseases. Here, we compare the GTPase reaction of the slower hydrolyzing GTPase Ran with Ras. By combination of time-resolved FTIR difference spectroscopy and QM/MM simulations we elucidate that the Mg(2+) coordination by the phosphate groups, which varies largely among the x-ray structures, is the same for Ran and Ras. A new x-ray structure of a Ran·RanBD1 complex with improved resolution confirmed this finding and revealed a general problem with the refinement of Mg(2+) in GTPases. The Mg(2+) coordination is not responsible for the much slower GTPase reaction of Ran. Instead, the location of the Tyr-39 side chain of Ran between the γ-phosphate and Gln-69 prevents the optimal positioning of the attacking water molecule by the Gln-69 relative to the γ-phosphate. This is confirmed in the RanY39A·RanBD1 crystal structure. The QM/MM simulations provide IR spectra of the catalytic center, which agree very nicely with the experimental ones. The combination of both methods can correlate spectra with structure at atomic detail. For example the FTIR difference spectra of RasA18T and RanT25A mutants show that spectral differences are mainly due to the hydrogen bond of Thr-25 to the α-phosphate in Ran. By integration of x-ray structure analysis, experimental, and theoretical IR spectroscopy the catalytic center of the x-ray structural models are further refined to sub-Å resolution, allowing an improved understanding of catalysis. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

  16. Catalysis of GTP Hydrolysis by Small GTPases at Atomic Detail by Integration of X-ray Crystallography, Experimental, and Theoretical IR Spectroscopy*

    Science.gov (United States)

    Rudack, Till; Jenrich, Sarah; Brucker, Sven; Vetter, Ingrid R.; Gerwert, Klaus; Kötting, Carsten

    2015-01-01

    Small GTPases regulate key processes in cells. Malfunction of their GTPase reaction by mutations is involved in severe diseases. Here, we compare the GTPase reaction of the slower hydrolyzing GTPase Ran with Ras. By combination of time-resolved FTIR difference spectroscopy and QM/MM simulations we elucidate that the Mg2+ coordination by the phosphate groups, which varies largely among the x-ray structures, is the same for Ran and Ras. A new x-ray structure of a Ran·RanBD1 complex with improved resolution confirmed this finding and revealed a general problem with the refinement of Mg2+ in GTPases. The Mg2+ coordination is not responsible for the much slower GTPase reaction of Ran. Instead, the location of the Tyr-39 side chain of Ran between the γ-phosphate and Gln-69 prevents the optimal positioning of the attacking water molecule by the Gln-69 relative to the γ-phosphate. This is confirmed in the RanY39A·RanBD1 crystal structure. The QM/MM simulations provide IR spectra of the catalytic center, which agree very nicely with the experimental ones. The combination of both methods can correlate spectra with structure at atomic detail. For example the FTIR difference spectra of RasA18T and RanT25A mutants show that spectral differences are mainly due to the hydrogen bond of Thr-25 to the α-phosphate in Ran. By integration of x-ray structure analysis, experimental, and theoretical IR spectroscopy the catalytic center of the x-ray structural models are further refined to sub-Å resolution, allowing an improved understanding of catalysis. PMID:26272610

  17. Time-resolved materials science opportunities using synchrotron x-ray sources

    International Nuclear Information System (INIS)

    Larson, B.C.; Tischler, J.Z.

    1995-06-01

    The high brightness, high intensity, and pulsed time-structure of synchrotron sources provide new opportunities for time-resolved x-ray diffraction investigations. With third generation synchrotron sources coming on line, high brilliance and high brightness are now available in x-ray beams with the highest flux. In addition to the high average flux, the instantaneous flux available in synchrotron beams is greatly enhanced by the pulsed time structure, which consists of short bursts of x-rays that are separated by ∼tens to hundreds of nanoseconds. Time-resolved one- and two-dimensional position sensitive detection techniques that take advantage of synchrotron radiation for materials science x-ray diffraction investigations are presented, and time resolved materials science applications are discussed in terms of recent diffraction and spectroscopy results and materials research opportunities

  18. Time-resolved imaging of purely valence-electron dynamics during a chemical reaction

    DEFF Research Database (Denmark)

    Hockett, Paul; Bisgaard, Christer Z.; Clarkin, Owen J.

    2011-01-01

    Chemical reactions are manifestations of the dynamics of molecular valence electrons and their couplings to atomic motions. Emerging methods in attosecond science can probe purely electronic dynamics in atomic and molecular systems(1-6). By contrast, time-resolved structural-dynamics methods...... such as electron(7-10) or X-ray diffraction(11) and X-ray absorption(12) yield complementary information about the atomic motions. Time-resolved methods that are directly sensitive to both valence-electron dynamics and atomic motions include photoelectron spectroscopy(13-15) and high-harmonic generation(16......,17): in both cases, this sensitivity derives from the ionization-matrix element(18,19). Here we demonstrate a time-resolved molecular-frame photoelectron-angular-distribution (TRMFPAD) method for imaging the purely valence-electron dynamics during a chemical reaction. Specifically, the TRMFPADs measured during...

  19. Study of the Pyrrol/Diphenylamine Copolymer by FT-IR spectroscopy and conductivity

    Directory of Open Access Journals (Sweden)

    Carlos Alberto Perez

    2004-01-01

    Full Text Available The main goal of this study was to analyze the physical properties of the copolymer formed by the electrochemical deposition of the polydiphenylamine (PDPA on polypyrrole (Ppy and Ppy on PDPA, in different conditions, through the characterization of the materials formed by the resonant Raman, FT-IR and conductivity techniques. The interactions among the species which are present in the new copolymer structure and the changes in electronic conductivity, were verified. The copolymer was also synthesized electrochemically in the presence of iodide species and the material was characterized by FT-IR spectroscopy and conductivity. The role of the dopant was studied in the process of charge transfer between the copolymer-dopant, acting in the stabilization of the species in the polymer backbone and the increase of the electronic conductivity.

  20. Application of FT-IR spectroscopy on breast cancer serum analysis

    Science.gov (United States)

    Elmi, Fatemeh; Movaghar, Afshin Fayyaz; Elmi, Maryam Mitra; Alinezhad, Heshmatollah; Nikbakhsh, Novin

    2017-12-01

    Breast cancer is regarded as the most malignant tumor among women throughout the world. Therefore, early detection and proper diagnostic methods have been known to help save women's lives. Fourier Transform Infrared (FT-IR) spectroscopy, coupled with PCA-LDA analysis, is a new technique to investigate the characteristics of serum in breast cancer. In this study, 43 breast cancer and 43 healthy serum samples were collected, and the FT-IR spectra were recorded for each one. Then, PCA analysis and linear discriminant analysis (LDA) were used to analyze the spectral data. The results showed that there were differences between the spectra of the two groups. Discriminating wavenumbers were associated with several spectral differences over the 950-1200 cm- 1(sugar), 1190-1350 cm- 1 (collagen), 1475-1710 cm- 1 (protein), 1710-1760 cm- 1 (ester), 2800-3000 cm- 1 (stretching motions of -CH2 & -CH3), and 3090-3700 cm- 1 (NH stretching) regions. PCA-LDA performance on serum IR could recognize changes between the control and the breast cancer cases. The diagnostic accuracy, sensitivity, and specificity of PCA-LDA analysis for 3000-3600 cm- 1 (NH stretching) were found to be 83%, 84%, 74% for the control and 80%, 76%, 72% for the breast cancer cases, respectively. The results showed that the major spectral differences between the two groups were related to the differences in protein conformation in serum samples. It can be concluded that FT-IR spectroscopy, together with multivariate data analysis, is able to discriminate between breast cancer and healthy serum samples.

  1. Ultrafast Time-Resolved Photoluminescence Studies of Gallium-Arsenide

    Science.gov (United States)

    Johnson, Matthew Bruce

    This thesis concerns the study of ultrafast phenomena in GaAs using time-resolved photoluminescence (PL). The thesis consists of five chapters. Chapter one is an introduction, which discusses the study of ultrafast phenomena in semiconductors. Chapter two is a description of the colliding-pulse mode-locked (CPM) ring dye laser, which is at the heart of the experimental apparatus used in this thesis. Chapter three presents a detailed experimental and theoretical investigation of photoluminescence excitation correlation spectroscopy (PECS), the novel technique which is used to time-resolve ultrafast PL phenomena. Chapters 4 and 5 discuss two applications of the PECS technique. In Chapter 4 the variation of PL intensity in In-alloyed GaAs substrate material is studied, while Chapter 5 discusses the variation of carrier lifetimes in ion-damaged GaAs used in photo-conductive circuit elements (PCEs). PECS is a pulse-probe technique that measures the cross correlation of photo-excited carrier populations. The theoretical model employed in this thesis is based upon the rate equation for a simple three-level system consisting of valence and conduction bands and a single trap level. In the limit of radiative band-to-band dominated recombination, no PECS signal should be observed; while in the capture -dominated recombination limit, the PECS signal from the band-to-band PL measures the cross correlation of the excited electron and hole populations and thus, the electron and hole lifetimes. PECS is experimentally investigated using a case study of PL in semi-insulating (SI) GaAs and In -alloyed GaAs. At 77 K, the PECS signal is characteristic of a capture-dominated system, yielding an electron-hole lifetime of about 200 ps. However, at 5 K the behavior is more complicated and shows saturation effects due to the C acceptor level, which is un-ionized at 5 K. As a first application, PECS is used to investigate the large band-to-band PL contrast observed near dislocations in In

  2. Matrix isolation FT-IR spectroscopy and molecular orbital study of sarcosine methyl ester

    OpenAIRE

    Gómez-Zavaglia, Andrea; Fausto, R.

    2004-01-01

    N-methylglycine methyl ester (sarcosine-Me) has been studied by matrix isolation FT-IR spectroscopy and molecular orbital calculations undertaken at the DFT/B3LYP and MP2 levels of theory with the 6-311++G(d,p) and 6-31++G(d,p) basis set, respectively. Twelve different conformers were located in the potential energy surface of the studied compound, with the ASC conformer being the ground conformational state. This form is analogous to the dimethylglycine methyl ester most stable conformer and...

  3. Study on high-silicon boron-containing zeolite by thermogravimetric and IR-spectroscopy techniques

    International Nuclear Information System (INIS)

    Chukin, G.D.; Nefedov, B.K.; Surin, S.A.; Polinina, E.V.; Khusid, B.L.; Sidel'kovskaya, V.G.

    1985-01-01

    The structure identity of initial Na-forms of boron-containing and aluminosilicate high-silicon zeolites is established by thermogravimetric and IR-spectroscopy methods. The presence of boron in Na-forms of high-silicon zeolites is shown to lead to reduction of structure thermal stability. It is noted that thermal stability of the H-form of both high-silicon boron-containing and boron-free zeolites is practically equal and considerably higher than that of Na-forms

  4. Using FT-IR Spectroscopy to Elucidate the Structures of Ablative Polymers

    Science.gov (United States)

    Fan, Wendy

    2011-01-01

    The composition and structure of an ablative polymer has a multifaceted influence on its thermal, mechanical and ablative properties. Understanding the molecular level information is critical to the optimization of material performance because it helps to establish correlations with the macroscopic properties of the material, the so-called structure-property relationship. Moreover, accurate information of molecular structures is also essential to predict the thermal decomposition pathways as well as to identify decomposition species that are fundamentally important to modeling work. In this presentation, I will describe the use of infrared transmission spectroscopy (FT-IR) as a convenient tool to aid the discovery and development of thermal protection system materials.

  5. Novel lanthanide doped micro- and mesoporous solids. Characterization of ion-host-interactions, species distribution and luminescence properties using time-resolved luminescence spectroscopy; Neuartige Lanthanoid-dotierte mikro- und mesoporoese Feststoffe. Charakterisierung von Ion-Wirt-Wechselwirkungen, Speziesverteilung und Lumineszenzeigenschaften mittels zeitaufgeloester Lumineszenzspektroskopie

    Energy Technology Data Exchange (ETDEWEB)

    Gessner, Andre

    2010-12-15

    In this work lanthanide-doped microporous zeolites, microporous-mesoporous hybrid materials and mesoporous silicates were investigated regarding their luminescence properties and the ion-host-interactions using time-resolved luminescence spectroscopy. Thereby, time-resolved emission spectra (TRES) provide information in the wavelength and time domain. For the analysis of the TRES a broad set of analytic methods was applied and thus a corresponding ''toolbox'' developed. Fitting of the luminescence decays was performed with a discrete number of exponentials and supported by luminescence decay times distributions. Time-resolved area normalized emission spectra (TRANES), an advancement of TRES, could be used for the determination of the number of emissive lanthanide species in porous materials for the first time. Calculation of the decay-associated spectra (DAS) allowed the correlation of spectral information with luminescence decay times and thus delivered the luminescence spectra of the different europium species. For europium(III) we could use in addition the time-dependent asymmetry ratio and spectral evolution of the {sup 5}D{sub 0}-{sup 7}F{sub 0}-transition with time to obtain further information about the distribution of the lanthanide ions in the host material. Luminescence decay times and spectra allowed conclusions on the number of OH-oscillators in and the symmetry of the first coordination sphere. For the microporous and microporous-mesoporous materials were found different lanthanide species, which were characterized by the above mentioned methods. These lanthanide species can be found on different positions in the host material. One position is located deep in the pore system. Here, lanthanide ions are hardly accessible for water and mainly coordinated by framework oxygens. This results in long luminescence decay times and distorted coordination spheres. The second position can be found near or on the outer surface or in the

  6. Weak carbonyl-methyl intermolecular interactions in acetone clusters explored by IR plus VUV spectroscopy

    International Nuclear Information System (INIS)

    Guan, Jiwen; Hu, Yongjun; Xie, Min; Bernstein, Elliot R.

    2012-01-01

    Highlights: ► The carbonyl overtone of acetone clusters is observed by IR-VUV spectroscopy. ► Acetone molecules in the dimer are stacked with an antiparallel way. ► The structure of the acetone trimer and the tetramer are the cyclic structures. ► The carbonyl groups would interact with the methyl groups in acetone clusters. ► These weak interactions are further confirmed by H/D substitution experiment. -- Abstract: Size-selected IR–VUV spectroscopy is employed to detect vibrational characteristics in the region 2850 ∼ 3550 cm −1 of neutral acetone and its clusters (CH 3 COCH 3 ) n (n = 1–4). Features around 3440 cm −1 in the spectra of acetone monomer and its clusters are assigned to the carbonyl stretch (CO) overtone. These features red-shift from 3455 to 3433 cm −1 as the size of the clusters increases from the monomer to the tetramer. Based on calculations, the experimental IR spectra in the C=O overtone region suggest that the dominant structures for the acetone trimer and tetramer should be cyclic in the supersonic expansion sample. This study also suggests that the carbonyl groups interact with the methyl groups in the acetone clusters. These weak interactions are further confirmed by the use of deuterium substitution.

  7. Evaluation of Polymerization Efficacy in Composite Resins via FT-IR Spectroscopy and Vickers Microhardness Test

    Directory of Open Access Journals (Sweden)

    Tahereh-Sadat Jafarzadeh

    2015-12-01

    Full Text Available Background and aims. Polymerization efficacy affects the properties and performance of composite resin restorations.The purpose of this study was to evaluate the effectiveness of polymerization of two micro-hybrid, two nano-hybrid and one nano-filled ormocer-based composite resins, cured by two different light-curing systems, using Fourier transformation infrared (FT-IR spectroscopy and Vickers microhardness testing at two different depths (top surface, 2 mm. Materials and methods. For FT-IR spectrometry, five cylindrical specimens (5mm in diameter × 2 mm in length were prepared from each composite resin using Teflon molds and polymerized for 20 seconds. Then, 70-μm wafers were sectioned at the top surface and at2mm from the top surface. The degree of conversion for each sample was calculated using FT-IR spectroscopy. For Vickers micro-hardness testing, three cylindrical specimens were prepared from each composite resin and polymerized for 20 seconds. The Vickers microhardness test (Shimadzu, Type M, Japan was performed at the top and bottom (depth=2 mm surfaces of each specimen. Three-way ANOVA with independent variables and Tukey tests were performed at 95% significance level. Results. No significant differences were detected in degree of conversion and microhardness between LED and QTH light-curing units except for the ormocer-based specimen, CeramX, which exhibited significantly higher DC by LED. All the composite resins showed a significantly higher degree of conversion at the surface. Microhardness was not significantly affected by depth, except for Herculite XRV Ultra and CeramX, which showed higher values at the surface. Conclusion. Composite resins containing nano-particles generally exhibited more variations in degree of conversion and microhardness.

  8. Effect of Water on HEMA Conversion by FT-IR Spectroscopy

    Directory of Open Access Journals (Sweden)

    TS. Jafarzadeh Kashi

    2007-09-01

    Full Text Available Objective: The use of HEMA as a biocompatible material in dentin bonding systems and its potential for clinical applications has been well established. Excess water can affect conversion of bonding resins. The aim of this study was to survey the effect of water on the degree of conversion of HEMA by Fourier Transform Infra-red Spectroscopy (FT-IR.Materials and Methods: In this experimental study, distilled water was added in amounts of 0, 0.05, 0.1, 0.2, and 0.4 ml to 1 ml of curable HEMA solution. Six repetitions per wa-ter ratio were made and investigated. Each sample was polymerized for 60 seconds. De-gree of conversion was obtained from the absorbance IR-Spectrum of the materials before and after polymerization by FT-IR spectroscopy. One way ANOVA and Tukey-HSD were carried out to compare and detect any differences among groups.Results: Statistical analysis indicates highly significant difference between pairs of groups at level (P<0.001. The results showed a trend of decreasing in HEMA conversion with increasing water. Degree of conversion changes significantly within the 0.05 ml to 0.2 ml water range. However, degree of conversion did not change after reaching 0.02 ml and before 0.05.Conclusion: Degree of conversion of HEMA decreased by increasing water. The most dramatic effect of water on the polymerization process occurs within a range which exists under clinical conditions. The reason that the degree of conversion did not show signifi-cant result before 0.05 ml may be related to the hydrophilic nature of HEMA.

  9. Evaluation of Polymerization Efficacy in Composite Resins via FT-IR Spectroscopy and Vickers Microhardness Test.

    Science.gov (United States)

    Jafarzadeh, Tahereh-Sadat; Erfan, Mohammad; Behroozibakhsh, Marjan; Fatemi, Mostafa; Masaeli, Reza; Rezaei, Yashar; Bagheri, Hossein; Erfan, Yasaman

    2015-01-01

    Background and aims. Polymerization efficacy affects the properties and performance of composite resin restorations.The purpose of this study was to evaluate the effectiveness of polymerization of two micro-hybrid, two nano-hybrid and one nano-filled ormocer-based composite resins, cured by two different light-curing systems, using Fourier transformation infrared (FT-IR) spectroscopy and Vickers microhardness testing at two different depths (top surface, 2 mm). Materials and methods. For FT-IR spectrometry, five cylindrical specimens (5mm in diameter × 2 mm in length) were prepared from each composite resin using Teflon molds and polymerized for 20 seconds. Then, 70-μm wafers were sectioned at the top surface and at2mm from the top surface. The degree of conversion for each sample was calculated using FT-IR spectroscopy. For Vickers micro-hardness testing, three cylindrical specimens were prepared from each composite resin and polymerized for 20 seconds. The Vickers microhardness test (Shimadzu, Type M, Japan) was performed at the top and bottom (depth=2 mm) surfaces of each specimen. Three-way ANOVA with independent variables and Tukey tests were performed at 95% significance level. Results. No significant differences were detected in degree of conversion and microhardness between LED and QTH light-curing units except for the ormocer-based specimen, CeramX, which exhibited significantly higher DC by LED. All the composite resins showed a significantly higher degree of conversion at the surface. Microhardness was not significantly affected by depth, except for Herculite XRV Ultra and CeramX, which showed higher values at the surface. Conclusion. Composite resins containing nano-particles generally exhibited more variations in degree of conversion and microhardness.

  10. Drift and transmission FT-IR spectroscopy of forest soils: an approach to determine decomposition processes of forest litter

    International Nuclear Information System (INIS)

    Haberhauer, G.; Gerzabek, M.H.

    1999-06-01

    A method is described to characterize organic soil layers using Fourier transformed infrared spectroscopy. The applicability of FT-IR, either dispersive or transmission, to investigate decomposition processes of spruce litter in soil originating from three different forest sites in two climatic regions was studied. Spectral information of transmission and diffuse reflection FT-IR spectra was analyzed and compared. For data evaluation Kubelka Munk (KM) transformation was applied to the DRIFT spectra. Sample preparation for DRIFT is simpler and less time consuming in comparison to transmission FT-IR, which uses KBr pellets. A variety of bands characteristics of molecular structures and functional groups has been identified for these complex samples. Analysis of both transmission FT-IR and DRIFT, showed that the intensity of distinct bands is a measure of the decomposition of forest litter. Interferences due to water adsorption spectra were reduced by DRIFT measurement in comparison to transmission FT-IR spectroscopy. However, data analysis revealed that intensity changes of several bands of DRIFT and transmission FT-IR were significantly correlated with soil horizons. The application of regression models enables identification and differentiation of organic forest soil horizons and allows to determine the decomposition status of soil organic matter in distinct layers. On the basis of the data presented in this study, it may be concluded that FT-IR spectroscopy is a powerful tool for the investigation of decomposition dynamics in forest soils. (author)

  11. Time-resolved biophysical approaches to nucleocytoplasmic transport

    Directory of Open Access Journals (Sweden)

    Francesco Cardarelli

    Full Text Available Molecules are continuously shuttling across the nuclear envelope barrier that separates the nucleus from the cytoplasm. Instead of being just a barrier to diffusion, the nuclear envelope is rather a complex filter that provides eukaryotes with an elaborate spatiotemporal regulation of fundamental molecular processes, such as gene expression and protein translation. Given the highly dynamic nature of nucleocytoplasmic transport, during the past few decades large efforts were devoted to the development and application of time resolved, fluorescence-based, biophysical methods to capture the details of molecular motion across the nuclear envelope. These methods are here divided into three major classes, according to the differences in the way they report on the molecular process of nucleocytoplasmic transport. In detail, the first class encompasses those methods based on the perturbation of the fluorescence signal, also known as ensemble-averaging methods, which average the behavior of many molecules (across many pores. The second class comprises those methods based on the localization of single fluorescently-labelled molecules and tracking of their position in space and time, potentially across single pores. Finally, the third class encompasses methods based on the statistical analysis of spontaneous fluorescence fluctuations out of the equilibrium or stationary state of the system. In this case, the behavior of single molecules is probed in presence of many similarly-labelled molecules, without dwelling on any of them. Here these three classes, with their respective pros and cons as well as their main applications to nucleocytoplasmic shuttling will be briefly reviewed and discussed. Keywords: Fluorescence recovery after photobleaching, Single particle tracking, Fluorescence correlation spectroscopy, Diffusion, Transport, GFP, Nuclear pore complex, Live cell, Confocal microscopy

  12. Adding a dimension to the infrared spectra of interfaces: 2D SFG spectroscopy via mid-IR pulse shaping

    Science.gov (United States)

    Zanni, Martin

    2012-02-01

    Sum-frequency generation spectroscopy provides an infrared spectrum of interfaces and thus has widespread use in the materials and chemical sciences. In this presentation, I will present our recent work in developing a 2D pulse sequence to generate 2D SFG spectra of interfaces, in analogy to 2D infrared spectra used to measure bulk species. To develop this spectroscopy, we have utilized many of the tricks-of-the-trade developed in the 2D IR and 2D Vis communities in the last decade, including mid-IR pulse shaping. With mid-IR pulse shaping, the 2D pulse sequence is manipulated by computer programming in the desired frequency resolution, rotating frame, and signal pathway. We believe that 2D SFG will become an important tool in the interfacial sciences in an analogous way that 2D IR is now being used in many disciplines.

