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Sample records for picosecond time-resolved fluorescence

  1. Time-resolved microspectrofluorometry and fluorescence lifetime imaging of photosensitizers using picosecond pulsed diode lasers in laser scanning microscopes.

    Science.gov (United States)

    Kress, Matthias; Meier, Thomas; Steiner, Rudolf; Dolp, Frank; Erdmann, Rainer; Ortmann, Uwe; Rück, Angelika

    2003-01-01

    This work describes the time-resolved fluorescence characteristics of two different photosensitizers in single cells, in detail mTHPC and 5-ALA induced PPIX, which are currently clinically used in photodynamic therapy. The fluorescence lifetime of the drugs was determined in the cells from time-gated spectra as well as single photon counting, using a picosecond pulsed diode laser for fluorescence excitation. The diode laser, which emits pulses at 398 nm with 70 ps full width at half maximum duration, was coupled to a confocal laser scanning microscope. For time-resolved spectroscopy a setup consisting of a Czerny Turner spectrometer and a MCP-gated and -intensified CCD camera was used. Time-gated spectra within the cells were acquired by placing the laser beam in "spot scan" mode. In addition, a time-correlated single