  13. Time-resolved far-infrared experiments at the National Synchrotron Light Source. Final report

    International Nuclear Information System (INIS)

    Tanner, D.B.; Reitze, D.H.; Carr, G.L.

    1999-01-01

    A facility for time-resolved infrared and far-infrared spectroscopy has been built and commissioned at the National Synchrotron Light Source. This facility permits the study of time dependent phenomena over a frequency range from 2-8000cm -1 (0.25 meV-1 eV). Temporal resolution is approximately 200 psec and time dependent phenomena in the time range out to 100 nsec can be investigated

  14. Cold, Gas-Phase UV and IR Spectroscopy of Protonated Leucine Enkephalin and its Analogues

    Science.gov (United States)

    Burke, Nicole L.; Redwine, James; Dean, Jacob C.; McLuckey, Scott A.; Zwier, Timothy S.

    2014-06-01

    The conformational preferences of peptide backbones and the resulting hydrogen bonding patterns provide critical biochemical information regarding the structure-function relationship of peptides and proteins. The spectroscopic study of cryogenically-cooled peptide ions in a mass spectrometer probes these H-bonding arrangements and provides information regarding the influence of a charge site. Leucine enkephalin, a biologically active endogenous opiod peptide, has been extensively studied as a model peptide in mass spectrometry. This talk will present a study of the UV and IR spectroscopy of protonated leucine enkephalin [YGGFL+H]+ and two of its analogues: the sodiated [YGGFL+Na]+ and C-terminally methyl esterified [YGGFL-OMe+H]+ forms. All experiments were performed in a recently completed multi-stage mass spectrometer outfitted with a cryocooled ion trap. Ions are generated via nano-electrospray ionization and the analyte of interest is isolated in a linear ion trap. The analyte ions are trapped in a 22-pole ion trap held at 5 K by a closed cycle helium cryostat and interrogated via UV and IR lasers. Photofragments are trapped and isolated in a second LIT and mass analyzed. Double-resonance UV and IR methods were used to assign the conformation of [YGGFL+H]+, using the NH/OH stretch, Amide I, and Amide II regions of the infrared spectrum. The assigned structure contains a single backbone conformation at vibrational/rotational temperatures of 10 K held together with multiple H-bonds that self-solvate the NH3+ site. A "proton wire" between the N and C termini reinforces the H-bonding activity of the COO-H group to the F-L peptide bond, whose cleavage results in formation of the b4 ion, which is a prevalent, low-energy fragmentation pathway for [YGGFL+H]+. The reinforced H-bonding network in conjunction with the mobile proton theory may help explain the prevalence of the b4 pathway. In order to elucidate structural changes caused by modifying this H-bonding activity

  15. Phase-Sensitive Control Of Molecular Dissociation Through Attosecond Pump/Strong-Field Mid-IR Probe Spectroscopy

    Science.gov (United States)

    2016-04-15

    splitter (consisting of a thin, uncoated, silicon plate at brewsters angle) and the beams were focused onto the OPA crystal. For this work two...experiments in the future. These technologies include • Two-color driven (EUV/mid-IR) ion spectroscopy: we designed an interferometer combining EUV...isolated single-femtosecond EUV pulse generation: combining the use of low ionization threshold gas, an annual near-IR drive beam , polarization

  16. [A new measurement method of time-resolved spectrum].

    Science.gov (United States)

    Shi, Zhi-gang; Huang, Shi-hua; Liang, Chun-jun; Lei, Quan-sheng

    2007-02-01

    A new method for measuring time-resolved spectrum (TRS) is brought forward. Programming with assemble language controlled the micro-control-processor (AT89C51), and a kind of peripheral circuit constituted the drive circuit, which drived the stepping motor to run the monochromator. So the light of different kinds of expected wavelength could be obtained. The optical signal was transformed to electrical signal by optical-to-electrical transform with the help of photomultiplier tube (Hamamatsu 1P28). The electrical signal of spectrum data was transmitted to the oscillograph. Connecting the two serial interfaces of RS232 between the oscillograph and computer, the electrical signal of spectrum data could be transmitted to computer for programming to draw the attenuation curve and time-resolved spectrum (TRS) of the swatch. The method for measuring time-resolved spectrum (TRS) features parallel measurement in time scale but serial measurement in wavelength scale. Time-resolved spectrum (TRS) and integrated emission spectrum of Tb3+ in swatch Tb(o-BBA)3 phen were measured using this method. Compared with the real time-resolved spectrum (TRS). It was validated to be feasible, credible and convenient. The 3D spectra of fluorescence intensity-wavelength-time, and the integrated spectrum of the swatch Tb(o-BBA)3 phen are given.

  17. X-ray diffraction, IR spectroscopy and thermal characterization of partially hydrolyzed guar gum.

    Science.gov (United States)

    Mudgil, Deepak; Barak, Sheweta; Khatkar, B S

    2012-05-01

    Guar gum was hydrolyzed using cellulase from Aspergillus niger at 5.6 pH and 50°C temperature. Hydrolyzed guar gum sample was characterized using Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analysis, X-ray diffraction, dilute solution viscometry and rotational viscometry. Viscometry analysis of native guar gum showed a molecular weight of 889742.06, whereas, after enzymatic hydrolysis, the resultant product had a molecular weight of 7936.5. IR spectral analysis suggests that after enzymatic hydrolysis of guar gum there was no major transformation of functional group. Thermal analysis revealed no major change in thermal behavior of hydrolyzed guar gum. It was shown that partial hydrolysis of guar gum could be achieved by inexpensive and food grade cellulase (Aspergillus niger) having commercial importance and utilization as a functional soluble dietary fiber for food industry. Copyright © 2012 Elsevier B.V. All rights reserved.

  18. Detecting infrared luminescence and non-chemical signaling of living cells: single cell mid-IR spectroscopy in cryogenic environments

    Science.gov (United States)

    Pereverzev, Sergey

    2017-02-01

    Many life-relevant interaction energies are in IR range, and it is reasonable to believe that some biochemical reactions inside cells can results in emission of IR photons. Cells can use this emission for non-chemical and non-electrical signaling. Detecting weak infrared radiation from live cells is complicated because of strong thermal radiation background and absorption of radiation by tissues. A microfluidic device with live cells inside a vacuum cryogenic environment should suppress this background, and thereby permit observation of live cell auto-luminescence or signaling in the IR regime. One can make IR-transparent windows not emitting in this range, so only the cell and a small amount of liquid around it will emit infrared radiation. Currently mid-IR spectroscopy of single cells requires the use of a synchrotron source to measure absorption or reflection spectra. Decreasing of thermal radiation background will allow absorption and reflection spectroscopy of cells without using synchrotron light. Moreover, cell auto-luminescence can be directly measured. The complete absence of thermal background radiation for cryogenically cooled samples allows the use IR photon-sensitive detectors and obtaining single molecule sensitivity in IR photo-luminescence measurements. Due to low photon energies, photo-luminescence measurements will be non-distractive for pressures samples. The technique described here is based upon US patent 9366574.

  19. Monitoring wine aging with Fourier transform infrared spectroscopy (FT-IR

    Directory of Open Access Journals (Sweden)

    Basalekou Marianthi

    2015-01-01

    Full Text Available Oak wood has commonly been used in wine aging but recently other wood types such as Acacia and Chestnut, have attracted the interest of the researchers due to their possible positive contribution to wine quality. However, only the use of oak and chestnut woods is approved by the International Enological Codex of the International Organisation of Vine and Wine. In this study Fourier Transform (FT-mid-infrared spectroscopy combined with Discriminant Analysis was used to differentiate wines aged in barrels made from French oak, American oak, Acacia and Chestnut and in tanks with oak chips, over a period of 12 months. Two red (Mandilaria, Kotsifali and two white (Vilana, Dafni native Greek grape varieties where used to produce four wines. The Fourier Transform Infrared (FT-IR spectra of the samples were recorded on a Zinc Selenide (ZnSe window after incubation at 40 °C for 30 min. A complete differentiation of the samples according to both the type of wood used and the contact time was achieved based on their FT-IR spectra.

  20. Identification of forged Bank of England £20 banknotes using IR spectroscopy.

    Science.gov (United States)

    Sonnex, Emily; Almond, Matthew J; Baum, John V; Bond, John W

    2014-01-24

    Bank of England notes of £20 denomination have been studied using infrared spectroscopy in order to generate a method to identify forged notes. An aim of this work was to develop a non-destructive method so that a small, compact Fourier transform infrared spectrometer (FT-IR) instrument could be used by bank workers, police departments or others such as shop assistants to identify forged notes in a non-lab setting. The ease of use of the instrument is the key to this method, as well as the relatively low cost. The presence of a peak at 1400 cm(-1) arising from νasym (CO3(2-)) from the blank paper section of a forged note proved to be a successful indicator of the note's illegality for the notes that we studied. Moreover, differences between the spectra of forged and genuine £20 notes were observed in the ν(OH) (ca. 3500 cm(-1)), ν(C-H) (ca. 2900 cm(-1)) and ν(C=O) (ca. 1750 cm(-1)) regions of the IR spectrum recorded for the polymer film covering the holographic strip. In cases where these simple tests fail, we have shown how an infrared microscope can be used to further differentiate genuine and forged banknotes by producing infrared maps of selected areas of the note contrasting inks with background paper. Copyright © 2013 Elsevier B.V. All rights reserved.

  1. Identification of forged Bank of England £20 banknotes using IR spectroscopy

    Science.gov (United States)

    Sonnex, Emily; Almond, Matthew J.; Baum, John V.; Bond, John W.

    2014-01-01

    Bank of England notes of £20 denomination have been studied using infrared spectroscopy in order to generate a method to identify forged notes. An aim of this work was to develop a non-destructive method so that a small, compact Fourier transform infrared spectrometer (FT-IR) instrument could be used by bank workers, police departments or others such as shop assistants to identify forged notes in a non-lab setting. The ease of use of the instrument is the key to this method, as well as the relatively low cost. The presence of a peak at 1400 cm-1 arising from νasym (CO32-) from the blank paper section of a forged note proved to be a successful indicator of the note's illegality for the notes that we studied. Moreover, differences between the spectra of forged and genuine £20 notes were observed in the ν(OH) (ca. 3500 cm-1), ν(Csbnd H) (ca. 2900 cm-1) and ν(Cdbnd O) (ca. 1750 cm-1) regions of the IR spectrum recorded for the polymer film covering the holographic strip. In cases where these simple tests fail, we have shown how an infrared microscope can be used to further differentiate genuine and forged banknotes by producing infrared maps of selected areas of the note contrasting inks with background paper.

  2. Development of a method for determination of fatty acid using FT-IR spectroscopy

    Directory of Open Access Journals (Sweden)

    Dimas Augusto Morozin Zaia

    2011-05-01

    Full Text Available In the present paper a new methodology has been developed for determination of fatty acids in biological systems using FT-IR spectroscopy. For this method is not necessary chromophore reagent or pre sample preparation. Palmitic acid was chosen as standard, because it is found in several biological systems. The FT-IR spectrum of palmitic acid showed two absorption bands in the region of 2852 and 2920 cm-1 attributed to CH stretching. The results for these bands showed that the Beer-Lambert Law was followed in wide range of concentration of palmitic acid (14 to 257 mmol L-1. Potassium ferricyanide (K3[Fe(CN6] was used as internal standard. Several interferents were tested and only cholesterol, ferric chloride (higher concentration, mixture of amino acids for the band at 2919 cm-1 (higher concentration and triglyceride could be interferent if they appear in high concentration. Thus, this new methodology has advantage to be not expensive and simple.

  3. Surface enhanced imaging and IR spectroscopy of the biological cells on the nanostructured gold film

    Directory of Open Access Journals (Sweden)

    G.I. Dovbeshko

    2017-07-01

    Full Text Available New approach for optical imaging, structural study and cell cultivation based on the effect of the enhancement of optical signals from biomolecules and biological cells near nanostructured rough gold surface is proposed. The surface enhanced IR absorption (SEIRA spectroscopy and confocal microscopy experiments were made using the culture of SPEV (porcine embryonic kidney epithelium transplantable line and fibroblast cells, cultivated and/or adsorbed on the gold substrate. The SEIRA spectra registered from monolayer of the SPEV cells cultivated on the rough gold showed a low frequency shift of about 2 to 7 cm 1 for the most characteristic IR vibrations, compared with those adsorbed from suspension on the same substrate. An enhancement factor of 15…30 was obtained for different molecular vibrations. The confocal microscopy contrast images of the SPEV cells on rough gold substrate were obtained in laser fluorescence mode. This approach opens new possibilities for visualization of the living cells in vivo without staining. The fluorescence of the rough gold surfaces and effects responsible for our findings have been discussed.

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

    Science.gov (United States)

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

    2014-03-01

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

  5. Time-resolved emission from laser-ablated uranium

    International Nuclear Information System (INIS)

    Stoffels, E.; Mullen, J. van der; Weijer, P. van de

    1991-01-01

    Time-resolved emission spectra from the plasma, induced by laser ablation of uranium samples have been studied. The dependence of the emission intensity on time is strongly affected by the nature and pressure of the buffer gas. Air and argon have been used in the pressure range 0.002 to 5 mbar. The emission intensity as a function of time displays three maxima, indicating that three different processes within the expanding plasma plume are involved. On basis of the time-resolved spectra we propose a model that explains qualitatively the phenomena that are responsible for this time behaviour. (author)

  6. Gaz Phase IR and UV Spectroscopy of Neutral Contact Ion Pairs

    Science.gov (United States)

    Habka, Sana; Brenner, Valerie; Mons, Michel; Gloaguen, Eric

    2016-06-01

    Cations and anions, in solution, tend to pair up forming ion pairs. They play a crucial role in many fundamental processes in ion-concentrated solutions and living organisms. Despite their importance and vast applications in physics, chemistry and biochemistry, they remain difficult to characterize namely because of the coexistence of several types of pairing in solution. However, an interesting alternative consists in applying highly selective gas phase spectroscopy which can offer new insights on these neutral ion pairs. Our study consists in characterizing contact ion pairs (CIPs) in isolated model systems (M+, Ph-(CH2)n-COO- with M=Li, Na, K, Rb, Cs, and n=1-3), to determine their spectral signatures and compare them to ion pairs in solution. We have used laser desorption to vaporize a solid tablet containing the desired salt. Structural information for each system was obtained by mass-selective, UV and IR laser spectroscopy combined with high level quantum chemistry calculations1. Evidence of the presence of neutral CIPs was found by scanning the π-π* transition of the phenyl ring using resonant two-photon ionization (R2PI). Then, conformational selective IR/UV double resonance spectra were recorded in the CO2- stretch region for each conformation detected. The good agreement between theoretical data obtained at the BSSE-corrected-fullCCSD(T)/dhf-TZVPP//B97-D3/dhf-TZVPP level and experimental IR spectra led us to assign the 3D structure for each ion pair formed. Spectral signatures of (M+, Ph-CH2-COO-) pairs, were assigned to a bidentate CIPs between the alkali cation and the carboxylate group. In the case of (Li+, Ph-(CH2)3-COO-) pairs, the presence of a flexible side chain promotes a cation-π interaction leading to a tridentate O-O-π structure with its unique IR and UV signatures. IR spectra obtained on isolated CIPs were found very much alike the ones published on lithium and sodium acetate in solution2. However, in the case of sodium acetate, solution

  7. THE STUDY OF CLINOPTILOLITE MODIFIED WITH3d METALS HALIDES BY IR AND DIFFUSE REFLECTANCE SPECTROSCOPY

    Directory of Open Access Journals (Sweden)

    T. L. Rakitskaya

    2015-11-01

    Full Text Available The results of investigation of natural clinoptilolite (N-CLI and that modified with 3d metal halides (MeCl2/N-CLI, where Me are Cu, Co, and Mn by IR and diffuse reflectance spectroscopy are summarized. A band at 3437 cm-1 assigned to stretching vibrations of hydroxyl groups (nOH is found in the IR spectrum of the N-CLI sample. A location of the band was practically the same as for all above MeCl2/N-CLI samples. A band of middle intensity at 1638 cm-1 in the range of deformation vibrations of zeolite water observed in the IR spectrum of N-CLI slightly displays to lower frequencies in the case of the modified samples. An intensive wide band of a complex shape in the range from 1250 to 980 cm-1 assigned to Si–O–Si and Si–O–Al vibrations appears in IR spectra of all samples. A doublet band of middle intensity at 797 and 778 cm-1 is assigned to external symmetric stretching T-O vibrations and a band at 606 cm-1-to vibrations of a double ring. A location of the above bands is the same for all listed samples but their intensity is higher for MnCl2/N-CLI and CoCl2/N-CLI samples. After the reaction with ozone, significant changes in the IR spectra are observed only for MnCl2/N-CLI. They are due to MnO2 formation on the clinoptilolite surface resulting in a high frequency displacement of some bands. Based on UV-vi spectroscopy results, it is reasonable to make conclusions about the coordination and valence state of a central atom in the MeCl2/N-CLI samples under study. A location of charge transfer bands for these samples only slightly differs from that for N-CLI however the intensity of such bands increases for the MeCl2/N-CLI samples. The UV-vis spectrum of MnCl2/N-CLI changes after the reaction with ozone: the appearance of new bands of  charge transfer at 363 and 354 nm and also the two-fold increase in intensity of a charge transfer band at 272 nm in comparison with those of N-CLI and MnCl2/N-CLI are the evidence of change in both the

  8. Photoexcitation dynamics of nitric oxide bound ferric myoglobin probed by femtosecond IR spectroscopy

    Directory of Open Access Journals (Sweden)

    Park Jaehun

    2013-03-01

    Full Text Available Time-resolved vibrational spectra show that photolysis quantum yield of NO bound ferric myoglobin is smaller than 0.86, the deligated NO geminately rebinds with subnanosecond time scale, and the rebinding kinetics depends on protein conformation.

  9. Multi-frame pyramid correlation for time-resolved PIV

    NARCIS (Netherlands)

    Sciacchitano, A.; Scarano, F.; Wieneke, B.

    2012-01-01

    A novel technique is introduced to increase the precision and robustness of time-resolved particle image velocimetry (TR-PIV) measurements. The innovative element of the technique is the linear combination of the correlation signal computed at different separation time intervals. The domain of the

  10. Time-resolved fluorescence analysis of the mobile flavin cofactor

    Indian Academy of Sciences (India)

    Conformational heterogeneity of the FAD cofactor in -hydroxybenzoate hydroxylase (PHBH) was investigated with time-resolved polarized flavin fluorescence. For binary enzyme/substrate (analogue) complexes of wild-type PHBH and Tyr222 mutants, crystallographic studies have revealed two distinct flavin conformations ...

  11. An x-ray detector for time-resolved studies

    International Nuclear Information System (INIS)

    Rodricks, B.; Brizard, C.; Clarke, R.; Lowe, W.

    1992-01-01

    The development of ultrahigh-brightness x-ray sources makes time-resolved x-ray studies more and more feasible. Improvements in x-ray optics components are also critical for obtaining the appropriate beam for a particular type of experiment. Moreover, fast parallel detectors will be essential in order to exploit the combination of high intensity x-ray sources and novel optics for time-resolved experiments. A CCD detector with a time resolution of microseconds has been developed at the Advanced Photon Source (APS). This detector is fully programmable using CAMAC electronics and a Micro Vax computer. The techniques of time-resolved x-ray studies, which include scattering, microradiography, microtomography, stroboscopy, etc., can be applied to a range of phenomena (including rapid thermal annealing, surface ordering, crystallization, and the kinetics of phase transition) in order to understand these time-dependent microscopic processes. Some of these applications will be illustrated by recent results performed at synchrotrons. New powerful x-ray sources now under construction offer the opportunity to apply innovative approaches in time-resolved work

  12. Time-Resolved Small-Angle X-Ray Scattering

    NARCIS (Netherlands)

    ten Elshof, Johan E.; Besselink, R.; Stawski, Tomasz; Castricum, H.L.; Levy, D.; Zayat, M.

    2015-01-01

    This chapter focuses on time-resolved studies of nanostructure development in sol-gel liquids, that is, diluted sols, wet gels, and drying thin fffilms. The most commonly investigated classes of sol-gel materials are silica, organically modified silica, template-directed mesostructured silica,

  13. NMR and IR Spectroscopy for the Structural Characterization of Edible Fats and Oils: An Instrumental Analysis Laboratory

    Science.gov (United States)

    Crowther, Molly W.

    2008-01-01

    This article describes an upper-level instrumental laboratory for undergraduates that explores the complementary nature of IR and NMR spectroscopy for analysis of several edible fats and oils that are structurally similar but differ in physical properties and health implications. Five different fats and oils are analyzed for average chain length,…

  14. Ultra-Broadband Infrared Pulses from a Potassium-Titanyl Phosphate Optical Parametric Amplifier for VIS-IR-SFG Spectroscopy

    Science.gov (United States)

    Isaienko, Oleksandr; Borguet, Eric

    A non-collinear KTP-OPA to provide ultra-broadband mid-infrared pulses was designed and characterized. With proper pulse-front and phase correction, the system has a potential for high-time resolution vibrational VIS-IR-SFG spectroscopy.

  15. Detection and classification of salmonella serotypes using spectral signatures collected by fourier transform infrared (FT-IR) spectroscopy

    Science.gov (United States)

    Spectral signatures of Salmonella serotypes namely Salmonella Typhimurium, Salmonella Enteritidis, Salmonella Infantis, Salmonella Heidelberg and Salmonella Kentucky were collected using Fourier transform infrared spectroscopy (FT-IR). About 5-10 µL of Salmonella suspensions with concentrations of 1...

  16. Numerical simulations of time-resolved quantum electronics

    International Nuclear Information System (INIS)

    Gaury, Benoit; Weston, Joseph; Santin, Matthieu; Houzet, Manuel; Groth, Christoph; Waintal, Xavier

    2014-01-01

    Numerical simulation has become a major tool in quantum electronics both for fundamental and applied purposes. While for a long time those simulations focused on stationary properties (e.g. DC currents), the recent experimental trend toward GHz frequencies and beyond has triggered a new interest for handling time-dependent perturbations. As the experimental frequencies get higher, it becomes possible to conceive experiments which are both time-resolved and fast enough to probe the internal quantum dynamics of the system. This paper discusses the technical aspects–mathematical and numerical–associated with the numerical simulations of such a setup in the time domain (i.e. beyond the single-frequency AC limit). After a short review of the state of the art, we develop a theoretical framework for the calculation of time-resolved observables in a general multiterminal system subject to an arbitrary time-dependent perturbation (oscillating electrostatic gates, voltage pulses, time-varying magnetic fields, etc.) The approach is mathematically equivalent to (i) the time-dependent scattering formalism, (ii) the time-resolved non-equilibrium Green’s function (NEGF) formalism and (iii) the partition-free approach. The central object of our theory is a wave function that obeys a simple Schrödinger equation with an additional source term that accounts for the electrons injected from the electrodes. The time-resolved observables (current, density, etc.) and the (inelastic) scattering matrix are simply expressed in terms of this wave function. We use our approach to develop a numerical technique for simulating time-resolved quantum transport. We find that the use of this wave function is advantageous for numerical simulations resulting in a speed up of many orders of magnitude with respect to the direct integration of NEGF equations. Our technique allows one to simulate realistic situations beyond simple models, a subject that was until now beyond the simulation

  17. Characterization of Paracoccidioides brasiliensis by FT-IR spectroscopy and nanotechnology

    Science.gov (United States)

    Ferreira, Isabelle; Ferreira-Strixino, Juliana; Castilho, Maiara L.; Campos, Claudia B. L.; Tellez, Claudio; Raniero, Leandro

    2016-01-01

    Paracoccidioides brasiliensis, the etiological agent of paracoccidioidomycosis, is a dimorphic fungus existing as mycelia in the environment (or at 25 °C in vitro) and as yeast cells in the human host (or at 37 °C in vitro). Because mycological examination of lesions in patients frequently is unable to show the presence of the fungus and serological tests can misdiagnose the disease with other mycosis, the development of new approach's for molecular identification of P. brasiliensis spurges is needed. This study describes the use of a gold nanoprobe of a known gene sequence of P. brasiliensis as a molecular tool to identify P. brasiliensis by regular polymerase chain reaction (PCR) associated with a colorimetric methods. This approach is suitable for testing in remote areas because it does not require any further step than gene amplification, being safer and cheaper than electrophoresis methods. The proposed test showed a color change of the PCR reaction mixture from red to blue in negative samples, whereas the solution remains red in positive samples. We also performed a Fourier Transform Infrared (FT-IR) Spectroscopy analysis to characterize and compare the chemical composition between yeast and mycelia forms, which revealed biochemical differences between these two forms. The analysis of the spectra showed that differences were distributed in chemical bonds of proteins, lipids and carbohydrates. The most prominent difference between both forms was vibration modes related to 1,3-β-glucan usually found in mycelia and 1,3-α-glucan found in yeasts and also chitin forms. In this work, we introduce FT-IR as a new method suitable to reveal overall differences that biochemically distinguish each form of P. brasiliensis that could be additionally used to discriminate biochemical differences among a single form under distinct environmental conditions.

  18. Communication: IR spectroscopy of neutral transition metal clusters through thermionic emission

    NARCIS (Netherlands)

    Lapoutre, V. J. F.; Haertelt, M.; Meijer, G.; Fielicke, A.; Bakker, J. M.

    2013-01-01

    The resonant multiple photon excitation of neutral niobium clusters using tunable infrared (IR) radiation leads to thermionic emission. By measuring the mass-resolved ionization yield as a function of IR wavenumber species selective IR spectra are obtained for Nb-n (n = 5-20) over the 200-350 cm(-1)

  19. Programming for time resolved spectrum in pulse radiolysis experiments

    International Nuclear Information System (INIS)

    Betty, C.A.; Panajkar, M.S.; Shirke, N.D.

    1993-01-01

    A user friendly program in Pascal has been developed for data acquisition and subsequent processing of time resolved spectra of transient species produced in pulse radiolysis experiments. The salient features of the program are (i) thiocyanate dosimetry and (ii) spectrum acquisition. The thiocyanate dosimetry is carried out to normalize experimental conditions to a standard value as determined by computing absorbance of the transient signal CNS -2 that is produced from thiocyanate solution by a 7 MeV electron pulse. Spectrum acquisition allows the acquisition of the time resolved data at 20 different times points and subsequent display of the plots of absorbance vs. wavelength for the desired time points during the experiment. It is also possible to plot single time point spectrum as well as superimposed spectra for different time points. Printing, editing and merging facilities are also provided. (author). 2 refs., 7 figs

  20. XRD, TEM, IR, Raman and NMR Spectroscopy of In Situ Crystallization of Lithium Disilicate Glass

    Science.gov (United States)

    Fuss, T.; Mogus-Milankovic, A.; Ray, C. S.; Lesher, C. E.; Youngman, R.; Day, D. E.

    2006-01-01

    The structure of a Li2O-2SiO2 (LS2) glass was investigated as a function of pressure and temperature up to 6 GPa and 750 C respectively, using XRD, TEM, IR, Raman and NMR spectroscopy. Glass densified at 6 GPa has an average Si-O-Si bond angle approx.7deg lower than that found in glass processed at 4.5 GPa. At 4.5 GPa, lithium disilicate crystallizes from the glass, while at 6 GPa a new high pressure form of lithium metasilicate crystallizes. The new phase, while having lithium metasilicate crystal symmetry, contains at least 4 different Si sites. NMR results for 6 GPa sample indicate the presence of Q4 species with (Q(sup 4))Si-O-Si(Q(sup 4)) bond angles of approx.157deg. This is the first reported occurrence of Q(sup 4) species with such large bond angles in alumina free alkali silicate glass. No five- or six- coordinated Si are found.

  1. Identification of Forged Bank of England 20 Gbp Banknotes Using IR Spectroscopy

    Science.gov (United States)

    Sonnex, Emily

    2014-06-01

    Bank of England notes of 20 GBP denomination have been studied using infrared spectroscopy in order to generate a method to identify forged notes. A principal aim of this work was to develop a method so that a small, compact ATR FTIR instrument could be used by bank workers, police departments or others such as shop assistants to identify forged notes in a non-lab setting. The ease of use of the instrument is the key to this method, as well as the relatively low cost. The presence of a peak at 1400 wn from the blank paper section of a forged note proved to be a successful indicator of the note's illegality for the notes that we studied. Moreover, differences between the spectra of forged and genuine 20 GBP notes were observed in the ν(OH) (ca. 3500 wn), ν(C-H) (ca. 2900 wn) and ν(C=O) (ca. 1750 wn) regions of the IR spectrum recorded for the polymer film covering the holographic strip. In cases where these simple tests fail, we have shown how an infrared microscope can be used to further differentiate genuine and forged banknotes by producing infrared maps of selected areas of the note contrasting inks with background paper. Further to this, with an announcement by the Bank of England to produce polymer banknotes in the future, the work has been extended using Australian polymer banknotes to show that the method would be transferable.

  2. Investigation of the hydrated 7-hydroxy-4-methylcoumarin dimer by combined IR/UV spectroscopy

    International Nuclear Information System (INIS)

    Stamm, A.; Schwing, K.; Gerhards, M.

    2014-01-01

    The first molecular beam investigations on a coumarin dimer and clusters of a coumarin dimer with water both in the neutral (S 0 ) and cationic (D 0 ) electronic ground state are performed. The structure and structural changes due to ionization of the isolated 7-hydroxy-4-methylcoumarin dimer (7H4MC) 2 as well as its mono- and dihydrate (7H4MC) 2 (H 2 O) 1-2 are analyzed by applying combined IR/UV spectroscopy compared with density functional theory calculations. In case of the neutral dimer of 7H4MC a doubly hydrogen-bonded structure is formed. This doubly hydrogen-bonded arrangement opens to a singly hydrogen-bonded structure in the ion presenting a rearrangement reaction within an isolated dimer. By attaching one or two water molecules to the neutral 7H4MC dimer water is inserted into the hydrogen bonds. In contrast to the non-hydrated species this general binding motif with water in a bridging function does not change via ionization but especially for the dihydrate the spatial arrangement of the two 7H4MC units changes strengthening the interaction between the aromatic chromophores. The presented analyses illustrate the strong dependence of binding motifs as a function of successive hydration and charge including a rearrangement reaction

  3. Forensic Hair Differentiation Using Attenuated Total Reflection Fourier Transform Infrared (ATR FT-IR) Spectroscopy.

    Science.gov (United States)

    Manheim, Jeremy; Doty, Kyle C; McLaughlin, Gregory; Lednev, Igor K

    2016-07-01

    Hair and fibers are common forms of trace evidence found at crime scenes. The current methodology of microscopic examination of potential hair evidence is absent of statistical measures of performance, and examiner results for identification can be subjective. Here, attenuated total reflection (ATR) Fourier transform-infrared (FT-IR) spectroscopy was used to analyze synthetic fibers and natural hairs of human, cat, and dog origin. Chemometric analysis was used to differentiate hair spectra from the three different species, and to predict unknown hairs to their proper species class, with a high degree of certainty. A species-specific partial least squares discriminant analysis (PLSDA) model was constructed to discriminate human hair from cat and dog hairs. This model was successful in distinguishing between the three classes and, more importantly, all human samples were correctly predicted as human. An external validation resulted in zero false positive and false negative assignments for the human class. From a forensic perspective, this technique would be complementary to microscopic hair examination, and in no way replace it. As such, this methodology is able to provide a statistical measure of confidence to the identification of a sample of human, cat, and dog hair, which was called for in the 2009 National Academy of Sciences report. More importantly, this approach is non-destructive, rapid, can provide reliable results, and requires no sample preparation, making it of ample importance to the field of forensic science. © The Author(s) 2016.

  4. Time-resolved crystallography using the Hadamard Transform

    Science.gov (United States)

    Yorke, Briony A.; Beddard, Godfrey S.; Owen, Robin L.; Pearson, Arwen R.

    2014-01-01

    A new method for performing time-resolved X-ray crystallographic experiments based on the Hadamard Transform is proposed and demonstrated. The time-resolution is defined by the underlying periodicity of the probe pulse sequence and the signal to noise is greatly improved compared to the fastest experiments depending on a single pulse. This approach is general and equally applicable to any spectroscopic or imaging measurement where the probe can be encoded. PMID:25282611

  5. Time-resolved spectral measurements above 80 A

    International Nuclear Information System (INIS)

    Kauffman, R.L.; Ceglio, N.; Medecki, H.

    1983-01-01

    We have made time-resolved spectral measurements above 80 A from laser-produced plasmas. These are made using a transmission grating spectrograph whose primary components are a cylindrically-curved x-ray mirror for light collection, a transmission grating for spectral dispersions, and an x-ray streak camera for temporal resolution. A description of the instrument and an example of the data are given

  6. The RATIO method for time-resolved Laue crystallography

    International Nuclear Information System (INIS)

    Coppens, P.; Pitak, M.; Gembicky, M.; Messerschmidt, M.; Scheins, S.; Benedict, J.; Adachi, S.-I.; Sato, T.; Nozawa, S.; Ichiyanagi, K.; Chollet, M.; Koshihara, S.-Y.

    2009-01-01

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

  7. Theory of time-resolved inelastic x-ray diffraction

    DEFF Research Database (Denmark)

    Lorenz, Ulf; Møller, Klaus Braagaard; Henriksen, Niels Engholm

    2010-01-01

    Starting from a general theory of time-resolved x-ray scattering, we derive a convenient expression for the diffraction signal based on a careful analysis of the relevant inelastic scattering processes. We demonstrate that the resulting inelastic limit applies to a wider variety of experimental...... conditions than similar, previously derived formulas, and it directly allows the application of selection rules when interpreting diffraction signals. Furthermore, we present a simple extension to systems simultaneously illuminated by x rays and a laser beam....

  8. Time-resolved CT angiography in aortic dissection

    International Nuclear Information System (INIS)

    Meinel, Felix G.; Nikolaou, Konstantin; Weidenhagen, Rolf; Hellbach, Katharina; Helck, Andreas; Bamberg, Fabian; Reiser, Maximilian F.; Sommer, Wieland H.

    2012-01-01

    Objectives: We performed this study to assess feasibility and additional diagnostic value of time-resolved CT angiography of the entire aorta in patients with aortic dissection. Materials and methods: 14 consecutive patients with known or suspected aortic dissection (aged 60 ± 9 years) referred for aortic CT angiography were scanned on a dual-source CT scanner (Somatom Definition Flash; Siemens, Forchheim, Germany) using a shuttle mode for multiphasic image acquisition (range 48 cm, time resolution 6 s, 6 phases, 100 kV, 110 mAs/rot). Effective radiation doses were calculated from recorded dose length products. For all phases, CT densities were measured in the aortic lumen and renal parenchyma. From the multiphasic data, 3 phases corresponding to a triphasic standard CT protocol, served as a reference and were compared against findings from the time-resolved datasets. Results: Mean effective radiation dose was 27.7 ± 3.5 mSv. CT density of the true lumen peaked at 355 ± 53 HU. Compared to the simulated triphasic protocol, time-resolved CT angiography added diagnostic information regarding a number of important findings: the enhancement delay between true and false lumen (n = 14); the degree of membrane oscillation (n = 14); the perfusion delay in arteries originating from the false lumen (n = 9). Other additional information included true lumen collapse (n = 4), quantitative assessment of renal perfusion asymmetry (n = 2), and dynamic occlusion of aortic branches (n = 2). In 3/14 patients (21%), these additional findings of the multiphasic protocol altered patient management. Conclusions: Multiphasic, time-resolved CT angiography covering the entire aorta is feasible at a reasonable effective radiation dose and adds significant diagnostic information with therapeutic consequences in patients with aortic dissection.

  9. Thermo-oxidative degradation study of melt-processed polyethylene and its blend with polyamide using time-resolved rheometry

    CSIR Research Space (South Africa)

    Salehiyan, Reza

    2017-05-01

    Full Text Available Time-resolved mechanical spectroscopy (TRMS) was conducted to study the thermo-oxidative degradation of linear low density polyethylene (LLDPE) samples with different thermal histories and their blends with a polyamide (PA6) in the melt state. Neat...

  10. Time-resolved cathodoluminescence microscopy with sub-nanosecond beam blanking for direct evaluation of the local density of states

    NARCIS (Netherlands)

    Moerland, R.J.; Weppelman, I.G.C.; Garming, M.W.H.; Kruit, P.; Hoogenboom, J.P.

    2016-01-01

    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

  11. Timely resolved measurements on CdSe nanoparticles

    International Nuclear Information System (INIS)

    Holt, B.E. von

    2006-01-01

    By means of infrared spectroscopy the influence of the organic cover on structure and dynamics of CdSe nanoparticles was studied. First a procedure was developed, which allows to get from the static infrared spectrum informations on the quality of the organic cover and the binding behaviour of the ligands. On qualitatively high-grade and well characterized samples thereafter the dynamics of the lowest-energy electron level 1S e was time-resolvedly meausred in thew visible range. As reference served CdSe TOPO, which was supplemented by samples with the ligands octanthiole, octanic acid, octylamine, naphthoquinone, benzoquinone, and pyridine. The studied nanoparticles had a diameter of 4.86 nm. By means of the excitation-scanning or pump=probe procedure first measurements in the picosecond range were performed. The excitation wavelengths were thereby spectrally confined and so chosen that selectively the transitions 1S 3/2 -1S-e and 1P 3/2 -1P e but not the intermediately lyingt transition 2S 3/2 -1S e were excited. The excitation energies were kept so low that the excitation of several excitons in one crystal could be avoided. The scanning wavelength in the infrared corresponded to the energy difference between the electron levels 1S e and 1P e . The transients in the picosecond range are marked by a steep increasement of the signal, on which a multi-exponential decay follows. The increasement, which reproduces the popiulation of the excited state, isa inependent on the choice of the ligands. The influence of the organic cover is first visible in the different decay times of the excited electron levels. the decay of the measurement signal of CdSe TOPO can be approximatively described by three time constants: a decay constant in the early picosecond region, a time constant around hundert picoseconds, and a time constant of some nanoseconds. At increasing scanning wavelength the decay constants become longer. By directed excitation of the 1S 3/2 -1S e and the 1P 3

  12. Alignment of time-resolved data from high throughput experiments.

    Science.gov (United States)

    Abidi, Nada; Franke, Raimo; Findeisen, Peter; Klawonn, Frank

    2016-12-01

    To better understand the dynamics of the underlying processes in cells, it is necessary to take measurements over a time course. Modern high-throughput technologies are often used for this purpose to measure the behavior of cell products like metabolites, peptides, proteins, [Formula: see text]RNA or mRNA at different points in time. Compared to classical time series, the number of time points is usually very limited and the measurements are taken at irregular time intervals. The main reasons for this are the costs of the experiments and the fact that the dynamic behavior usually shows a strong reaction and fast changes shortly after a stimulus and then slowly converges to a certain stable state. Another reason might simply be missing values. It is common to repeat the experiments and to have replicates in order to carry out a more reliable analysis. The ideal assumptions that the initial stimulus really started exactly at the same time for all replicates and that the replicates are perfectly synchronized are seldom satisfied. Therefore, there is a need to first adjust or align the time-resolved data before further analysis is carried out. Dynamic time warping (DTW) is considered as one of the common alignment techniques for time series data with equidistant time points. In this paper, we modified the DTW algorithm so that it can align sequences with measurements at different, non-equidistant time points with large gaps in between. This type of data is usually known as time-resolved data characterized by irregular time intervals between measurements as well as non-identical time points for different replicates. This new algorithm can be easily used to align time-resolved data from high-throughput experiments and to come across existing problems such as time scarcity and existing noise in the measurements. We propose a modified method of DTW to adapt requirements imposed by time-resolved data by use of monotone cubic interpolation splines. Our presented approach

  13. Photodissociation Spectroscopy of Cold Protonated Synephrine: Surprising Differences between IR-UV Hole-Burning and IR Photodissociation Spectroscopy of the O-H and N-H Modes.

    Science.gov (United States)

    Nieuwjaer, N; Desfrançois, C; Lecomte, F; Manil, B; Soorkia, S; Broquier, M; Grégoire, G

    2018-04-19

    We report the UV and IR photofragmentation spectroscopies of protonated synephrine in a cryogenically cooled Paul trap. Single (UV or IR) and double (UV-UV and IR-UV) resonance spectroscopies have been performed and compared to quantum chemistry calculations, allowing the assignment of the lowest-energy conformer with two rotamers depending on the orientation of the phenol hydroxyl (OH) group. The IR-UV hole burning spectrum exhibits the four expected vibrational modes in the 3 μm region, i.e., the phenol OH, C β -OH, and two NH 2 + stretches. The striking difference is that, among these modes, only the free phenol OH mode is active through IRPD. The protonated amino group acts as a proton donor in the internal hydrogen bond and displays large frequency shifts upon isomerization expected during the multiphoton absorption process, leading to the so-called IRMPD transparency. More interestingly, while the C β -OH is a proton acceptor group with moderate frequency shift for the different conformations, this mode is still inactive through IRPD.

  14. Matrix isolation FT-IR spectroscopy and molecular orbital study of sarcosine methyl ester

    Science.gov (United States)

    Gómez-Zavaglia, A.; Fausto, R.

    2004-02-01

    N-methylglycine methyl ester (sarcosine-Me) has been studied by matrix isolation FT-IR spectroscopy and molecular orbital calculations undertaken at the DFT/B3LYP and MP2 levels of theory with the 6-311++G(d,p) and 6-31++G(d,p) basis set, respectively. Twelve different conformers were located in the potential energy surface of the studied compound, with the ASC conformer being the ground conformational state. This form is analogous to the dimethylglycine methyl ester most stable conformer and is characterized by a NH⋯O intramolecular hydrogen bond; in this form, the ester group assumes the cis configuration and the OC-C-N and Lp-N-C-C (where Lp is the nitrogen lone electron pair) dihedral angles are ca. -17.8 and 171.3°, respectively. The second most stable conformer ( GSC) differs from the ASC conformer essentially in the conformation assumed by the methylamino group, which in this case is gauche ( Lp-N-C-C dihedral angle equal to 79.4°). On the other hand, the third most stable conformer ( AAC) differs from the most stable form in the conformation of the OC-C-N axis (151.4°). These three forms were predicted to differ in energy by less than ca. 5 kJ mol -1 and represent ≈95% of the total conformational population at room temperature. FT-IR spectra were obtained for sarcosine-Me isolated in argon matrices (T=9 K) revealing the presence in the matrices of the three lowest energy conformers predicted by the calculations. The matrices were prepared by deposition of the vapour of the compound using two different nozzle temperatures, 25 and 60 °C. The relative populations of the three conformers trapped in the matrices were found to be consistent with occurrence of conformational cooling during matrix deposition and with a stabilization of the most polar GSC and AAC conformers in the matrices compared to the gas phase. Indeed, like it was previously observed for the methyl ester of dimethylglycine [Phys. Chem. Chem. Phys. 5 (2003) 52] the different

  15. Ultrafast time-resolved faraday rotation in EuO thin films.

    Science.gov (United States)

    Liu, F; Makino, T; Yamasaki, T; Ueno, K; Tsukazaki, A; Fukumura, T; Kong, Y; Kawasaki, M

    2012-06-22

    We have investigated the ultrafast spin dynamics in EuO thin films by time-resolved Faraday rotation spectroscopy. The photoinduced magnetization is found to be increased in a transient manner, accompanied with subsequent demagnetization. The dynamical magnetization enhancement showed a maximum slightly below the Curie temperature with prolonged tails toward both lower and higher temperatures and dominates the demagnetization counterpart at 55 K. The magnetization enhancement component decays in ~1 ns. The realization of the transient collective ordering is attributable to the enhancement of the f-d exchange interaction.

  16. Unfolding of Ubiquitin Studied by Picosecond Time-Resolved Fluorescence of the Tyrosine Residue

    OpenAIRE

    Noronha, Melinda; Lima, João C.; Bastos, Margarida; Santos, Helena; Maçanita, António L.

    2004-01-01

    The photophysics of the single tyrosine in bovine ubiquitin (UBQ) was studied by picosecond time-resolved fluorescence spectroscopy, as a function of pH and along thermal and chemical unfolding, with the following results: First, at room temperature (25°C) and below pH 1.5, native UBQ shows single-exponential decays. From pH 2 to 7, triple-exponential decays were observed and the three decay times were attributed to the presence of tyrosine, a tyrosine-carboxylate hydrogen-bonded complex, and...

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

    Science.gov (United States)

    Nomura, Y; Hazeki, O; Tamura, M

    1997-06-01

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

  18. Differentiation of Body Fluid Stains on Fabrics Using External Reflection Fourier Transform Infrared Spectroscopy (FT-IR) and Chemometrics.

    Science.gov (United States)

    Zapata, Félix; de la Ossa, Ma Ángeles Fernández; García-Ruiz, Carmen

    2016-04-01

    Body fluids are evidence of great forensic interest due to the DNA extracted from them, which allows genetic identification of people. This study focuses on the discrimination among semen, vaginal fluid, and urine stains (main fluids in sexual crimes) placed on different colored cotton fabrics by external reflection Fourier transform infrared spectroscopy (FT-IR) combined with chemometrics. Semen-vaginal fluid mixtures and potential false positive substances commonly found in daily life such as soaps, milk, juices, and lotions were also studied. Results demonstrated that the IR spectral signature obtained for each body fluid allowed its identification and the correct classification of unknown stains by means of principal component analysis (PCA) and soft independent modeling of class analogy (SIMCA). Interestingly, results proved that these IR spectra did not show any bands due to the color of the fabric and no substance of those present in daily life which were analyzed, provided a false positive. © The Author(s) 2016.

  19. Tunable Microcavity-Stabilized Quantum Cascade Laser for Mid-IR High-Resolution Spectroscopy and Sensing

    Directory of Open Access Journals (Sweden)

    Simone Borri

    2016-02-01

    Full Text Available The need for highly performing and stable methods for mid-IR molecular sensing and metrology pushes towards the development of more and more compact and robust systems. Among the innovative solutions aimed at answering the need for stable mid-IR references are crystalline microresonators, which have recently shown excellent capabilities for frequency stabilization and linewidth narrowing of quantum cascade lasers with compact setups. In this work, we report on the first system for mid-IR high-resolution spectroscopy based on a quantum cascade laser locked to a CaF2 microresonator. Electronic locking narrows the laser linewidth by one order of magnitude and guarantees good stability over long timescales, allowing, at the same time, an easy way for finely tuning the laser frequency over the molecular absorption line. Improvements in terms of resolution and frequency stability of the source are demonstrated by direct sub-Doppler recording of a molecular line.

  20. Tunable Microcavity-Stabilized Quantum Cascade Laser for Mid-IR High-Resolution Spectroscopy and Sensing.

    Science.gov (United States)

    Borri, Simone; Siciliani de Cumis, Mario; Insero, Giacomo; Bartalini, Saverio; Cancio Pastor, Pablo; Mazzotti, Davide; Galli, Iacopo; Giusfredi, Giovanni; Santambrogio, Gabriele; Savchenkov, Anatoliy; Eliyahu, Danny; Ilchenko, Vladimir; Akikusa, Naota; Matsko, Andrey; Maleki, Lute; De Natale, Paolo

    2016-02-17

    The need for highly performing and stable methods for mid-IR molecular sensing and metrology pushes towards the development of more and more compact and robust systems. Among the innovative solutions aimed at answering the need for stable mid-IR references are crystalline microresonators, which have recently shown excellent capabilities for frequency stabilization and linewidth narrowing of quantum cascade lasers with compact setups. In this work, we report on the first system for mid-IR high-resolution spectroscopy based on a quantum cascade laser locked to a CaF₂ microresonator. Electronic locking narrows the laser linewidth by one order of magnitude and guarantees good stability over long timescales, allowing, at the same time, an easy way for finely tuning the laser frequency over the molecular absorption line. Improvements in terms of resolution and frequency stability of the source are demonstrated by direct sub-Doppler recording of a molecular line.

  1. IR spectroscopy of synthetic glasses with Mercury surface composition: Analogs for remote sensing

    Science.gov (United States)

    Morlok, Andreas; Klemme, Stephan; Weber, Iris; Stojic, Aleksandra; Sohn, Martin; Hiesinger, Harald

    2017-11-01

    In a study to provide ground-truth data for mid-infrared observations of the surface of Mercury with the MERTIS (Mercury Radiometer and Thermal Infrared Spectrometer) instrument onboard the ESA/JAXA BepiColombo mission, we have studied 17 synthetic glasses. These samples have the chemical compositions of characteristic Hermean surface areas based on MESSENGER data. The samples have been characterized using optical microscopy, EMPA and Raman spectroscopy. Mid-infrared spectra have been obtained from polished thin sections using Micro-FTIR, and of powdered size fractions of bulk material (0-25, 25-63, 93-125 and 125-250 μm) in the 2.5-18 μm range. The synthetic glasses display mostly spectra typical for amorphous materials with a dominating, single Reststrahlen Band (RB) at 9.5-10.7 μm. RB Features of crystalline forsterite are found in some cases at 9.5-10.2 μm, 10.4-11.2 μm, and at 11.9 μm. Dendritic crystallization starts at a MgO content higher than 23 wt.% MgO. The Reststrahlen Bands, Christiansen Features (CF), and Transparency Features (TF) shift depending on the SiO2 and MgO contents. Also a shift of the Christiansen Feature of the glasses compared with the SCFM (SiO2/(SiO2+CaO+FeO+MgO)) index is observed. This shift could potentially help distinguish crystalline and amorphous material in remote sensing data. A comparison between the degree of polymerization of the glass and the width of the characteristic strong silicate feature shows a weak positive correlation. A comparison with a high-quality mid-IR spectrum of Mercury shows some moderate similarity to the results of this study, but does not explain all features.

  2. IGRINS NEAR-IR HIGH-RESOLUTION SPECTROSCOPY OF MULTIPLE JETS AROUND LkHα 234

    Energy Technology Data Exchange (ETDEWEB)

    Oh, Heeyoung; Yuk, In-Soo; Park, Byeong-Gon; Park, Chan; Chun, Moo-Young; Kim, Kang-Min; Oh, Jae Sok; Jeong, Ueejeong; Yu, Young Sam; Lee, Jae-Joon; Kim, Hwihyun; Hwang, Narae; Lee, Sungho [Korea Astronomy and Space Science Institute, 776 Daedeok-daero, Yuseong-gu, Daejeon 305-348 (Korea, Republic of); Pyo, Tae-Soo [Subaru Telescope, National Astronomical Observatory of Japan, 650 North A’ohoku Place, Hilo, HI 96720 (United States); Pak, Soojong; Lee, Hye-In; Le, Huynh Anh Nguyen [School of Space Research and Institute of Natural Sciences, Kyung Hee University, 1732 Deogyeong-daero, Giheung-gu, Yongin-si, Gyeonggi-do 17104 (Korea, Republic of); Kaplan, Kyle; Pavel, Michael; Mace, Gregory, E-mail: hyoh@kasi.re.kr [Department of Astronomy, University of Texas at Austin, Austin, TX (United States); and others

    2016-02-01

    We present the results of high-resolution near-IR spectroscopy toward the multiple outflows around the Herbig Be star LkHα 234 using the Immersion Grating Infrared Spectrograph. Previous studies indicate that the region around LkHα 234 is complex, with several embedded young stellar objects and the outflows associated with them. In simultaneous H- and K-band spectra from HH 167, we detected 5 [Fe ii] and 14 H{sub 2} emission lines. We revealed a new [Fe ii] jet driven by radio continuum source VLA 3B. Position–velocity diagrams of the H{sub 2} 1−0 S(1) λ2.122 μm line show multiple velocity peaks. The kinematics may be explained by a geometrical bow shock model. We detected a component of H{sub 2} emission at the systemic velocity (V{sub LSR} = −10.2 km s{sup −1}) along the whole slit in all slit positions, which may arise from the ambient photodissociation region. Low-velocity gas dominates the molecular hydrogen emission from knots A and B in HH 167, which is close to the systemic velocity; [Fe ii] emission lines are detected farther from the systemic velocity, at V{sub LSR} = −100–−130 km s{sup −1}. We infer that the H{sub 2} emission arises from shocked gas entrained by a high-velocity outflow. Population diagrams of H{sub 2} lines imply that the gas is thermalized at a temperature of 2500–3000 K and the emission results from shock excitation.

  3. Case study of chondrule alteration with IR spectroscopy in NWA 2086 CV3 meteorite

    Science.gov (United States)

    Kereszturi, A.; Gyollai, I.; Szabó, M.

    2015-02-01

    Analyzing the alteration in an olivine chondrule of the NWA 2086 CV3 meteorite, infrared spectral, electron microprobe and optical microscopic observations were correlated to each other. The intensity and wavelength positions of olivine peaks changed characteristically with the progression of alteration and related Fe/Mg substitution inward of the chondrule. Moderate to good correlations were identified between Fo% composition and positions of 830 and 860 cm-1 IR peaks. The disappearance of 1020 cm-1 peak by structural change happens already at a low level alteration without changing the optical appearance of the mineral. The existence of the 980 cm-1 peak is found to be an indicator of the intact phase of olivine. While profiles perpendicular to the chondrule's perimeter showed that the alteration progressed 15-20 μm distance inward without observable fractures (probablly by some diffusion related process), the "alteration distance" from various obvious fractures inside the chondrule was only 3-5 μm distance. These observations suggest that the substitution was more effective close to the matrix, and also related to some fluids that although were able to circulate along the large internal fractures too, did not produce such strong substitution there, like what happened close to the matrix. It was also demonstrated that the poorly exploited contact mode observations with ATR based reflection method in infrared spectroscopy provide a useful tool to analyze the alteration at micrometer scale without much sample preparation, and enable identifying alterations already at such a low level where the olivines still look optically intact.

  4. Time Resolved Detection of Infrared Synchrotron Radiation at DAΦNE

    International Nuclear Information System (INIS)

    Bocci, A.; Marcelli, A.; Drago, A.; Guidi, M. Cestelli; Pace, E.; Piccinini, M.; Sali, D.; Morini, P.; Piotrowski, J.

    2007-01-01

    Synchrotron radiation is characterized by a very wide spectral emission from IR to X-ray wavelengths and a pulsed structure that is a function of the source time structure. In a storage ring, the typical temporal distance between two bunches, whose duration is a few hundreds of picoseconds, is on the nanosecond scale. Therefore, synchrotron radiation sources are a very powerful tools to perform time-resolved experiments that however need extremely fast detectors. Uncooled IR devices optimized for the mid-IR range with sub-nanosecond response time, are now available and can be used for fast detection of intense IR sources such as synchrotron radiation storage rings. We present here different measurements of the pulsed synchrotron radiation emission at DAΦNE (Double Annular Φ-factory for Nice Experiments), the collider of the Laboratori Nazionali of Frascati (LNF) of the Istituto Nazionale di Fisica Nucleare (INFN), performed with very fast uncooled infrared detectors with a time resolution of a few hundreds of picoseconds. We resolved the emission time structure of the electron bunches of the DAΦNE collider when it works in a normal condition for high energy physics experiments with both photovoltaic and photoconductive detectors. Such a technology should pave the way to new diagnostic methods in storage rings, monitoring also source instabilities and bunch dynamics

  5. Lucas–Kanade fluid trajectories for time-resolved PIV

    International Nuclear Information System (INIS)

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

    2016-01-01

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

  6. Time-resolved explosion of intense-laser-heated clusters.

    Science.gov (United States)

    Kim, K Y; Alexeev, I; Parra, E; Milchberg, H M

    2003-01-17

    We investigate the femtosecond explosive dynamics of intense laser-heated argon clusters by measuring the cluster complex transient polarizability. The time evolution of the polarizability is characteristic of competition in the optical response between supercritical and subcritical density regions of the expanding cluster. The results are consistent with time-resolved Rayleigh scattering measurements, and bear out the predictions of a recent laser-cluster interaction model [H. M. Milchberg, S. J. McNaught, and E. Parra, Phys. Rev. E 64, 056402 (2001)

  7. Time-resolved explosion of intense-laser-heated clusters

    International Nuclear Information System (INIS)

    Kim, K.Y.; Alexeev, I.; Parra, E.; Milchberg, H.M.

    2003-01-01

    We investigate the femtosecond explosive dynamics of intense laser-heated argon clusters by measuring the cluster complex transient polarizability. The time evolution of the polarizability is characteristic of competition in the optical response between supercritical and subcritical density regions of the expanding cluster. The results are consistent with time-resolved Rayleigh scattering measurements, and bear out the predictions of a recent laser-cluster interaction model [H. M. Milchberg, S. J. McNaught, and E. Parra, Phys. Rev. E 64, 056402 (2001)

  8. Complementary online aerosol mass spectrometry and offline FT-IR spectroscopy measurements: Prospects and challenges for the analysis of anthropogenic aerosol particle emissions

    Science.gov (United States)

    Faber, Peter; Drewnick, Frank; Bierl, Reinhard; Borrmann, Stephan

    2017-10-01

    The aerosol mass spectrometer (AMS) is well established in investigating highly time-resolved dynamics of submicron aerosol chemical composition including organic aerosol (OA). However, interpretation of mass spectra on molecular level is limited due to strong fragmentation of organic substances and potential reactions inside the AMS ion chamber. Results from complementary filter-based FT-IR absorption measurements were used to explain features in high-resolution AMS mass spectra of different types of OA (e.g. cooking OA, cigarette smoking OA, wood burning OA). Using this approach some AMS fragment ions were validated in this study as appropriate and rather specific markers for a certain class of organic compounds for all particle types under investigation. These markers can therefore be used to get deeper insights in the chemical composition of OA based on AMS mass spectra in upcoming studies. However, the specificity of other fragment ions such as C2H4O2+ (m/z 60.02114) remains ambiguous. In such cases, complementary FT-IR measurements allow the interpretation of highly time-resolved AMS mass spectra at the level of molecular functional groups. Furthermore, this study discusses the challenges in reducing inorganic interferences (e.g. from water and ammonium salts) in FT-IR spectra of atmospheric aerosols to decrease spectral uncertainties for better comparisons and, thus, to get more robust results.

  9. Ultrafast stimulated Raman spectroscopy in the near-infrared region

    International Nuclear Information System (INIS)

    Takaya, Tomohisa

    2016-01-01

    A number of electronic transitions in the near-infrared wavelength region are associated with migration or delocalization of electrons in large molecules or molecular systems. Time-resolved near-infrared Raman spectroscopy will be a powerful tool for investigating the structural dynamic of samples with delocalized electrons. However, the sensitivity of near-infrared spontaneous Raman spectrometers is significantly low due to an extremely small probability of Raman scattering and a low sensitivity of near-infrared detectors. Nonlinear Raman spectroscopy is one of the techniques that can overcome the sensitivity problems and enable us to obtain time-resolved Raman spectra in resonance with near-IR transitions. In this article, the author introduces recent progress of ultrafast time-resolved near-infrared stimulated Raman spectroscopy. Optical setup, spectral and temporal resolution, and applications of the spectrometer are described. (author)

  10. A novel multiplex absorption spectrometer for time-resolved studies

    Science.gov (United States)

    Lewis, Thomas; Heard, Dwayne E.; Blitz, Mark A.

    2018-02-01

    A Time-Resolved Ultraviolet/Visible (UV/Vis) Absorption Spectrometer (TRUVAS) has been developed that can simultaneously monitor absorption at all wavelengths between 200 and 800 nm with millisecond time resolution. A pulsed photolysis laser (KrF 248 nm) is used to initiate chemical reactions that create the target species. The absorption signals from these species evolve as the composition of the gas in the photolysis region changes over time. The instrument can operate at pressures over the range ˜10-800 Torr and can measure time-resolved absorbances systems (in particular the Herriott cell), there are fundamental differences, most notably the ability to adjust each mirror to maximise the overlap between the probe beam and the photolysis laser. Another feature which aids the sensitivity and versatility of the system is the use of 2 high-throughput spectrographs coupled with sensitive line-array CCDs, which can measure absorbance from ˜200 to 800 nm simultaneously. The capability of the instrument is demonstrated via measurements of the absorption spectrum of the peroxy radical, HOCH2CH2O2, and its self-reaction kinetics.

  11. Time-resolved Laue diffraction from protein crystals: Instrumental considerations

    International Nuclear Information System (INIS)

    Bilderback, D.H.; Cornell Univ., Ithaca, NY; Moffat, K.; Szebenyi, D.M.E.

    1984-01-01

    A serious limitation of macromolecular crystallography has been its inability to determine changes in structure on a biochemical time scale of milliseconds or less. Recently, we have shown that X-ray exposures on single crystals of macromolecules may be obtained in the millisecond time range through the use of intense, polychromatic radiation with Δlambda/lambda approx.= 0.2 derived from the Cornell High Energy Synchrotron Source, CHESS. Such radiation falling on a stationary crystal yields a Laue diffraction pattern, in which almost all Laue reflections arise from a unique set of Miller indices and where their intensities are automatically integrated over wavelength. This Laue technique requires wide band pass optics, which may be obtained by a combination of reflection and transmission mirrors, filters or layered synthetic microstructures. Time-resolved macromolecular crystallography may be achieved by several data collection schemes: 'one-shot' recording coupled to a simple streak camera, repetitive sample perturbation coupled to a detector with temporal resolution and repetitive perturbation which uses the synchrotron pulses for stroboscopic triggering and detection. These schemes are appropriate for different time scales, roughly the milli-, micro- and nanosecond regimes. It appears that time-resolved crystallography is entirely feasible, with an ultimate time resolution limited only by the length of a synchrotron light pulse, some 150 ps at CHESS. (orig.)

  12. Time resolved fluorescence of cow and goat milk powder

    Science.gov (United States)

    Brandao, Mariana P.; de Carvalho dos Anjos, Virgílio; Bell., Maria José V.

    2017-01-01

    Milk powder is an international dairy commodity. Goat and cow milk powders are significant sources of nutrients and the investigation of the authenticity and classification of milk powder is particularly important. The use of time-resolved fluorescence techniques to distinguish chemical composition and structure modifications could assist develop a portable and non-destructive methodology to perform milk powder classification and determine composition. This study goal is to differentiate milk powder samples from cows and goats using fluorescence lifetimes. The samples were excited at 315 nm and the fluorescence intensity decay registered at 468 nm. We observed fluorescence lifetimes of 1.5 ± 0.3, 6.4 ± 0.4 and 18.7 ± 2.5 ns for goat milk powder; and 1.7 ± 0.3, 6.9 ± 0.2 and 29.9 ± 1.6 ns for cow's milk powder. We discriminate goat and cow powder milk by analysis of variance using Fisher's method. In addition, we employed quadratic discriminant analysis to differentiate the milk samples with accuracy of 100%. Our results suggest that time-resolved fluorescence can provide a new method to the analysis of powder milk and its composition.

  13. Time resolved plasma characterization in a long conduction time planar plasma opening switch

    International Nuclear Information System (INIS)

    Adler, L.K.; Greenly, J.B.; Qi, N.; Hammer, D.A.

    1989-01-01

    The authors discuss additional experiments in which the plasma dynamics and properties will be monitored in detail before and during opening. Space and time resolved density, temperature and motion information about the plasma and neutrals is given by emission spectroscopy and streak photography and correlated to the current and voltage traces. Specifically, we will look for the effects of neutrals evolving off of surfaces, stagnation of the switch plasma, and rvec J x rvec B motion of the plasma downstream of the switch. Diagnostics include current and voltage monitors, a multi-aperture biased Faraday cup, emission spectroscopy and streak photography. Pairs of B dot loops are positioned in the stripline just upstream and downstream of the POS. Also, two single B loops were placed further downstream to look for bulk plasma motion. An inductive monitor gives the voltage at the upstream side of the POS and the Faraday cup monitors the gun plasma consistency from shot to shot

  14. A time resolved microfocus XEOL facility at the Diamond Light Source

    International Nuclear Information System (INIS)

    Mosselmans, J F W; Taylor, R P; Quinn, P D; Cibin, G; Gianolio, D; Finch, A A; Sapelkin, A V

    2013-01-01

    We have constructed a Time-Resolved X-ray Excited Optical Luminescence (TR-XEOL) detection system at the Microfocus Spectroscopy beamline I18 at the Diamond Light Source. Using the synchrotron in h ybrid bunch mode , the data collection is triggered by the RF clock, and we are able to record XEOL photons with a time resolution of 6.1 ps during the 230 ns gap between the hybrid bunch and the main train of electron bunches. We can detect photons over the range 180-850 nm using a bespoke optical fibre, with X-ray excitation energies between 2 and 20 keV. We have used the system to study a range of feldspars. The detector is portable and has also been used on beamline B18 to collect Optically Determined X-ray Absorption Spectroscopy (OD-XAS) in QEXAFS mode.

  15. A time resolved microfocus XEOL facility at the Diamond Light Source

    Science.gov (United States)

    Mosselmans, J. F. W.; Taylor, R. P.; Quinn, P. D.; Finch, A. A.; Cibin, G.; Gianolio, D.; Sapelkin, A. V.

    2013-03-01

    We have constructed a Time-Resolved X-ray Excited Optical Luminescence (TR-XEOL) detection system at the Microfocus Spectroscopy beamline I18 at the Diamond Light Source. Using the synchrotron in "hybrid bunch mode", the data collection is triggered by the RF clock, and we are able to record XEOL photons with a time resolution of 6.1 ps during the 230 ns gap between the hybrid bunch and the main train of electron bunches. We can detect photons over the range 180-850 nm using a bespoke optical fibre, with X-ray excitation energies between 2 and 20 keV. We have used the system to study a range of feldspars. The detector is portable and has also been used on beamline B18 to collect Optically Determined X-ray Absorption Spectroscopy (OD-XAS) in QEXAFS mode.

  16. Towards a Molecular Movie: Real Time Observation of Hydrogen Bond Breaking by Transient 2D-IR Spectroscopy in a Cyclic Peptide

    Science.gov (United States)

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

    Transient two-dimensional infrared spectroscopy (T2D-IR) has been used to observe in real time the non-equilibrium structural dynamics of intramolecular hydrogen bond breaking in a small cyclic disulfide-bridged peptide.

  17. An IR and XPS spectroscopy assessment of the physico-chemical surface properties of alumina–YAG nanopowders

    Energy Technology Data Exchange (ETDEWEB)

    Spina, Giulia; Bonelli, Barbara, E-mail: barbara.bonelli@polito.it; Palmero, Paola, E-mail: paola.palmero@polito.it; Montanaro, Laura

    2013-12-16

    Well-dispersed nano-crystalline transition alumina suspensions were mixed with yttrium chloride aqueous solutions, with the aim of producing by spray-drying Al{sub 2}O{sub 3}–Y{sub 3}Al{sub 5}O{sub 12} (YAG) composite powders of increasing YAG vol.%. Two samples were prepared, with different Y content, corresponding to 5 and 20 YAG vol.%, respectively. Both samples were then treated at either 600 or 1150 °C. The obtained powders were characterized by X-Ray Diffraction (XRD), X-ray Photoelectron Spectroscopy (XPS), Fourier Transform Infra Red (FT-IR) spectroscopy and compared to three reference samples: commercial nano-crystalline transition alumina, YAG and Y{sub 2}O{sub 3}. YAG powders were obtained by co-precipitation route whereas Y{sub 2}O{sub 3} powders were yielded by spray-drying of a yttrium chloride aqueous solution. Modification of physico-chemical properties of the surface of alumina nanoparticles were assessed by combining XPS and FT-IR spectroscopies. On the basis of the results obtained, a possible model is proposed for the structure of the obtained composites, in which Y basically reacts with more acidic hydroxyls of alumina, by forming Y-rich surface grains, the extension of which depends on the thermal treatment. - Highlights: • Al{sub 2}O{sub 3}–Y{sub 3}Al{sub 5}O{sub 12} (YAG) composite nanopowders were prepared by spray drying. • Combined XPS and IR spectroscopy: effective tools to study surface modifications. • Y reacts with more acidic hydroxyls at alumina surface. • Y-rich surface grains form: their extension depends on the thermal treatment.

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

    Science.gov (United States)

    Benderskii, Alexander; Bordenyuk, Andrey; Weeraman, Champika

    2006-03-01

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

  19. Time-resolved Fourier transform infrared spectrometry using a microfabricated continuous flow mixer: application to protein conformation study using the example of ubiquitin.

    Science.gov (United States)

    Kakuta, Masaya; Hinsmann, Peter; Manz, Andreas; Lendl, Bernhard

    2003-05-01

    We report on the use of time-resolved Fourier transform infrared spectroscopy (FT-IR) to study chemically induced conformational changes of proteins using the example of ubiquitin. For this purpose a micromachined mixer is coupled to a conventional IR transmission cell with a pathlength of 25 microm and operated in both the continuous and the stopped-flow mode. This experimental set-up allows the elucidation of reaction pathways in the time frame of about 500 milliseconds to seconds with little reagent consumption and low pressure. For continuous flow measurements employed in the time frame from 0.5 to 1.4 s the reaction time is determined by the flow rate used as the connection between the point of confluence in the micromixer and the flow cell was kept constant in all experiments. For stopped-flow experiments (>1.4 s) the time is determined by data acquisition of the rapid scanning infrared spectrometer. Ubiquitin, a small well-known protein with 76 amino acid residues, changes its conformation from native to A-state with the addition of methanol under low pH conditions. We investigated the conformational change in the time frame from 0.5 to 10 s by mixing ubiquitin (20% methanol-d(4)) with an 80% methanol-d(4) solution at pD 2 by evaluating the time dependent changes in the amide I band of the protein.

  20. Perforated SiN membrane resonators for nanomechanical IR spectroscopy poster

    DEFF Research Database (Denmark)

    Kurek, Maksymilian; Carnoy, Matthias; Boisen, Anja

    Constant progress in micro- and nanofabrication provides a great opportunity in development of micro- and nanomechanical resonatorsthat can be used for sensing purposes. These sensors usually consist of singly-clamped cantilever beams, doubly-clamped bridges ormembranes that exhibit resonant......, lateral dimension of1×1 mm2 and 2 µm perforation grid pitch were used instead of strings which makes the IR beam alignment significantly simpler whilemaintaining similar sampling efficiency and photothermal IR absorption sensitivity....

  1. Time-resolving electron temperature diagnostic for ALCATOR C

    International Nuclear Information System (INIS)

    Fairfax, S.A.

    1984-05-01

    A diagnostic that provides time-resolved central electron temperatures has been designed, built, and tested on the ALCATOR C Tokamak. The diagnostic uses an array of fixed-wavelength x-ray crystal monochromators to sample the x-ray continuum and determine the absolute electron temperature. The resolution and central energy of each channel were chosen to exclude any contributions from impurity line radiation. This document describes the need for such a diagnostic, the design methodology, and the results with typical ALCATOR C plasmas. Sawtooth (m = 1) temperature oscillations were observed after pellet fueling of the plasma. This is the first time that such oscillations have been observed with an x-ray temperature diagnostic

  2. Fast time-resolved aerosol collector: proof of concept

    Science.gov (United States)

    Yu, X.-Y.; Cowin, J. P.; Iedema, M. J.; Ali, H.

    2010-10-01

    Atmospheric particles can be collected in the field on substrates for subsequent laboratory analysis via chemically sensitive single particle methods such as scanning electron microscopy with energy dispersive x-ray analysis. With moving substrates time resolution of seconds to minutes can be achieved. In this paper, we demonstrate how to increase the time resolution when collecting particles on a substrate to a few milliseconds to provide real-time information. Our fast time-resolved aerosol collector ("Fast-TRAC") microscopically observes the particle collection on a substrate and records an on-line video. Particle arrivals are resolved to within a single frame (4-17 ms in this setup), and the spatial locations are matched to the subsequent single particle analysis. This approach also provides in-situ information on particle size and number concentration. Applications are expected in airborne studies of cloud microstructure, pollution plumes, and surface long-term monitoring.

  3. Time-resolved tomographic images of a relativistic electron beam

    International Nuclear Information System (INIS)

    Koehler, H.A.; Jacoby, B.A.; Nelson, M.

    1984-07-01

    We obtained a sequential series of time-resolved tomographic two-dimensional images of a 4.5-MeV, 6-kA, 30-ns electron beam. Three linear fiber-optic arrays of 30 or 60 fibers each were positioned around the beam axis at 0 0 , 61 0 , and 117 0 . The beam interacting with nitrogen at 20 Torr emitted light that was focused onto the fiber arrays and transmitted to a streak camera where the data were recorded on film. The film was digitized, and two-dimensional images were reconstructed using the maximum-entropy tomographic technique. These images were then combined to produce an ultra-high-speed movie of the electron-beam pulse

  4. Photon-Counting Arrays for Time-Resolved Imaging

    Directory of Open Access Journals (Sweden)

    I. Michel Antolovic

    2016-06-01

    Full Text Available The paper presents a camera comprising 512 × 128 pixels capable of single-photon detection and gating with a maximum frame rate of 156 kfps. The photon capture is performed through a gated single-photon avalanche diode that generates a digital pulse upon photon detection and through a digital one-bit counter. Gray levels are obtained through multiple counting and accumulation, while time-resolved imaging is achieved through a 4-ns gating window controlled with subnanosecond accuracy by a field-programmable gate array. The sensor, which is equipped with microlenses to enhance its effective fill factor, was electro-optically characterized in terms of sensitivity and uniformity. Several examples of capture of fast events are shown to demonstrate the suitability of the approach.

  5. Evaluation of Turmeric Powder Adulterated with Metanil Yellow Using FT-Raman and FT-IR Spectroscopy

    Directory of Open Access Journals (Sweden)

    Sagar Dhakal

    2016-05-01

    Full Text Available Turmeric powder (Curcuma longa L. is valued both for its medicinal properties and for its popular culinary use, such as being a component in curry powder. Due to its high demand in international trade, turmeric powder has been subject to economically driven, hazardous chemical adulteration. This study utilized Fourier Transform-Raman (FT-Raman and Fourier Transform-Infra Red (FT-IR spectroscopy as separate but complementary methods for detecting metanil yellow adulteration of turmeric powder. Sample mixtures of turmeric powder and metanil yellow were prepared at concentrations of 30%, 25%, 20%, 15%, 10%, 5%, 1%, and 0.01% (w/w. FT-Raman and FT-IR spectra were acquired for these mixture samples as well as for pure samples of turmeric powder and metanil yellow. Spectral analysis showed that the FT-IR method in this study could detect the metanil yellow at the 5% concentration, while the FT-Raman method appeared to be more sensitive and could detect the metanil yellow at the 1% concentration. Relationships between metanil yellow spectral peak intensities and metanil yellow concentration were established using representative peaks at FT-Raman 1406 cm−1 and FT-IR 1140 cm−1 with correlation coefficients of 0.93 and 0.95, respectively.

  6. Understanding optically stimulated charge movement in quartz and feldspar using time-resolved measurements

    International Nuclear Information System (INIS)

    Ankjaergaard, C.

    2010-02-01

    Thermoluminescence (TL) and optically stimulated luminescence (OSL) from quartz and feldspar are widely used in accident dosimetry and luminescence dating. In order to improve already existing methods or to develop new methods towards extending the current limits of the technique, it is important to understand the charge movement within these materials. Earlier studies have primarily focussed on examination of the trap behaviour; however, this only tells half of the story as OSL is a combination of charge stimulation and recombination. By using time-resolved OSL (TR-OSL), one can directly examine the recombination route(s), and thus obtain insight into the other half of the process involved in luminescence emission. This thesis studies the TR-OSL and optically stimulated phosphorescence signals from quartz and feldspars spanning several orders of magnitude in time (few ns to the seconds time scale) in order to identify various charge transport mechanisms in the different time regimes. The techniques employed are time-resolved OSL, continuous-wave OSL, TL, optically stimulated exo-electron (OSE) emission and time-resolved OSE. These different techniques are used in combination with variable thermal or optical stimulation energy. The thesis first delves into three main methodological developments, namely (i) research and development of the equipment for TR-OSL measurements, (ii) finding the best method for multiple-exponential analysis of a TR-OSL curve, and (iii) optimisation of the pulsing configuration for the best separation of quartz OSL from a mixed quarts-feldspar sample. It then proceeds to study the different charge transport mechanisms subsequent to an optical stimulation pulse in quartz and feldspars. The results obtained for quartz conclude that the main lifetime component in quartz represents an excited state lifetime of the recombination centre, and the more slowly decaying components on the millisecond to seconds time scale arise from charge recycling

  7. Understanding optically stimulated charge movement in quartz and feldspar using time-resolved measurements

    Energy Technology Data Exchange (ETDEWEB)

    Ankjaergaard, C.

    2010-02-15

    Thermoluminescence (TL) and optically stimulated luminescence (OSL) from quartz and feldspar are widely used in accident dosimetry and luminescence dating. In order to improve already existing methods or to develop new methods towards extending the current limits of the technique, it is important to understand the charge movement within these materials. Earlier studies have primarily focussed on examination of the trap behaviour; however, this only tells half of the story as OSL is a combination of charge stimulation and recombination. By using time-resolved OSL (TR-OSL), one can directly examine the recombination route(s), and thus obtain insight into the other half of the process involved in luminescence emission. This thesis studies the TR-OSL and optically stimulated phosphorescence signals from quartz and feldspars spanning several orders of magnitude in time (few ns to the seconds time scale) in order to identify various charge transport mechanisms in the different time regimes. The techniques employed are time-resolved OSL, continuous-wave OSL, TL, optically stimulated exo-electron (OSE) emission and time-resolved OSE. These different techniques are used in combination with variable thermal or optical stimulation energy. The thesis first delves into three main methodological developments, namely (i) research and development of the equipment for TR-OSL measurements, (ii) finding the best method for multiple-exponential analysis of a TR-OSL curve, and (iii) optimisation of the pulsing configuration for the best separation of quartz OSL from a mixed quarts-feldspar sample. It then proceeds to study the different charge transport mechanisms subsequent to an optical stimulation pulse in quartz and feldspars. The results obtained for quartz conclude that the main lifetime component in quartz represents an excited state lifetime of the recombination centre, and the more slowly decaying components on the millisecond to seconds time scale arise from charge recycling

  8. Pressure-modulation dynamic attenuated-total-reflectance (ATR) FT-IR spectroscopy

    Science.gov (United States)

    Marcott, C.; Story, G. M.; Noda, I.; Bibby, A.; Manning, C. J.

    1998-06-01

    A single-reflectance attenuated-total-reflectance (ATR) accessory with a diamond internal-reflection element was modified by the addition of a piezoelectric transducer. Initial dynamic pressure-modulation experiments have been performed in the sample compartment of a step-scanning FT-IR spectrometer. A sinusoidal pressure modulation applied to samples of isotactic polypropylene and linear low density polyethylene resulted in dynamic responses which appear to be similar to those observed in previous dynamic 2D IR experiments. Preliminary pressure-modulation dynamic ATR results are also reported for a styrene-butadiene-styrene triblock copolymer. The new method has the advantages that a much wider variety of sample types and geometries can be studied and less sample preparation is required. Dynamic 2D IR experiments carried out by ATR no longer require thin films of large area and sufficient strength to withstand the dynamic strain applied by a rheometer. The ability to obtain dynamic IR spectroscopic information from a wider variety of sample types and thicknesses would greatly expand the amount of useful information that could be extracted from normally complicated, highly overlapped IR spectra.

  9. Raman and IR-ATR spectroscopy studies of heteroepitaxial structures with a GaN:C top layer

    Science.gov (United States)

    Cerqueira, M. F.; Vieira, L. G.; Alves, A.; Correia, R.; Huber, M.; Andreev, A.; Bonanni, A.; Vasilevskiy, M. I.

    2017-09-01

    This work, motivated by the technologically important task of determination of carbon dopant location in the GaN crystal lattice, employed Raman spectroscopy, with both resonant and non-resonant excitation, and infrared (IR) spectroscopy, in the attenuated total reflection (ATR) configuration, to study lattice vibration modes in a set of carbon-doped GaN (GaN:C) epilayers grown by metalorganic vapour phase epitaxy. We analyse Raman and IR-ATR spectra from the point of view of possible effects of the carbon doping, namely: (i) local vibration mode of C atoms in the nitrogen sublattice (whose frequency we theoretically estimate as 768 cm-1 using an isotope defect model), and (ii) shift in the positions of longitudinal modes owing to the phonon-plasmon coupling. We find only indirect hints of the doping effect on the resonant Raman spectra. However, we show theoretically and confirm experimentally that the IR-ATR spectroscopy can be a much more sensitive tool for this purpose, at least for the considered structures. A weak perturbation of the dielectric function of GaN:C, caused by the substitutional carbon impurity, is shown to produce a measurable dip in the ATR reflectivity spectra at  ≈770 cm-1 for both p- and s-polarizations. Moreover, it influences a specific (guided-wave type) mode observed at  ≈737 cm-1, originating from the GaN layer, which appears in the narrow frequency window where the real parts of the two components of the dielectric tensor of the hexagonal crystal have opposite signs. This interpretation is supported by our modelling of the whole multilayer structure, using a transfer matrix formalism.

  10. Conformational study of sarcosine as probed by matrix-isolation FT-IR spectroscopy and molecular orbital calculations

    OpenAIRE

    Gómez-Zavaglia, Andrea; Fausto, R.

    2003-01-01

    Sarcosine (N-methylglycine) has been studied by matrix-isolation FT-IR spectroscopy and molecular orbital calculations undertaken at the DFT/B3LYP and MP2 levels of theory with the 6-311++G(d, p) and 6-31++G(d, p) basis set, respectively. Eleven different conformers were located in the potential energy surface (PES) of sarcosine, with the ASC conformer being the ground conformational state. This form is analogous to the glycine most stable conformer and is characterized by a NH...O= intramole...

  11. Applications of a table-top time-resolved luminescence spectrometer with nanosecond soft X-ray pulse excitation

    Czech Academy of Sciences Publication Activity Database

    Brůža, P.; Pánek, D.; Fidler, V.; Benedikt, P.; Čuba, V.; Gbur, T.; Boháček, Pavel; Nikl, Martin

    2014-01-01

    Roč. 61, č. 1 (2014), s. 448-451 ISSN 0018-9499 R&D Projects: GA ČR GA13-09876S Institutional support: RVO:68378271 Keywords : LiCaAlF 6 * luminescence * scintillators * soft x-ray * SrHfO 3 * time-resolved spectroscopy * ZnO :Ga Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.283, year: 2014

  12. Spectroscopy and reactions of vibrationally excited transient molecules

    Energy Technology Data Exchange (ETDEWEB)

    Dai, H.L. [Univ. of Pennsylvania, Philadelphia (United States)

    1993-12-01

    Spectroscopy, energy transfer and reactions of vibrationally excited transient molecules are studied through a combination of laser-based excitation techniques and efficient detection of emission from the energized molecules with frequency and time resolution. Specifically, a Time-resolved Fourier Transform Emission Spectroscopy technique has been developed for detecting dispersed laser-induced fluorescence in the IR, visible and UV regions. The structure and spectroscopy of the excited vibrational levels in the electronic ground state, as well as energy relaxation and reactions induced by specific vibronic excitations of a transient molecule can be characterized from time-resolved dispersed fluorescence in the visible and UV region. IR emissions from highly vibrational excited levels, on the other hand, reveal the pathways and rates of collision induced vibrational energy transfer.

  13. Evidence for resonant bonding in phase-change materials studied by IR spectroscopy

    Directory of Open Access Journals (Sweden)

    K. Shportko

    2017-04-01

    Full Text Available Phase-change materials (PCM attract attention due to their unique properties. This remarkable portfolio also makes them promising for applications in novel data storage devices. In this study, we discuss differences in the optical properties of PCM and non-PCM in the IR caused by presence or absence of resonant bonding.

  14. Organic Spectroscopy Laboratory: Utilizing IR and NMR in the Identification of an Unknown Substance

    Science.gov (United States)

    Glagovich, Neil M.; Shine, Timothy D.

    2005-01-01

    A laboratory experiment that emphasizes the interpretation of both infrared (IR) and nuclear magnetic resonance (NMR) spectra in the elucidation of the structure of an unknown compound was developed. The method helps students determine [to the first power]H- and [to the thirteenth power]C-NMR spectra from the structures of compounds and to…

  15. A Rapid Method of Crude Oil Analysis Using FT-IR Spectroscopy

    African Journals Online (AJOL)

    HP USER

    Nigerian Journal of Basic and Applied Science (June,2016), 24(1): 47-55 ... ABSTRACT: This study determines the viability of the use of Fourier Transform ... IR spectra of Crude oil sample containing a mixture of both degraded (sample 151).

  16. Time-resolved laser-induced fluorescence system

    Science.gov (United States)

    Bautista, F. J.; De la Rosa, J.; Gallegos, F. J.

    2006-02-01

    Fluorescence methods are being used increasingly in the measurement of species concentrations in gases, liquids and solids. Laser induced fluorescence is spontaneous emission from atoms or molecules that have been excited by laser radiation. Here we present a time resolved fluorescence instrument that consists of a 5 μJ Nitrogen laser (337.1 nm), a sample holder, a quartz optical fiber, a spectrometer, a PMT and a PC that allows the measurement of visible fluorescence spectra (350-750 nm). Time response of the system is approximately 5 ns. The instrument has been used in the measurement of colored bond paper, antifreeze, diesel, cochineal pigment and malignant tissues. The data acquisition was achieved through computer control of a digital oscilloscope (using General Purpose Interface Bus GPIB) and the spectrometer via serial (RS232). The instrument software provides a graphic interface that lets make some data acquisition tasks like finding fluorescence spectra, and fluorescence lifetimes. The software was developed using the Lab-View 6i graphic programming package and can be easily managed in order to add more functions to it.

  17. In-pile Thermal Conductivity Characterization with Time Resolved Raman

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xinwei [Iowa State Univ., Ames, IA (United States). Dept. of Mechanical Engineering; Hurley, David H. [Idaho National Lab. (INL), Idaho Falls, ID (United States)

    2018-03-19

    The project is designed to achieve three objectives: (1) Develop a novel time resolved Raman technology for direct measurement of fuel and cladding thermal conductivity. (2) Validate and improve the technology development by measuring ceramic materials germane to the nuclear industry. (3) Conduct instrumentation development to integrate optical fiber into our sensing system for eventual in-pile measurement. We have developed three new techniques: time-domain differential Raman (TD-Raman), frequency-resolved Raman (FR-Raman), and energy transport state-resolved Raman (ET-Raman). The TD-Raman varies the laser heating time and does simultaneous Raman thermal probing, the FR-Raman probes the material’s thermal response under periodical laser heating of different frequencies, and the ET-Raman probes the thermal response under steady and pulsed laser heating. The measurement capacity of these techniques have been fully assessed and verified by measuring micro/nanoscale materials. All these techniques do not need the data of laser absorption and absolute material temperature rise, yet still be able to measure the thermal conductivity and thermal diffusivity with unprecedented accuracy. It is expected they will have broad applications for in-pile thermal characterization of nuclear materials based on pure optical heating and sensing.

  18. Time-Resolved Hard X-Ray Spectrometer

    International Nuclear Information System (INIS)

    Kenneth Moya; Ian McKennaa; Thomas Keenana; Michael Cuneob

    2007-01-01

    Wired array studies are being conducted at the SNL Z accelerator to maximize the x-ray generation for inertial confinement fusion targets and high energy density physics experiments. An integral component of these studies is the characterization of the time-resolved spectral content of the x-rays. Due to potential spatial anisotropy in the emitted radiation, it is also critical to diagnose the time-evolved spectral content in a space-resolved manner. To accomplish these two measurement goals, we developed an x-ray spectrometer using a set of high-speed detectors (silicon PIN diodes) with a collimated field-of-view that converged on a 1-cm-diameter spot at the pinch axis. Spectral discrimination is achieved by placing high Z absorbers in front of these detectors. We built two spectrometers to permit simultaneous different angular views of the emitted radiation. Spectral data have been acquired from recent Z shots for the radial and polar views. UNSPEC1 has been adapted to analyze and unfold the measured data to reconstruct the x-ray spectrum. The unfold operator code, UFO2, is being adapted for a more comprehensive spectral unfolding treatment

  19. Spectral and time-resolved studies on ocular structures

    Science.gov (United States)

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

    2007-07-01

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

  20. Time-resolved photoluminescence of SiOx encapsulated Si

    Science.gov (United States)

    Kalem, Seref; Hannas, Amal; Österman, Tomas; Sundström, Villy

    Silicon and its oxide SiOx offer a number of exciting electrical and optical properties originating from defects and size reduction enabling engineering new electronic devices including resistive switching memories. Here we present the results of photoluminescence dynamics relevant to defects and quantum confinement effects. Time-resolved luminescence at room temperature exhibits an ultrafast decay component of less than 10 ps at around 480 nm and a slower component of around 60 ps as measured by streak camera. Red shift at the initial stages of the blue luminescence decay confirms the presence of a charge transfer to long lived states. Time-correlated single photon counting measurements revealed a life-time of about 5 ns for these states. The same quantum structures emit in near infrared close to optical communication wavelengths. Nature of the emission is described and modeling is provided for the luminescence dynamics. The electrical characteristics of metal-oxide-semiconductor devices were correlated with the optical and vibrational measurement results in order to have better insight into the switching mechanisms in such resistive devices as possible next generation RAM memory elements. ``This work was supported by ENIAC Joint Undertaking and Laser-Lab Europe''.

  1. Time resolved EUV spectra from Zpinching capillary discharge plasma

    Science.gov (United States)

    Jancarek, Alexandr; Nevrkla, Michal; Nawaz, Fahad

    2015-09-01

    We developed symmetrically charged driver to obtain high voltage, high current Z-pinching capillary discharge. Plasma is created by up to 70 kA, 29 ns risetime current pulse passing through a 5 mm inner diameter, 224 mm long capillary filled with gas to initial pressure in the range of 1 kPa. Due to the low inductance design of the driver, the pinch is observable directly from the measured current curve. Time-integrated and time-resolved spectra of discharge plasma radiation are recorded together with the capillary current and analyzed. The most encouraging spectra were captured in the wavelength range 8.3 ÷ 14 nm. This spectral region contains nitrogen Balmer series lines including potentially lasing NVII 2 - 3 transition. Spectral lines are identified in the NIST database using the FLY kinetic code. The line of 13.38 nm wavelength, transition NVII 2 - 3, was observed in gated, and also in time-integrated spectra for currents >60 kA. This work has been supported by the Ministry of Education, Youth and Sports of the Czech Republic grants LG13029.

  2. Time-resolved pump-probe experiments at the LCLS

    Energy Technology Data Exchange (ETDEWEB)

    Glownia, James; /SLAC /Stanford U., Appl. Phys. Dept.; Cryan, J.; /SLAC /Stanford U., Phys. Dept.; Andreasson, J.; /Uppsala U.; Belkacem, A.; /LBNL, Berkeley; Berrah, N.; /Western Michigan U.; Blaga, C.L.; /Ohio State U.; Bostedt, C.; Bozek, J.; /SLAC; DiMauro, L.F.; /Ohio State U.; Fang, L.; /Western Michigan U.; Frisch, J.; /SLAC; Gessner, O.; /LBNL; Guhr, M.; /SLAC; Hajdu, J.; /Uppsala U.; Hertlein, M.P.; /LBNL; Hoener, M.; /Western Michigan U. /LBNL; Huang, G.; Kornilov, O.; /LBNL; Marangos, J.P.; /Imperial Coll., London; March, A.M.; /Argonne; McFarland, B.K.; /SLAC /Stanford U., Phys. Dept. /SLAC /IRAMIS, Saclay /Stanford U., Phys. Dept. /Georgia Tech /Argonne /Kansas State U. /SLAC /Stanford U., Phys. Dept. /SLAC /Stanford U., Appl. Phys. Dept. /Stanford U., Appl. Phys. Dept. /SLAC /LBNL /Argonne /SLAC /SLAC /Stanford U., Appl. Phys. Dept. /Stanford U., Phys. Dept.

    2011-08-12

    The first time-resolved x-ray/optical pump-probe experiments at the SLAC Linac Coherent Light Source (LCLS) used a combination of feedback methods and post-analysis binning techniques to synchronize an ultrafast optical laser to the linac-based x-ray laser. Transient molecular nitrogen alignment revival features were resolved in time-dependent x-ray-induced fragmentation spectra. These alignment features were used to find the temporal overlap of the pump and probe pulses. The strong-field dissociation of x-ray generated quasi-bound molecular dications was used to establish the residual timing jitter. This analysis shows that the relative arrival time of the Ti:Sapphire laser and the x-ray pulses had a distribution with a standard deviation of approximately 120 fs. The largest contribution to the jitter noise spectrum was the locking of the laser oscillator to the reference RF of the accelerator, which suggests that simple technical improvements could reduce the jitter to better than 50 fs.

  3. Geographic identification of Boletus mushrooms by data fusion of FT-IR and UV spectroscopies combined with multivariate statistical analysis

    Science.gov (United States)

    Yao, Sen; Li, Tao; Li, JieQing; Liu, HongGao; Wang, YuanZhong

    2018-06-01

    Boletus griseus and Boletus edulis are two well-known wild-grown edible mushrooms which have high nutrition, delicious flavor and high economic value distributing in Yunnan Province. In this study, a rapid method using Fourier transform infrared (FT-IR) and ultraviolet (UV) spectroscopies coupled with data fusion was established for the discrimination of Boletus mushrooms from seven different geographical origins with pattern recognition method. Initially, the spectra of 332 mushroom samples obtained from the two spectroscopic techniques were analyzed individually and then the classification performance based on data fusion strategy was investigated. Meanwhile, the latent variables (LVs) of FT-IR and UV spectra were extracted by partial least square discriminant analysis (PLS-DA) and two datasets were concatenated into a new matrix for data fusion. Then, the fusion matrix was further analyzed by support vector machine (SVM). Compared with single spectroscopic technique, data fusion strategy can improve the classification performance effectively. In particular, the accuracy of correct classification of SVM model in training and test sets were 99.10% and 100.00%, respectively. The results demonstrated that data fusion of FT-IR and UV spectra can provide higher synergic effect for the discrimination of different geographical origins of Boletus mushrooms, which may be benefit for further authentication and quality assessment of edible mushrooms.

  4. Classification of edible oils and modeling of their physico-chemical properties by chemometric methods using mid-IR spectroscopy

    Science.gov (United States)

    Luna, Aderval S.; da Silva, Arnaldo P.; Ferré, Joan; Boqué, Ricard

    This research work describes two studies for the classification and characterization of edible oils and its quality parameters through Fourier transform mid infrared spectroscopy (FT-mid-IR) together with chemometric methods. The discrimination of canola, sunflower, corn and soybean oils was investigated using SVM-DA, SIMCA and PLS-DA. Using FT-mid-IR, DPLS was able to classify 100% of the samples from the validation set, but SIMCA and SVM-DA were not. The quality parameters: refraction index and relative density of edible oils were obtained from reference methods. Prediction models for FT-mid-IR spectra were calculated for these quality parameters using partial least squares (PLS) and support vector machines (SVM). Several preprocessing alternatives (first derivative, multiplicative scatter correction, mean centering, and standard normal variate) were investigated. The best result for the refraction index was achieved with SVM as well as for the relative density except when the preprocessing combination of mean centering and first derivative was used. For both of quality parameters, the best results obtained for the figures of merit expressed by the root mean square error of cross validation (RMSECV) and prediction (RMSEP) were equal to 0.0001.

  5. The nature of hydrogen-bonding interactions in nonsteroidal anti-inflammatory drugs revealed by polarized IR spectroscopy

    Science.gov (United States)

    Hachuła, Barbara

    2018-01-01

    The influence of hydrogen-bonding interactions in the solid phase on the IR spectroscopic pattern of the νOsbnd H band of nonsteroidal anti-inflammatory drugs (NSAIDs) was studied experimentally by IR spectroscopy with the use of polarized light at two temperatures (293 K and 77 K) and in isotopic dilution. The neat and deuterated crystals of (S)-naproxen ((S)-NPX), (R)-flurbiprofen ((R)-FBP), (RS)-flurbiprofen ((RS)-FBP) and (RS)-ketoprofen ((RS)-KTP) were obtained by melt crystallization between the two squeezed CaF2 plates. The vibrational spectra of selected α-aryl propionic acid derivatives (2APAs) reflected the characteristics of their hydrogen-bond networks, i.e., 2APAs were characterized by the chain ((S)-NPX, (R)-FBP) and by dimeric ((RS)-FBP, (RS)-KTP) arrangement of hydrogen bonds in the crystal lattice. Spectroscopic results showed that the interchain (through-space) exciton coupling, between two laterally-spaced hydrogen bonds, dominates in the crystals of four NSAIDs. The same exciton coupled hydrogen bonds were also responsible for the H/D isotopic recognition mechanism in the crystalline spectra of deuterated 2APAs. The presented spectral results may help to predict the hydrogen bond motifs in the crystalline NSAIDs, which structures are not yet known, based on their IR spectra of hydrogen bond in the crystals.

  6. Application of fourier-transform infrared (ft-ir) spectroscopy for determination of total phenolics of freeze dried lemon juices

    International Nuclear Information System (INIS)

    Sherazi, S.T.H.; Bhutto, A.A.; Mehesar, S.A.

    2017-01-01

    A cost effective and environmentally safe analytical method for rapid assessment of total phenolic content (TPC) in freeze dried lemon juice samples was developed using transmission Fourier-transform infrared spectroscopy (FT-IR) in conjunction with chemometric techniques. Two types of calibrations i.e. simple Beer's law and partial least square (PLS) were applied to investigate most accurate calibration model based on region from1420 to 1330 cm-1. The better analytical performance was obtained by PLS technique coefficient of determination (R2), root mean square error of calibration (RMSEC) with the value of 0.999 and 0.00864, respectively. The results of TPC in freeze dried lemon juice samples obtained by transmission FT-IR were compared with TPC observed by Folin-Ciocalteu (FC) assay and found to be comparable. Outcomes of the present study indicate that transmission FT-IR spectroscopic approach could be used as an alternative approach in place of Folin-Ciocalteu (FC) assay which is expensive and time-consuming conventional chemical methods for determination of the total phenolic content of lemon fruits. (author)

  7. The characterization of natural gemstones using non-invasive FT-IR spectroscopy: New data on tourmalines.

    Science.gov (United States)

    Mercurio, Mariano; Rossi, Manuela; Izzo, Francesco; Cappelletti, Piergiulio; Germinario, Chiara; Grifa, Celestino; Petrelli, Maurizio; Vergara, Alessandro; Langella, Alessio

    2018-02-01

    Fourteen samples of tourmaline from the Real Museo Mineralogico of Federico II University (Naples) have been characterized through multi-methodological investigations (EMPA-WDS, SEM-EDS, LA-ICP-MS, and FT-IR spectroscopy). The samples show different size, morphology and color, and are often associated with other minerals. Data on major and minor elements allowed to identify and classify tourmalines as follows: elbaites, tsilaisite, schorl, dravites, uvites and rossmanite. Non-invasive, non-destructive FT-IR and in-situ analyses were carried out on the same samples to validate this chemically-based identification and classification. The results of this research show that a complete characterization of this mineral species, usually time-consuming and expensive, can be successfully achieved through non-destructive FT-IR technique, thus representing a reliable tool for a fast classification extremely useful to plan further analytical strategies, as well as to support gemological appraisals. Copyright © 2017 Elsevier B.V. All rights reserved.

  8. Biochemical Monitoring of Spinal Cord Injury by FT-IR Spectroscopy--Effects of Therapeutic Alginate Implant in Rat Models.

    Directory of Open Access Journals (Sweden)

    Sandra Tamosaityte

    Full Text Available Spinal cord injury (SCI induces complex biochemical changes, which result in inhibition of nervous tissue regeneration abilities. In this study, Fourier-transform infrared (FT-IR spectroscopy was applied to assess the outcomes of implants made of a novel type of non-functionalized soft calcium alginate hydrogel in a rat model of spinal cord hemisection (n = 28. Using FT-IR spectroscopic imaging, we evaluated the stability of the implants and the effects on morphology and biochemistry of the injured tissue one and six months after injury. A semi-quantitative evaluation of the distribution of lipids and collagen showed that alginate significantly reduced injury-induced demyelination of the contralateral white matter and fibrotic scarring in the chronic state after SCI. The spectral information enabled to detect and localize the alginate hydrogel at the lesion site and proved its long-term persistence in vivo. These findings demonstrate a positive impact of alginate hydrogel on recovery after SCI and prove FT-IR spectroscopic imaging as alternative method to evaluate and optimize future SCI repair strategies.

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

    Directory of Open Access Journals (Sweden)

    Klaus Mann

    2009-11-01

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

  10. ATR FT-IR spectroscopy on Vmh2 hydrophobin self-assembled layers for Teflon membrane bio-functionalization

    International Nuclear Information System (INIS)

    Portaccio, M.; Gravagnuolo, A.M.; Longobardi, S.; Giardina, P.; Rea, I.; De Stefano, L.; Cammarota, M.; Lepore, M.

    2015-01-01

    Graphical abstract: - Highlights: • Hydrophobin self-assembled layers on Teflon in different preparation conditions were investigated. • ATR collection data geometry allowed samples examination without any particular preparation. • Amide content, lipid/amide and carbohydrate/amide ratios of the protein layer were estimated. • Secondary structure of protein was determined for the examined samples. • FT-IR demonstrated to be of extreme relevance in monitoring hydrophobin self-assembled layers preparation. - Abstract: Surface functionalization by layers of hydrophobins, amphiphilic proteins produced by fungi offers a promising and green strategy for fabrication of biomedical and bioanalytical devices. The layering process of the Vmh2 hydrophobin from Pleurotus ostreatus on Teflon membrane has been investigated by Attenuated Total Reflection Fourier Transform Infrared (ATR FT-IR) spectroscopy. In particular, protein layers obtained with hydrophobin purified with two different procedures and in various coating conditions have been examined. The layers have been characterized by quantifying the amide I and amide II band area together with the lipid/amide ratio and carbohydrate/amide ratio. This characterization can be very useful in evaluating the best purification strategy and coating conditions. Moreover the analysis of the secondary structure of the layered protein using the deconvolution procedure of amide I band indicate the prevalent contribution from β-sheet state. The results inferred by infrared spectroscopy have been also confirmed by scanning electron microscopy imaging

  11. ATR FT-IR spectroscopy on Vmh2 hydrophobin self-assembled layers for Teflon membrane bio-functionalization

    Energy Technology Data Exchange (ETDEWEB)

    Portaccio, M., E-mail: marianna.portaccio@unina2.it [Dipartimento di Medicina Sperimentale – Seconda Università di Napoli, Via S.M. di Costantinopoli, 16-80134 Napoli (Italy); Gravagnuolo, A.M., E-mail: alfredomaria.gravagnuolo@unina.it [Dipartimento di Scienze Chimiche, Università “Federico II”, Via Cintia, 21- 80126 Napoli (Italy); Longobardi, S., E-mail: sara.longobardi@unina.it [Dipartimento di Scienze Chimiche, Università “Federico II”, Via Cintia, 21- 80126 Napoli (Italy); Giardina, P., E-mail: paola.giardina@unina.it [Dipartimento di Scienze Chimiche, Università “Federico II”, Via Cintia, 21- 80126 Napoli (Italy); Rea, I., E-mail: ilaria.rea@na.imm.cnr.it [Institute for Microelectronics and Microsystems, CNR, Via P. Castellino, 111-80131 Napoli (Italy); De Stefano, L., E-mail: luca.destefano@na.imm.cnr.it [Institute for Microelectronics and Microsystems, CNR, Via P. Castellino, 111-80131 Napoli (Italy); Cammarota, M., E-mail: marcella.cammarota@unina2.it [Dipartimento di Medicina Sperimentale – Seconda Università di Napoli, Via S.M. di Costantinopoli, 16-80134 Napoli (Italy); Lepore, M., E-mail: maria.lepore@unina2.it [Dipartimento di Medicina Sperimentale – Seconda Università di Napoli, Via S.M. di Costantinopoli, 16-80134 Napoli (Italy)

    2015-10-01

    Graphical abstract: - Highlights: • Hydrophobin self-assembled layers on Teflon in different preparation conditions were investigated. • ATR collection data geometry allowed samples examination without any particular preparation. • Amide content, lipid/amide and carbohydrate/amide ratios of the protein layer were estimated. • Secondary structure of protein was determined for the examined samples. • FT-IR demonstrated to be of extreme relevance in monitoring hydrophobin self-assembled layers preparation. - Abstract: Surface functionalization by layers of hydrophobins, amphiphilic proteins produced by fungi offers a promising and green strategy for fabrication of biomedical and bioanalytical devices. The layering process of the Vmh2 hydrophobin from Pleurotus ostreatus on Teflon membrane has been investigated by Attenuated Total Reflection Fourier Transform Infrared (ATR FT-IR) spectroscopy. In particular, protein layers obtained with hydrophobin purified with two different procedures and in various coating conditions have been examined. The layers have been characterized by quantifying the amide I and amide II band area together with the lipid/amide ratio and carbohydrate/amide ratio. This characterization can be very useful in evaluating the best purification strategy and coating conditions. Moreover the analysis of the secondary structure of the layered protein using the deconvolution procedure of amide I band indicate the prevalent contribution from β-sheet state. The results inferred by infrared spectroscopy have been also confirmed by scanning electron microscopy imaging.

  12. Time-resolved soft x-ray spectra from laser-produced Cu plasma

    International Nuclear Information System (INIS)

    Cone, K.V.; Dunn, J.; Baldis, H.A.; May, M.J.; Purvis, M.A.; Scott, H.A.; Schneider, M.B.

    2012-01-01

    The volumetric heating of a thin copper target has been studied with time resolved x-ray spectroscopy. The copper target was heated from a plasma produced using the Lawrence Livermore National Laboratory's Compact Multipulse Terrawatt (COMET) laser. A variable spaced grating spectrometer coupled to an x-ray streak camera measured soft x-ray emission (800-1550 eV) from the back of the copper target to characterize the bulk heating of the target. Radiation hydrodynamic simulations were modeled in 2-dimensions using the HYDRA code. The target conditions calculated by HYDRA were post-processed with the atomic kinetics code CRETIN to generate synthetic emission spectra. A comparison between the experimental and simulated spectra indicates the presence of specific ionization states of copper and the corresponding electron temperatures and ion densities throughout the laser-heated copper target.

  13. Time-resolved x-ray spectra from laser-generated high-density plasmas

    Science.gov (United States)

    Andiel, U.; Eidmann, Klaus; Witte, Klaus-Juergen

    2001-04-01

    We focused frequency doubled ultra short laser pulses on solid C, F, Na and Al targets, K-shell emission was systematically investigated by time resolved spectroscopy using a sub-ps streak camera. A large number of laser shots can be accumulated when triggering the camera with an Auston switch system at very high temporal precision. The system provides an outstanding time resolution of 1.7ps accumulating thousands of laser shots. The time duration of the He-(alpha) K-shell resonance lines was observed in the range of (2-4)ps and shows a decrease with the atomic number. The experimental results are well reproduced by hydro code simulations post processed with an atomic kinetics code.

  14. Spectroelectrochemical study of polyphenylene by in situ external reflection FT-IR spectroscopy. Pt. 2

    International Nuclear Information System (INIS)

    Kvarnstroem, C.; Ivaska, A.

    1994-01-01

    In situ external reflection FT-IR measurements are performed during cyclic voltammetric scans on electrochemically polymerized polyphenylene films. The films are polymerized either in 0.1 or 0.8 M biphenyl in 0.1 M TBABF 4 in acetonitrile. Changes in the IR spectrum of films of different thicknesses are studied when the films are potentially cycled from the neutral to the oxidized states of the polymer. No differences between films made in high or low dimer concentration can be observed in the spectra. The potential-dependent insertion and expulsion of solvent, residual water, anions and cations in and out of the film have different behaviour in films of different thicknesses. Changes in the structure of the segments in the film, from the benzenoid form into the quinoid form, can be followed. Differences between the first and subsequent cyclic potential scans are observed. (orig.)

  15. Identification of the fragment of the 1-methylpyrene cation by mid-IR spectroscopy

    Science.gov (United States)

    Jusko, Pavol; Simon, Aude; Wenzel, Gabi; Brünken, Sandra; Schlemmer, Stephan; Joblin, Christine

    2018-04-01

    The fragment of the 1-methylpyrene cation, 17C 11H+, is expected to exist in two isomeric forms, 1-pyrenemethylium PyrCH2+ and the tropylium containing species PyrC7+. We measured the infrared (IR) action spectrum of cold 17C 11H+ tagged with Ne using a cryogenic ion trap instrument coupled to the FELIX laser. Comparison of the experimental data with density functional theory calculations allows us to identify the PyrCH2+ isomer in our experiments. The IR Multi-Photon Dissociation spectrum was also recorded following the C2H2 loss channel. Its analysis suggests combined effects of anharmonicity and isomerisation while heating the trapped ions, as shown by molecular dynamics simulations.

  16. Time-resolved studies at PETRA III with a highly repetitive synchronized laser system

    Energy Technology Data Exchange (ETDEWEB)

    Schlie, Mortiz

    2013-09-15

    Atomic and molecular processes can nowadays be directly followed in the time domain. This is a core technique for a better understanding of the involved fundamental physics, thus auguring new applications in the future as well. Usually the so-called pump-probe technique making use of two synchronized ultrashort light pulses is utilized to obtain this time-resolved data. In this work, the development and characterization of a synchronization system enabling such pump-probe studies at the storage ring PETRA III in combination with an external, then synchronized fs-laser system is described. The synchronization is based on an extended PLL approach with three interconnected feedback loops allowing to monitor short-time losses of the lock and thus prevent them. This way, the jitter between the laser PHAROS and the PETRA III reference signal is reduced to {sigma} <5 ps. Thus the system allows to conduct experiments at a repetition rate of 130 kHz with a temporal resolution limited only by the X-ray pulse length. A major emphasis in the fundamental introductory chapters is an intuitive explanation of the basic principles of phase locked loops and the different aspects of phase noise to allow a deeper understanding of the synchronization. Furthermore, first pump-probe experiments conducted at different beamlines at PETRA III are presented, demonstrating the usability of the laser system in a scientific environment as well. In first characterizing experiments the pulse duration of PETRA III X-ray pulses has been measured to be 90 ps FWHM. In particular, there have been time resolved X-ray absorption spectroscopy experiments on Gaq3 and Znq2 conducted at beamline P11. First results show dynamics of the electronic excitation on the timescale of a few hundred pico seconds up to a few nano seconds and provide a basic understanding for further research on those molecules. For Gaq3 this data is analyzed in detail and compared with visible fluorescence measurements suggesting at

  17. Time-resolved studies at PETRA III with a highly repetitive synchronized laser system

    International Nuclear Information System (INIS)

    Schlie, Mortiz

    2013-09-01

    Atomic and molecular processes can nowadays be directly followed in the time domain. This is a core technique for a better understanding of the involved fundamental physics, thus auguring new applications in the future as well. Usually the so-called pump-probe technique making use of two synchronized ultrashort light pulses is utilized to obtain this time-resolved data. In this work, the development and characterization of a synchronization system enabling such pump-probe studies at the storage ring PETRA III in combination with an external, then synchronized fs-laser system is described. The synchronization is based on an extended PLL approach with three interconnected feedback loops allowing to monitor short-time losses of the lock and thus prevent them. This way, the jitter between the laser PHAROS and the PETRA III reference signal is reduced to σ <5 ps. Thus the system allows to conduct experiments at a repetition rate of 130 kHz with a temporal resolution limited only by the X-ray pulse length. A major emphasis in the fundamental introductory chapters is an intuitive explanation of the basic principles of phase locked loops and the different aspects of phase noise to allow a deeper understanding of the synchronization. Furthermore, first pump-probe experiments conducted at different beamlines at PETRA III are presented, demonstrating the usability of the laser system in a scientific environment as well. In first characterizing experiments the pulse duration of PETRA III X-ray pulses has been measured to be 90 ps FWHM. In particular, there have been time resolved X-ray absorption spectroscopy experiments on Gaq3 and Znq2 conducted at beamline P11. First results show dynamics of the electronic excitation on the timescale of a few hundred pico seconds up to a few nano seconds and provide a basic understanding for further research on those molecules. For Gaq3 this data is analyzed in detail and compared with visible fluorescence measurements suggesting at least

  18. Ultrasensitive time-resolved immunofluorometric assay of pepsinogen I

    International Nuclear Information System (INIS)

    Huang Biao; Xiao Hualong; Zhang Xiangrui; Zhu Lan; Jiang Menjun

    2004-01-01

    Purpose: To construct a two-site sandwich-type assay for pepsinogen I with time-resolved fluoroimmunoassay (TRFIA) as a detection technique. Methods: On the noncompetitive assay, one monoclonal antibody (McAb) coating on wells directed against a specific antigenic site on the pepsinogen I, the europium-labelled McAb which was prepared by with helpful of the europium-chelate of N-(p-isothiocyanatobenzyl)- diethylenetriamine-N, N, N, N-tetraacetic acid directed against a different antigenic site on the pepsinogen I molecule we called labelling McAb. The luminescent enhancement system was enhancement solution which contained mainly 2-naphthoyltrifluoroacetone. 25μl of Calibrators or samples and 200 μl of the assay buffer were pipetted into coated microtiter wells. The plates were incubated with mechanical shaking for 1 h at 25 degree C, washed two times, then added 100 μl Eu3+- McAb solution diluted 50-fold in assay buffer. The plates were incubated again with mechanical shaking for 1 h at 25 degree C,After six washings, 200 μl of enhancement solution were dispense into each well. The plates were shaken for 5 min and fluorescence readings. All the proceeding were done by auto DELFIA1235, software was designed by our lab. The calibration curve and calculation of the concentrations in the unknown samples were performed automatically by using Multicalc software program, where a spline algorithm on logarithmically transformed data was employed. Results: The average labelling yield is 8.6 Eu3+/McAb giving high sensitivity with low background(<1000 cps). The measurement range was 3.5-328 μ g /L with ED25, ED50, ED80 of 11.34 ±0.2 μ g/L, 38.73±0.8 μ g /L and 132,3±2.9 μ g/L. The detection limit, defined as the concentration of PGI corresponding to the fluorescence of the zero calibrators plus two SDs, is 0..05μg/L. Within-run and between-run precision was l.9% and 4.7% which assessed at various PGI concentrations between 5 and 300 μg/L. We checked for cross

  19. Rapid authentication and identification of different types of A. roxburghii by Tri-step FT-IR spectroscopy

    Science.gov (United States)

    Chen, Ying; Huang, Jinfang; Yeap, Zhao Qin; Zhang, Xue; Wu, Shuisheng; Ng, Chiew Hoong; Yam, Mun Fei

    2018-06-01

    Anoectochilus roxburghii (Wall.) Lindl. (Orchidaceae) is a precious traditional Chinese medicinal herb and has been perennially used to treat various illness. However, there were unethical sellers who adulterated wild A. roxburghii with tissue cultured and cultivated ones. Therefore, there is an urgent need for an effective authentication method to differentiate between these different types of A. roxburghii. In this research, the infrared spectroscopic tri-step identification approach including Fourier transform infrared spectroscopy (FT-IR), Second derivative infrared spectra (SD-IR) and two-dimensional correlation infrared spectra (2D-IR) was used to develop a simple and rapid method to discriminate between wild, cultivated and tissue cultivated A. roxburghii plant. Through this study, all three types of A. roxburghii plant were successfully identified and discriminated through the infrared spectroscopic tri-step identification method. Besides that, all the samples of wild, cultivated and tissue cultivated A. roxburghii plant were analysed with the Soft Independent Modelling of Class Analogy (SIMCA) pattern recognition technique to test and verify the experimental results. The results showed that the three types of A. roxburghii can be discriminated clearly as the recognition rate was 100% for all three types and the rejection rate was more than 60%. 70% of the validated samples were also identified correctly by the SIMCA model. The SIMCA model was also validated by comparing 70 standard herbs to the model. As a result, it was demonstrated that the macroscopic IR fingerprint method and the classification analysis could discriminate not only between the A. roxburghi samples and the standard herbs, it could also distinguish between the three different types of A. roxburghi plant in a direct, rapid and holistic manner.

  20. The study of the radiation chemical transformation of the hexane on the surface of aluminium by IR-spectroscopy method

    International Nuclear Information System (INIS)

    Rimikhanova, A.N.

    2006-01-01

    Full text: In this work the experimental results of the radiation-chemical transformation of hexane on the aluminum surface obtained by IR spectroscopy method at room temperature have been presented. The metallic aluminum plates which was obtained by stage pressing granules by mark of AD-00 with the reflection coefficient R=0,85 in the middle infrared range of waves length λ=15 ± 2,2 mkm were used. As an adsorbate unsaturated vapors of hexane were used, the absorption of which was being carried out at the room temperature by the method. The radiation of system was carried out with γ-quanta of Co 60 with doze rate of 1,03 Gy/s - 1, and the absorbed doze in the system was (0,5-2)10 4 Gy. IR reflection spectra when beams fall on the sample under angle near the slipping were measured in diapason of 3600-650 cm - 1 by the spectrophotometer S pecord 71IR . The radiation chemical decomposition of hexane in heterosystem was being traced in stretching (3000-2700 cm - 1) and deformation (1500-1300 cm - 1) vibration diapasons of C-H bonds. The analysis of IR reflection spectra of Al-ads.hexane heterosystem showed that the main products of radiation chemical transformation are hydrocarbons C1-C5, olefins: propylene, butene-1, hexene-1, transhexene-3 and hydrocarbons more heavy than hexane. In frequency range of 1700-2000 cm - 1 the absorption bands of Al-H vibration which concern to aluminum hydrides are founded. By increasing of radiation dose the tendency of increasing of hydrogen accumulation as aluminum hydrides has been established

  1. The Influence of Cholesterol on Fast Dynamics Inside of Vesicle and Planar Phospholipid Bilayers Measured with 2D IR Spectroscopy.

    Science.gov (United States)

    Kel, Oksana; Tamimi, Amr; Fayer, Michael D

    2015-07-23

    Phospholipid bilayers are frequently used as models for cell membranes. Here the influence of cholesterol on the structural dynamics in the interior of 1,2-dilauroyl-sn-glycero-3-phosphocholine (dilauroylphosphatidylcholine, DLPC) vesicles and DLPC planar bilayers are investigated as a function of cholesterol concentration. 2D IR vibrational echo spectroscopy was performed on the antisymmetric CO stretch of the vibrational probe molecule tungsten hexacarbonyl, which is located in the interior alkyl regions of the bilayers. The 2D IR experiments measure spectral diffusion, which is caused by the structural fluctuations of the bilayers. The 2D IR measurements show that the bilayer interior alkyl region dynamics occur on time scales ranging from a few picoseconds to many tens of picoseconds. These are the time scales of the bilayers' structural dynamics, which act as the dynamic solvent bath for chemical processes of membrane biomolecules. The results suggest that at least a significant fraction of the dynamics arise from density fluctuations. Samples are studied in which the cholesterol concentration is varied from 0% to 40% in both the vesicles (72 nm diameter) and fully hydrated planar bilayers in the form of aligned multibilayers. At all cholesterol concentrations, the structural dynamics are faster in the curved vesicle bilayers than in the planar bilayers. As the cholesterol concentration is increased, at a certain concentration there is a sudden change in the dynamics, that is, the dynamics abruptly slow down. However, this change occurs at a lower concentration in the vesicles (between 10% and 15% cholesterol) than in the planar bilayers (between 25% and 30% cholesterol). The sudden change in the dynamics, in addition to other IR observables, indicates a structural transition. However, the results show that the cholesterol concentration at which the transition occurs is influenced by the curvature of the bilayers.

  2. Application of Fourier-transform infrared (FT-IR) spectroscopy for simple and easy determination of chylomicron-triglyceride and very low density lipoprotein-triglyceride.

    Science.gov (United States)

    Sato, Kenichi; Seimiya, Masanori; Kodera, Yoshio; Kitamura, Akihide; Nomura, Fumio

    2010-02-01

    Fourier-transform infrared (FT-IR) spectroscopy is a simple and reagent-free physicochemical analysis method, and is a potential alternative to more time-consuming and labor-intensive procedures. In this study, we aimed to use FT-IR spectroscopy to determine serum concentrations of chylomicron-triglyceride (TG) and very low density lipoprotein (VLDL)-TG. We analyzed a chylomicron fraction and VLDL fraction, which had been obtained by ultracentrifugation, to search for wavelengths to designate to each fraction. Then, partial least square (PLS) calibrations were developed using a training set of samples, for which TG concentrations had been determined by conventional procedures. Validation was conducted with another set of samples using the PLS model to predict serum TG concentrations on the basis of the samples' IR spectra. We analyzed a total of 150 samples. Serum concentrations of chylomicron-TG and VLDL-TG estimated by FT-IR spectroscopy agreed well with those obtained by the reference method (r=0.97 for both lipoprotein fractions). FT-IR spectrometric analysis required 15mul of serum and was completed within 1min. Serum chylomicron-TG and VLDL-TG concentrations can be determined with FT-IR spectroscopy. This rapid and simple test may have a great impact on the management of patients with dyslipidemia. Copyright 2009. Published by Elsevier B.V.

  3. Experimental Visualizations of a Generic Launch Vehicle Flow Field: Time-Resolved Shadowgraph and Infrared Imaging

    Science.gov (United States)

    Garbeff, Theodore J., II; Panda, Jayanta; Ross, James C.

    2017-01-01

    Time-Resolved shadowgraph and infrared (IR) imaging were performed to investigate off-body and on-body flow features of a generic, 'hammer-head' launch vehicle geometry previously tested by Coe and Nute (1962). The measurements discussed here were one part of a large range of wind tunnel test techniques that included steady-state pressure sensitive paint (PSP), dynamic PSP, unsteady surface pressures, and unsteady force measurements. Image data was captured over a Mach number range of 0.6 less than or equal to M less than or equal to 1.2 at a Reynolds number of 3 million per foot. Both shadowgraph and IR imagery were captured in conjunction with unsteady pressures and forces and correlated with IRIG-B timing. High-speed shadowgraph imagery was used to identify wake structure and reattachment behind the payload fairing of the vehicle. Various data processing strategies were employed and ultimately these results correlated well with the location and magnitude of unsteady surface pressure measurements. Two research grade IR cameras were positioned to image boundary layer transition at the vehicle nose and flow reattachment behind the payload fairing. The poor emissivity of the model surface treatment (fast PSP) proved to be challenging for the infrared measurement. Reference image subtraction and contrast limited adaptive histogram equalization (CLAHE) were used to analyze this dataset. Ultimately turbulent boundary layer transition was observed and located forward of the trip dot line at the model sphere-cone junction. Flow reattachment location was identified behind the payload fairing in both steady and unsteady thermal data. As demonstrated in this effort, recent advances in high-speed and thermal imaging technology have modernized classical techniques providing a new viewpoint for the modern researcher

  4. Spectroscopic techniques in the study of human tissues and their components. Part I: IR spectroscopy.

    Science.gov (United States)

    Olsztyńska-Janus, Sylwia; Szymborska-Małek, Katarzyna; Gąsior-Głogowska, Marlena; Walski, Tomasz; Komorowska, Małgorzata; Witkiewicz, Wojciech; Pezowicz, Celina; Kobielarz, Magdalena; Szotek, Sylwia

    2012-01-01

    Among the currently used methods of monitoring human tissues and their components many types of research are distinguished. These include spectroscopic techniques. The advantage of these techniques is the small amount of sample required, the rapid process of recording the spectra, and most importantly in the case of biological samples - preparation of tissues is not required. In this work, vibrational spectroscopy: ATR-FTIR and Raman spectroscopy will be used. Studies are carried out on tissues: tendons, blood vessels, skin, red blood cells and biological components: amino acids, proteins, DNA, plasma, and deposits.

  5. IR reflectance spectroscopy of carbon dioxide clathrate hydrates. Implications for Saturn's icy moons.

    Science.gov (United States)

    Oancea, A.; Grasset, O.; Le Menn, E.; Bezacier, L.; Bollengier, O.; Le Mouélic, S.; Tobie, G.

    2012-04-01

    A CO2 spectral band was discovered by VIMS on the Saturn's satellites Dione, Hyperion, Iapetus and Phoebe [1]. The band position on the three first satellites corresponds to CO2 trapped in a complex material, but no indication exists whether this latter is water ice or some mineral or complex organic compound [1]. On Phoebe, the CO2 spectral band is consistent with solid CO2 or CO2 molecules trapped in the small cages of a clathrate hydrate structure [2]. It is thought that clathrate hydrates could play a significant role in the chemistry of the solar nebula [3] and in the physical evolution of astrophysical objects [4]. But so far, no clathrate hydrate structure has been observed in astrophysical environments. Moreover, identification of molecules trapped in a clathrate hydrate structure is extremely difficult because of the strong IR vibration modes of the water ice matrix. In this work, experimental IR reflectance spectra for CO2 clathrate hydrates are studied on grains and films. Clathrates are synthesized in a high pressure autoclave at low temperatures. IR spectral analysis is made with a low pressure and low temperature cryostat. These experimental conditions - 80 spectrum will be presented. A comparison between the absorption bands of CO2 clathrate hydrates obtained in our lab and CO2 absorption bands as detected by VIMS on the icy satellites of Saturn will be shown. This experimental work confirms that VIMS data are not consistent with the presence of structure I CO2 clathrate hydrates on the surface of the icy moons. Possibility of having metastable structure II still remains unsolved and will be discussed. [1] Dalton et al., Space Sci. Rev. 2010, 153 : 113-154. [2] Cruikshank D.P. et al, Icarus, 2010, 206: 561-572. [3] Mousis O. et al , Ap. J. 2009, 691: 1780-1786. [4] Choukroun M. et al, in Solar System Ices, edited by Castillo-Rogez, J. et al., 2011.

  6. Characterization of proton in Y-doped SrZrO3 polycrystal by IR spectroscopy

    International Nuclear Information System (INIS)

    Hibino, T.; Mizutani, K.; Yajima, T.; Iwahara, H.

    1992-01-01

    To characterize proton in Y-doped SrZrO 3 polycrystal, protonic conductivities and infrared spectra were measured. IR spectra exhibited 2 OH bands in 3500-2800 and 2650-2300 cm -1 regions, indicating that proton was bound to lattice oxide ion and that its strength of bonding was rather weak. The decrease in conductivity by replacing H + with D + suggested that the conducting ion was not hydroxide but proton and that it migrated via the dissociation of O-H bond. (author). 15 refs., 5 figs

  7. A Controlled-Environment Chamber for Atmospheric Chemistry Studies Using FT-IR Spectroscopy

    Science.gov (United States)

    1990-06-01

    necessary and identify by block number) FELD GROUP SUB-GROUP i >Chamber, controlled environment; long-path cell ; 07 04 FT-IR; Hydrazine decay...modification doubles the useable path length of the original multipass cell described by White (Reference 8). The pattern of images formed on the nesting...system is shown in Figure 13. 24 z C C02, Ibm, El4 944 C3 ta) caC E-4- 252 14 $4 41) 41) 0. 0 04 04 4 41) ~0 to 0.0 V-4 (A q14 0~ 1% 4-r4 $4 0 u P416 4 4

  8. Identification of herbarium whole-leaf samples of Epilobium species by ATR-IR spectroscopy.

    Science.gov (United States)

    Strgulc Krajsek, Simona; Buh, Primoz; Zega, Anamarija; Kreft, Samo

    2008-02-01

    A simple, high-accuracy FT-IR method based on attenuated total reflection (ATR) was developed for the rapid determination of leaf samples of Epilobium species. The method is superior to other analytical techniques, since there is no need of laborious sample preparation such as grinding or extraction and solvent removal. A total of 70 herbarium specimens, belonging to all 13 Epilobium and to 2 Chamerion species growing in Slovenia, were analyzed. With the 100 most-informative wavenumbers in the range 700-1800 cm(-1), we obtained over 90% accuracy of species identification, with discriminant multivariate statistical analysis on the measurements made on whole dried leaves.

  9. Time-resolved diffraction studies of muscle using synchrotron radiation

    International Nuclear Information System (INIS)

    Harford, Jeffrey; Squire, John

    1997-01-01

    details the practical methods involved in recording time-resolved x-ray diffraction patterns from active muscles and the theoretical approaches that are being used to interpret the diffraction patterns that are obtained. The ultimate aim is to produce a series of time-sliced images of the changing molecular arrangements and shapes in the muscle as force is produced; together these images will form 'Muscle - The Movie'. (author)

  10. Time-resolved soft x-ray absorption setup using multi-bunch operation modes at synchrotrons

    International Nuclear Information System (INIS)

    Stebel, L.; Sigalotti, P.; Ressel, B.; Cautero, G.; Malvestuto, M.; Capogrosso, V.; Bondino, F.; Magnano, E.; Parmigiani, F.

    2011-01-01

    Here, we report on a novel experimental apparatus for performing time-resolved soft x-ray absorption spectroscopy in the sub-ns time scale using non-hybrid multi-bunch mode synchrotron radiation. The present setup is based on a variable repetition rate Ti:sapphire laser (pump pulse) synchronized with the ∼500 MHz x-ray synchrotron radiation bunches and on a detection system that discriminates and singles out the significant x-ray photon pulses by means of a custom made photon counting unit. The whole setup has been validated by measuring the time evolution of the L 3 absorption edge during the melting and the solidification of a Ge single crystal irradiated by an intense ultrafast laser pulse. These results pave the way for performing synchrotron time-resolved experiments in the sub-ns time domain with variable repetition rate exploiting the full flux of the synchrotron radiation.

  11. Chemical Sensors Based on IR Spectroscopy and Surface-Modified Waveguides

    Science.gov (United States)

    Lopez, Gabriel P.; Niemczyk, Thomas

    1999-01-01

    Sol-gel processing techniques have been used to apply thin porous films to the surfaces of planar infrared (IR) waveguides to produce widely useful chemical sensors. The thin- film coating serves to diminish the concentration of water and increase the concentration of the analyte in the region probed by the evanescent IR wave. These porous films are composed of silica, and therefore, conventional silica surface modification techniques can be used to give the surface a specific functional character. The sol-gel film was surface-modified to make the film highly hydrophobic. These sensors were shown to be capable of detecting non-polar organic analytes, such as benzonitrile, in aqueous solution with detection limits in the ppb range. Further, these porous sol-gel structures allow the analytes to diffuse into and out of the films rapidly, thus reaching equilibrium in less than ten seconds. These sensors are unique because of the fact that their operation is based on the measurement of an IR absorption spectrum. Thus, these sensors are able to identify the analytes as well as measure concentration with high sensitivity. These developments have been documented in previous reports and publications. Recently, we have also targeted detection of the polar organic molecules acetone and isopropanol in aqueous solution. Polar organics are widely used in industrial and chemical processes, hence it is of interest to monitor their presence in effluents or decontamination process flows. Although large improvements in detection limits were expected with non-polar organic molecules in aqueous solutions using very hydrophobic porous sol-gel films on silicon attenuated total reflectance (Si ATR) waveguides, it was not as clear what the detection enhancements might be for polar organic molecules. This report describes the use of modified sol-gel-coated Si ATR sensors for trace detection and quantitation of small polar organic molecules in aqueous solutions. The detection of both acetone

  12. Study of the processes of carbonization and oxidation of porous silicon by Raman and IR spectroscopy

    International Nuclear Information System (INIS)

    Vasin, A. V.; Okholin, P. N.; Verovsky, I. N.; Nazarov, A. N.; Lysenko, V. S.; Kholostov, K. I.; Bondarenko, V. P.; Ishikawa, Y.

    2011-01-01

    Porous silicon layers were produced by electrochemical etching of single-crystal silicon wafers with the resistivity 10 Ω cm in the aqueous-alcohol solution of hydrofluoric acid. Raman spectroscopy and infrared absorption spectroscopy are used to study the processes of interaction of porous silicon with undiluted acetylene at low temperatures and the processes of oxidation of carbonized porous silicon by water vapors. It is established that, even at the temperature 550°C, the silicon-carbon bonds are formed at the pore surface and the graphite-like carbon condensate emerges. It is shown that the carbon condensate inhibits oxidation of porous silicon by water vapors and contributes to quenching of white photoluminescence in the oxidized carbonized porous silicon nanocomposite layer.

  13. The use of XPS and i.r. spectroscopy in zinc mineral flotation studies

    International Nuclear Information System (INIS)

    Garbassi, F.; Morabini, A.; Cozza, C.

    1985-01-01

    In this work, XPS (X-ray photoelectron spectroscopy) is applied to the study of the interaction of dodecylamine acetate with smithsonite ZnCo 3 , in relation with the problem of flotation of the mineral. This study confirms that, in spite of ultra-high conditions during analysis XPS is a technique offering a very valuable contribution to the elucidation of mineral flotation problems

  14. IR and Raman spectroscopy of sodium aluminophosphate vitreous materials for immobilization of high level wastes from nuclear fuel reprocessing

    International Nuclear Information System (INIS)

    Stefanovskij, S.V.; Myasoedov, B.F.; Remizov, M.B.; Belanova, E.A.

    2014-01-01

    The structure of sodium aluminophosphate vitreous materials containing constituents of high level wastes (cesium, magnesium, copper and molybdenum oxides) from uranium-graphite reactor has been studied by IR and Raman spectroscopy techniques coupled with X-ray diffraction. The structural network has been shown to be composed of short phosphorus-oxygen chains with embedded aluminum-oxygen tetrahedra. In the magnesium-bearing samples the cross-linking with Mg 2+ ions is possible. The effect of other oxides (Cs 2 O, MoO 3 , CuO) on the glass structure is negligible for the occuring amounts. The glasses have been devitrified partly at the quenching and much stronger at the annealing. It is reflected in splitting of the vibration bands of the bonds in structural units of the anionic motif of the vitreous materials. (authors)

  15. Impact of Humidity on Quartz-Enhanced Photoacoustic Spectroscopy Based CO Detection Using a Near-IR Telecommunication Diode Laser

    Directory of Open Access Journals (Sweden)

    Xukun Yin

    2016-01-01

    Full Text Available A near-IR CO trace gas sensor based on quartz-enhanced photoacoustic spectroscopy (QEPAS is evaluated using humidified nitrogen samples. Relaxation processes in the CO-N2-H2O system are investigated. A simple kinetic model is used to predict the sensor performance at different gas pressures. The results show that CO has a ~3 and ~5 times slower relaxation time constant than CH4 and HCN, respectively, under dry conditions. However, with the presence of water, its relaxation time constant can be improved by three orders of magnitude. The experimentally determined normalized detection sensitivity for CO in humid gas is 1.556 × 10 − 8   W ⋅ cm − 1 / Hz 1 / 2 .

  16. Investigation of hydrogen adsorption centers on Y2O3 by IR-spectroscopy method in diffusive-scattered light

    International Nuclear Information System (INIS)

    Zubkov, S.A.; Borovkov, V.Yu.

    1985-01-01

    Adsorption of hydrogen and carbon oxide at the yttrium oxide at 80 K (5x30 3 PaH 2 ) and 300 K (6.5x10 2 PaCO) respectively are studied by the method of IR spectroscopy. It is shown, that at the surface of yttrium oxide trained in vacuum at 970 K, at least four types of centres of hydrogen adsorption, able to polarize H-H bond in a molecule, exist. Acid-base couple is the highest polarized centre, in the content of which there is a coordination-unsaturated highly-charged yttrium cation. Low-temperature dissociation of hydrogen on Y 2 O 3 surface occurs on the centres which polarized H-H bond in molecule comparatively slow

  17. Studies of Eu2O3 - Bi2O3 - B2O3 glasses using Raman and IR spectroscopy

    International Nuclear Information System (INIS)

    Pop, Lidia; Culea, Eugen N.; Bratu, I.

    2004-01-01

    The bismuth borate (3Bi 2 O 3 ·B 2 O 3 ) glasses were prepared with different concentrations of Eu 3+ . The structure of these systems were investigated by Raman and IR spectroscopy. The structural study reveals that the glasses contain BiO 3 , BiO 6 , BO 3 , BO 4 and Eu-O structural units. For the samples with a higher content of Eu 2 O 3 , the spectra became very large indicating a more disordered structure. The hygroscopic character of the 3Bi 2 O 3 ·B 2 O 3 glass matrix and the progressive decrease of this behaviour with increasing the Eu 2 O 3 content was observed. Therefore, we conclude that the europium oxide acts as a network modifier in these glasses. (authors)

  18. Structure and Absolute Configuration of Ginkgolide B Characterized by IR- and VCD Spectroscopy

    DEFF Research Database (Denmark)

    Andersen, Niels Højmark; Christensen, N.J.; Lassen, Peter Rygaard

    2010-01-01

    Experimental and calculated (B3LYP/6-31G(d)) vibrational Circular dichroism (VCD) and IR spectra are compared, illustrating that the structure and absolute configuration of ginkgolide B (GB) may be characterized directly in solution. A conformational search for GB using MacroModel and subsequent...... DFT optimizations (B3LYP/6-31G(d)) provides a structure for the lowest energy conformer which agrees well with the structure determined by X-ray diffraction. In addition, a conformer at all energy of 7 kJ mol(-1) (B3LYP/6-311+G(2d,2p)) with respect to the lowest energy conformer is predicted...

  19. Solute-solvent complex switching dynamics of chloroform between acetone and dimethylsulfoxide-two-dimensional IR chemical exchange spectroscopy.

    Science.gov (United States)

    Kwak, Kyungwon; Rosenfeld, Daniel E; Chung, Jean K; Fayer, Michael D

    2008-11-06

    Hydrogen bonds formed between C-H and various hydrogen bond acceptors play important roles in the structure of proteins and organic crystals, and the mechanisms of C-H bond cleavage reactions. Chloroform, a C-H hydrogen bond donor, can form weak hydrogen-bonded complexes with acetone and with dimethylsulfoxide (DMSO). When chloroform is dissolved in a mixed solvent consisting of acetone and DMSO, both types of hydrogen-bonded complexes exist. The two complexes, chloroform-acetone and chloroform-DMSO, are in equilibrium, and they rapidly interconvert by chloroform exchanging hydrogen bond acceptors. This fast hydrogen bond acceptor substitution reaction is probed using ultrafast two-dimensional infrared (2D-IR) vibrational echo chemical exchange spectroscopy. Deuterated chloroform is used in the experiments, and the 2D-IR spectrum of the C-D stretching mode is measured. The chemical exchange of the chloroform hydrogen bonding partners is tracked by observing the time-dependent growth of off-diagonal peaks in the 2D-IR spectra. The measured substitution rate is 1/30 ps for an acetone molecule to replace a DMSO molecule in a chloroform-DMSO complex and 1/45 ps for a DMSO molecule to replace an acetone molecule in a chloroform-acetone complex. Free chloroform exists in the mixed solvent, and it acts as a reactive intermediate in the substitution reaction, analogous to a SN1 type reaction. From the measured rates and the equilibrium concentrations of acetone and DMSO, the dissociation rates for the chloroform-DMSO and chloroform-acetone complexes are found to be 1/24 ps and 1/5.5 ps, respectively. The difference between the measured rate for the complete substitution reaction and the rate for complex dissociation corresponds to the diffusion limited rate. The estimated diffusion limited rate agrees well with the result from a Smoluchowski treatment of diffusive reactions.

  20. Rapid Quantitative Determination of Squalene in Shark Liver Oils by Raman and IR Spectroscopy.

    Science.gov (United States)

    Hall, David W; Marshall, Susan N; Gordon, Keith C; Killeen, Daniel P

    2016-01-01

    Squalene is sourced predominantly from shark liver oils and to a lesser extent from plants such as olives. It is used for the production of surfactants, dyes, sunscreen, and cosmetics. The economic value of shark liver oil is directly related to the squalene content, which in turn is highly variable and species-dependent. Presented here is a validated gas chromatography-mass spectrometry analysis method for the quantitation of squalene in shark liver oils, with an accuracy of 99.0 %, precision of 0.23 % (standard deviation), and linearity of >0.999. The method has been used to measure the squalene concentration of 16 commercial shark liver oils. These reference squalene concentrations were related to infrared (IR) and Raman spectra of the same oils using partial least squares regression. The resultant models were suitable for the rapid quantitation of squalene in shark liver oils, with cross-validation r (2) values of >0.98 and root mean square errors of validation of ≤4.3 % w/w. Independent test set validation of these models found mean absolute deviations of the 4.9 and 1.0 % w/w for the IR and Raman models, respectively. Both techniques were more accurate than results obtained by an industrial refractive index analysis method, which is used for rapid, cheap quantitation of squalene in shark liver oils. In particular, the Raman partial least squares regression was suited to quantitative squalene analysis. The intense and highly characteristic Raman bands of squalene made quantitative analysis possible irrespective of the lipid matrix.

  1. Infrared Spectroscopy of Gas-Phase M+(CO2)n (M = Co, Rh, Ir) Ion-Molecule Complexes.

    Science.gov (United States)

    Iskra, Andreas; Gentleman, Alexander S; Kartouzian, Aras; Kent, Michael J; Sharp, Alastair P; Mackenzie, Stuart R

    2017-01-12

    The structures of gas-phase M + (CO 2 ) n (M = Co, Rh, Ir; n = 2-15) ion-molecule complexes have been investigated using a combination of infrared resonance-enhanced photodissociation (IR-REPD) spectroscopy and density functional theory. The results provide insight into fundamental metal ion-CO 2 interactions, highlighting the trends with increasing ligand number and with different group 9 ions. Spectra have been recorded in the region of the CO 2 asymmetric stretch around 2350 cm -1 using the inert messenger technique and their interpretation has been aided by comparison with simulated infrared spectra of calculated low-energy isomeric structures. All vibrational bands in the smaller complexes are blue-shifted relative to the asymmetric stretch in free CO 2 , consistent with direct binding to the metal center dominated by charge-quadrupole interactions. For all three metal ions, a core [M + (CO 2 ) 2 ] structure is identified to which subsequent ligands are less strongly bound. No evidence is observed in this size regime for complete activation or insertion reactions.

  2. Sensing the Structural Differences in Cellulose from Apple and Bacterial Cell Wall Materials by Raman and FT-IR Spectroscopy

    Science.gov (United States)

    Szymańska-Chargot, Monika; Cybulska, Justyna; Zdunek, Artur

    2011-01-01

    Raman and Fourier Transform Infrared (FT-IR) spectroscopy was used for assessment of structural differences of celluloses of various origins. Investigated celluloses were: bacterial celluloses cultured in presence of pectin and/or xyloglucan, as well as commercial celluloses and cellulose extracted from apple parenchyma. FT-IR spectra were used to estimate of the Iβ content, whereas Raman spectra were used to evaluate the degree of crystallinity of the cellulose. The crystallinity index (XCRAMAN%) varied from −25% for apple cellulose to 53% for microcrystalline commercial cellulose. Considering bacterial cellulose, addition of xyloglucan has an impact on the percentage content of cellulose Iβ. However, addition of only xyloglucan or only pectins to pure bacterial cellulose both resulted in a slight decrease of crystallinity. However, culturing bacterial cellulose in the presence of mixtures of xyloglucan and pectins results in an increase of crystallinity. The results confirmed that the higher degree of crystallinity, the broader the peak around 913 cm−1. Among all bacterial celluloses the bacterial cellulose cultured in presence of xyloglucan and pectin (BCPX) has the most similar structure to those observed in natural primary cell walls. PMID:22163913

  3. Optical Determination of Lead Chrome Green in Green Tea by Fourier Transform Infrared (FT-IR Transmission Spectroscopy.

    Directory of Open Access Journals (Sweden)

    Xiaoli Li

    Full Text Available The potential of Fourier transform infrared (FT-IR transmission spectroscopy for determination of lead chrome green in green tea was investigated based on chemometric methods. Firstly, the qualitative analysis of lead chrome green in tea was performed based on partial least squares discriminant analysis (PLS-DA, and the correct rate of classification was 100%. And then, a hybrid method of interval partial least squares (iPLS regression and successive projections algorithm (SPA was proposed to select characteristic wavenumbers for the quantitative analysis of lead chrome green in green tea, and 19 wavenumbers were obtained finally. Among these wavenumbers, 1384 (C = C, 1456, 1438, 1419(C = N, and 1506 (CNH cm-1 were the characteristic wavenumbers of lead chrome green. Then, these 19 wavenumbers were used to build determination models. The best model was achieved by least squares support vector machine (LS-SVMalgorithm with high coefficient of determination and low root-mean square error of prediction set (R2p = 0.864 and RMSEP = 0.291. All these results indicated the feasibility of IR spectra for detecting lead chrome green in green tea.

  4. Development of C-lignin with G/S-lignin and lipids in orchid seed coats – an unexpected diversity exposed by ATR-FT-IR spectroscopy

    DEFF Research Database (Denmark)

    Barsberg, Søren Talbro; Lee, Y.-I.; Rasmussen, Hanne Nina

    2018-01-01

    Cite this article: Barsberg ST, Lee Y-I, Rasmussen HN. Development of C-lignin with G/S-lignin and lipids in orchid seed coats – an unexpected diversity exposed by ATR-FT-IR spectroscopy. Seed Science Research https:// doi.org/10.1017/S0960258517000344......Cite this article: Barsberg ST, Lee Y-I, Rasmussen HN. Development of C-lignin with G/S-lignin and lipids in orchid seed coats – an unexpected diversity exposed by ATR-FT-IR spectroscopy. Seed Science Research https:// doi.org/10.1017/S0960258517000344...

  5. Verification of Ganoderma (lingzhi) commercial products by Fourier Transform infrared spectroscopy and two-dimensional IR correlation spectroscopy

    Science.gov (United States)

    Choong, Yew-Keong; Sun, Su-Qin; Zhou, Qun; Lan, Jin; Lee, Han-Lim; Chen, Xiang-Dong

    2014-07-01

    Ganoderma commercial products are typically based on two sources, raw material (powder form and/or spores) and extract (water and/or solvent). This study compared three types of Ganoderma commercial products using 1 Dimensional Fourier Transform infrared and second derivative spectroscopy. The analyzed spectra of Ganoderma raw material products were compared with spectra of cultivated Ganoderma raw material powder from different mushroom farms in Malaysia. The Ganoderma extract product was also compared with three types of cultivated Ganoderma extracts. Other medicinal Ganoderma contents in commercial extract product that included glucan and triterpenoid were analyzed by using FTIR and 2DIR. The results showed that water extract of cultivated Ganoderma possessed comparable spectra with that of Ganoderma product water extract. By comparing the content of Ganoderma commercial products using FTIR and 2DIR, product content profiles could be detected. In addition, the geographical origin of the Ganoderma products could be verified by comparing their spectra with Ganoderma products from known areas. This study demonstrated the possibility of developing verification tool to validate the purity of commercial medicinal herbal and mushroom products.

  6. IR-spectroscopy as an analytical method for identification of horticultural peat

    International Nuclear Information System (INIS)

    Lehtovaara, J.; Herranen, M.; Nyroenen, T.; MacDonald, A.

    1988-01-01

    The process of selecting different peat types for horticultural purposes involves many physical and chemical determinations. Infrared spectroscopy could be used together with the usual methods for the evaluation of peat quality. Due to the fact that different peats contain different amounts of infrared absorbing functional groups, each peat produces a characteristic spectrum. From the spectrum, one may determine the botanical composition, degree of humification, ash content, cation exchange capacity, nitrogen content and carbon content, of the natural peat. The spectrum also shows whether the peat has been fertilized and limed and in some cases the presence of mineral soil or wetting agent mixed in the peat may be detected

  7. Electronic processes in TTF-derived complexes studied by IR spectroscopy

    Science.gov (United States)

    Graja, Andrzej

    2001-09-01

    We focus our attention on the plasma-edge-like dispersion of the reflectance spectra of the selected bis(ethylenodithio)tetrathiafulvalene (BEDT-TTF)-derived organic conductors. The standard procedure to determine the electron transport parameters in low-dimensional organic conductors consists of fitting the appropriate theoretical models with the experimental reflectance data. This procedure provides us with basic information like plasma frequency, the optical effective mass of charge carriers, their number, mean free path and damping constant. Therefore, it is concluded that the spectroscopy is a powerful tool to study the electronic processes in conducting organic solids.

  8. Investigation of Sm(3) and Eu(3) coordination compounds with pyrazolones by IR spectroscopy method

    International Nuclear Information System (INIS)

    Panyushkin, V.T.; Grishenko, T.V.; Afanas'ev, Yu.A.; Garnovskij, A.D.; Osipov, O.A.

    1978-01-01

    The synthesis is described of the coordination nitrate compounds of Sm(3) and Eu(3) with pyrazolones: 4-aminoantipyrine (A), 1-ethylpyridyl- 3-phenyl-pyrazolone-5(B); 1-(3'-ethylpyridyl)-3(phenylamine-n)-pyrazolone-5(C). It has been determined by the infrared spectroscopy method that exocyclic oxygen atom is the place of coordination bond localization in the pentioned compounds. The infrared spectra analysis of complexes in the 1700-1800 cm -1 region makes it possible to mention bidentate character of NO 3 -groups in the studied complex compounds

  9. Investigation of thermochemical conversions of coal pitches using high resolution PMR and IR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Kekin, N.A.; Belkina, T.V.; Stepanenko, M.A.; Gordienko, V.G.

    1982-01-01

    The hydrogen bonds in organic compounds present in coal pitch and fractions were investigated by infrared spectroscopy and proton magnetic resonance. The investigation was extended to include pitch that was thermally treated at 360 degrees C to raise the softening point to 85-90 degrees C. The infrared spectra revealed hydrogen present in OH groups, NH groups, COOH groups, unsaturated carbon double bonds, and multiple carbon double bonds. It was also determined that thermal treating increased the hydrogen present in aromatic compounds and decreased hydrogen present in aliphatic forms. (JMT)

  10. The applicability of Fourier transform infrared (FT-IR) spectroscopy in waste management

    International Nuclear Information System (INIS)

    Smidt, Ena; Meissl, Katharina

    2007-01-01

    State and stability or reactivity of waste materials are important properties that must be determined to obtain information about the future behavior and the emission potential of the materials. Different chemical and biological parameters are used to describe the stage of organic matter in waste materials. Fourier transform infrared spectroscopy provides information about the chemistry of waste materials in a general way. Several indicator bands that are referred to functional groups represent components or metabolic products. Their presence and intensity or their absence shed light on the phase of degradation or stabilization. The rapid assessment of the stage of organic matter decomposition is a very important field of application. Therefore, infrared spectroscopy is an appropriate tool for process and quality control, for the assessment of abandoned landfills and for checking of the successful landfill remediation. A wide range of applications are presented in this study for different waste materials. Progressing stages of a typical yard/kitchen waste composting process are shown. The fate of anaerobically 'stabilized' leftovers in a subsequent liquid aerobic process is revealed by spectroscopic characteristics. A compost that underwent the biological stabilization process is distinguished from a 'substrate' that comprises immature biogenic waste mixed with mineral compounds. Infrared spectra of freeze-dried leachate from untreated and aerated landfill material prove the effect of the aerobic treatment during 10 weeks in laboratory-scale experiments

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

    Science.gov (United States)

    Purwar, Namrta

    crystal. Time-resolved X-ray data collected at pH's of 4, 7 and 9 demonstrate that pH alters the kinetics of the PYP photocycle dramatically. At pH 4 the photocycle lasts almost one order of magnitude longer in time compared to pH 7. The final intermediate that accumulates at both pH 7 and pH 4 is absent at pH 9. Results from the dose- and the pH-dependent time-resolved crystallographic experiments show that it is imperative to carefully control the conditions under which time-resolved data are collected. With these considerations we collected a comprehensive time-series from nanoseconds to seconds at 14 different temperature settings from -40 °C to 70 °C. Results from time-resolved crystallography are corroborated by employing time-resolved absorption spectroscopy. For this, absorption spectra on crystals and solution are collected by a fast micro-spectrophotometer custom-designed in our lab. We identify kinetic phases of the PYP photocycle at all 14 temperature settings. Relaxation times associated with these phases are temperature-dependent and can be fit by the Van't Hoff-Arrhenius equation. Kinetic modeling yields entropy and enthalpy values at the barriers of the activation solely from the time-resolved crystallographic data. With this, we advance crystallography to a new frontier: the determination of free energy surfaces. Investigating enzymatic reactions can be challenging, because they are non-cyclic. After one turnover product must be washed away and substrate must be reloaded. A promising approach for routine application can be envisioned at the new 4th generation X-ray sources, such as X-ray free electron lasers (XFELs). With our results we set the scene to comprehensively investigate all kinds of enzymatic reactions with these instruments.

  12. Characterization of silicon-oxide interfaces and organic monolayers by IR-UV ellipsometry and FTIR spectroscopy

    Science.gov (United States)

    Hess, P.; Patzner, P.; Osipov, A. V.; Hu, Z. G.; Lingenfelser, D.; Prunici, P.; Schmohl, A.

    2006-08-01

    VUV-laser-induced oxidation of Si(111)-(1×1):H, Si(100):H, and a-Si:H at 157 nm (F II laser) in pure O II and pure H IIO atmospheres was studied between 30°C and 250°C. The oxidation process was monitored in real time by spectroscopic ellipsometry (NIR-UV) and FTIR spectroscopy. The ellipsometric measurements could be simulated with a three-layer model, providing detailed information on the variation of the suboxide interface with the nature of the silicon substrate surface. Besides the silicon-dioxide and suboxide layer, a dense, disordered, roughly monolayer thick silicon layer was included, as found previously by molecular dynamics calculations. The deviations from the classical Deal-Grove mechanism and the self-limited growth of the ultrathin dioxide layers (TMS) groups and n-alkylthiol monolayers on gold-coated silicon. The C-H stretching vibrations of the methylene and methyl groups could be identified by FTIR spectroscopy and IR ellipsometry.

  13. HIGH-RESOLUTION IR ABSORPTION SPECTROSCOPY OF POLYCYCLIC AROMATIC HYDROCARBONS: THE REALM OF ANHARMONICITY

    Energy Technology Data Exchange (ETDEWEB)

    Maltseva, Elena; Buma, Wybren Jan [University of Amsterdam, Science Park 904, 1098 XH Amsterdam (Netherlands); Petrignani, Annemieke; Candian, Alessandra; Mackie, Cameron J.; Tielens, Alexander G. G. M. [Leiden Observatory, Niels Bohrweg 2, 2333 CA Leiden (Netherlands); Huang, Xinchuan; Lee, Timothy J. [SETI Institute, 189 Bernardo Avenue, Suite 100, Mountain View, CA 94043 (United States); Oomens, Jos, E-mail: w.j.buma@uva.nl, E-mail: petrignani@strw.leidenuniv.nl [Radboud University, Toernooiveld 7, 6525 ED Nijmegen (Netherlands)

    2015-11-20

    We report on an experimental and theoretical investigation of the importance of anharmonicity in the 3-μm CH stretching region of polycyclic aromatic hydrocarbon (PAH) molecules. We present mass-resolved, high-resolution spectra of the gas-phase cold (∼4 K) linear PAH molecules naphthalene, anthracene, and tetracene. The measured IR spectra show a surprisingly high number of strong vibrational bands. For naphthalene, the observed bands are well separated and limited by the rotational contour, revealing the band symmetries. Comparisons are made to the harmonic and anharmonic approaches of the widely used Gaussian software. We also present calculated spectra of these acenes using the computational program SPECTRO, providing anharmonic predictions with a Fermi-resonance treatment that utilizes intensity redistribution. We demonstrate that the anharmonicity of the investigated acenes is strong, dominated by Fermi resonances between the fundamental and double combination modes, with triple combination bands as possible candidates to resolve remaining discrepancies. The anharmonic spectra as calculated with SPECTRO lead to predictions of the main bands that fall within 0.5% of the experimental frequencies. The implications for the aromatic infrared bands, specifically the 3-μm band, are discussed.

  14. Spectroelectrochemical study of polyphenylene by in situ external reflection FT-IR spectroscopy. Pt. 1

    International Nuclear Information System (INIS)

    Kvarnstroem, C.; Ivaska, A.

    1994-01-01

    In situ spectroelectrochemical measurements with external reflection FT-IR are performed at different stages of polymerization of 0.05, 0.1 and 0.8 M biphenyl in 0.1 M TBABF 4 in acetonitrile. The biphenyl concentration is not found to have any effect on the structure of the polymer formed. Formation of oligomers and the ratio of ortho/para-substituted polymer chains during film growth are studied. The first coupling of dimers to oligomers is found to take place in the vicinity of the electrode surface and at a later stage of polymerization the oligomers start to form polymer film on the electrode. A mixed para and ortho coupling resulting in crosslinking between chains is observed already at the early stage of polymerization. However, when a lower current density is used a more ordered polymer structure is obtained. A breakdown of the polymer film due to overoxidation can be seen when the potential is increased to 2.0 V. (orig.)

  15. High-Resolution IR Absorption Spectroscopy of Polycyclic Aromatic Hydrocarbons: The Realm of Anharmonicity

    Science.gov (United States)

    Maltseva, Elena; Petrignani, Annemieke; Candian, Alessandra; Mackie, Cameron J.; Huang, Xinchuan; Lee, Timothy J.; Tielens, Alexander G. G. M.; Oomens, Jos; Buma, Wybren Jan

    2016-01-01

    We report on an experimental and theoretical investigation of the importance of anharmonicity in the 3 micrometers CH stretching region of Polycyclic Aromatic Hydrocarbon (PAH) molecules. We present mass-resolved, high-resolution spectra of the gas-phase cold ((is) approximately 4K) linear PAH molecules naphthalene, anthracene, and tetracene. The measured IR spectra show a surprisingly high number of strong vibrational bands. For naphthalene, the observed bands are well separated and limited by the rotational contour, revealing the band symmetries. Comparisons are made to the harmonic and anharmonic approaches of the widely used Gaussian software. We also present calculated spectra of these acenes using the computational program SPECTRO, providing anharmonic predictions enhanced with a Fermi-resonance treatment that utilizes intensity redistribution. We demonstrate that the anharmonicity of the investigated acenes is strong, dominated by Fermi resonances between the fundamental and double combination modes, with triple combination bands as possible candidates to resolve remaining discrepancies. The anharmonic spectra as calculated with SPECTRO lead to predictions of the main modes that fall within 0.5% of the experimental frequencies. The implications for the Aromatic Infrared Bands, specifically the 3-m band are discussed.

  16. The analysis of time-resolved optically stimulated luminescence: I. Theoretical considerations

    International Nuclear Information System (INIS)

    Chithambo, M L

    2007-01-01

    This is the first of two linked papers on the analysis of time-resolved optically stimulated luminescence. This paper focusses on a theoretical basis of analytical methods and on methods for interpretation of time-resolved luminescence spectra and calculation of luminescence throughput. Using a comparative analysis of the principal features of time-resolved luminescence and relevant analogues from steady state optical stimulation, formulae for configuring a measurement system for optimum performance are presented. We also examine the possible use of stretched-exponential functions for analysis of time-resolved optically stimulated luminescence spectra

  17. The influence of optical parameters on impurity determinations by IR spectroscopy

    International Nuclear Information System (INIS)

    Lombard, O.J.

    1985-01-01

    The important role of impurities in semiconductor materials is the subject of continuous research. The concentration of interstitial oxygen impurities in silicon are determined with the aid of infrared spectroscopy. The maximum absorption coefficient of the oxygen absorption peak, centered at 9,06 μm, is determined and the impurity concentration is then calculated using a calibration factor. This procedure was evaluated, paying particular attention to those optical parameters which may influence these impurity determinations. A thorough discussion of the theoretical and experimental aspects of infrared spectroscopy in general is followed by an overview of previous experimental work. This lead to some theoretical analysis regarding the influence of the index of refraction, the index of absorption and multiple reflections in the silicon wafer on impurity determinations. This lead to specific experimental investigations. The influence of the surface morphology of samples on impurity determinations was studied by determining the reflectance of silicon surfaces. It was established that the surface reflectance plays a role and that it must be taken into consideration for accurate impurity concentration determinations. The most accurate values for the absorption coefficient due to oxygen in silicon are calculated. This requires that the surface of the silicon wafers must be highly polished for the formula to be valid. Acceptable values for the absorption coefficient of damaged surfaces are obtained if the uncorrected formula is used. Experimental results may deviate as much as 32% from the real impurity concentration if the wrong formula is used to calculate the absorption coefficient of oxygen in silicon at 9,06 μm

  18. Characterization of a new Tc (V) - glucosazine complex by UV - VIS and IR spectroscopy

    International Nuclear Information System (INIS)

    Ganzerli Valentini, M.T.; Stella, R.; Maggi, L.

    1989-01-01

    A new radiopharmaceutical is proposed for brain and heart functional and radiodiagnostic studies. A Tc complex containing the glucose molecule and chelating groups that do not alter the basic chemical features of the molecule has been prepared. The ligand is formed by the combination of one hydrazine molecule with two sugar molecules and is the first product of the D-glucose-hydrazine reaction that in aqueous basic medium may proceed up to hydrazone and in acid medium up to osazone. These transformations are observed at pH>5 through the UV absorption peaks at 274 and 224 nm, and at pH 1 . UV absorption spectra of the complex, dissolved in water as well as in acetonitrile, have been recorded: the characteristic single peak at 274 nm and at 276 nm respectively for the two solvents is unaffected by the presence of free ligand, due to the quasi null absorption in this spectral region. Molar extinction coefficient is found equal to 20850 L.mol 1 .cm 1 in solutions whose Tc concentration was in the range 2x10 5 -5x10 4 M and the ligand 10 2 - 10 1 M. The IR absorption spectrum has a C=N stretching band at 1620 cm 1 which means that the acyclic form of the azine is predominant; other large and strong bands refer to OH stretching at 3300 cm 1 , to C-O stretching at 1020 cm 1 and to C-N stretching (typical of the cyclic form) at 1080 cm 1 . (author)

  19. Characterization of soil organic matter by FT-IR spectroscopy and its relationship with chlorpyrifos sorption.

    Science.gov (United States)

    Parolo, María Eugenia; Savini, Mónica Claudia; Loewy, Ruth Miriam

    2017-07-01

    Sorption of non-ionic organic compounds to soil is usually expressed as the carbon-normalized partition coefficient (K OC ) assuming that the main factor that influences the amount sorbed is the organic carbon content (OC) of the soil. However, K OC can vary across a range of soils. The influence of certain soil characteristics on the chlorpyrifos K OC values variation for 12 representative soils of the Northpatagonian Argentinian region with different physicochemical properties was investigated for this study. The chlorpyrifos sorption coefficients normalized by the OC content were experimentally obtained using the batch equilibrium method; the K OC values ranged between 9000-20,000 L kg -1 . The soil characteristics assessed were pH, clay content and spectral data indicative of soil organic matter (SOM) quality measured by FT-IR on the whole soil. The bands considered in the spectroscopic analyses were those corresponding to the aliphatic components, 2947-2858 cm -1 (band A) and the hydrophilic components, 1647-1633 cm -1 (band B). A significant relationship was found (R 2  = 0.66) between chlorpyrifos sorption (K OC ) and the variables pH and A/B height band ratio. The correlation between the values predicted by the derived model and the experimental data was significant (r = 0.89 p chlorpyrifos sorption coefficient through the use of a simple, rapid, and environmentally-friendly measurement. K OC analysis in relation to soil properties represents a valuable contribution to the understanding of the attenuation phenomena of the organic contaminants off-site migration in the environment. Copyright © 2017 Elsevier Ltd. All rights reserved.

  20. Femtosecond time-resolved two-photon photoemission study of organic semiconductor copper phthalocyanine film

    International Nuclear Information System (INIS)

    Tanaka, A.; Tohoku University; University of Rochester, NY; Yan, L.; Watkins, N.J.; Gao, Y.

    2004-01-01

    Full text: Organic semiconductors are recently attracting much interest from the viewpoints of both device and fundamental physics. These organic semiconductors are considered to be important constituents of the future devices, such as organic light-emitting diode, organic field effect transistor, and organic solid-state injection laser. In order to elucidate their detailed physical properties and to develop the future devices, it is indispensable to understand their excited-state dynamics as well as their electronic structures. The femtosecond time-resolved two-photon photoemission (TR-2PPE) spectroscopy is attracting much interest because of its capability to observe the energy-resolved excited electron dynamics. In this work, we have carried out a TR-2PPE study of the organic semiconductor copper phthalocyanine (CuPc) film. Furthermore, we have investigated the detailed electronic structure of CuPc film using the photoemission (PES) and inverse photoemission (IPES) spectroscopies. From the simultaneous PES and IPES measurements for CuPc film with a thickness of 100 nm, the lowest unoccupied molecular orbital (LUMO), highest occupied molecular orbital, and ionization potential of CuPc film have been directly determined. The observed two-photon photoemission (2PPE) spectrum of the present CuPc film, measured with photon energy of about hv=3.3 eV, exhibits a broad feature. From the energy diagram of CuPc film determined by the PES and IPES measurements, the intermediate state observed in the present 2PPE spectrum of CuPc film corresponds to the energy region between about 0.4 and 1.7 eV above the LUMO energy. From the time-resolved pump-probe measurements, it is found that the relaxation lifetimes of excited states in the present CuPc films are very short (all below 50 fs) and monotonously become faster with increasing excitation energy. We attribute this extremely fast relaxation process of photoexcitation to a rapid internal conversion process. From these results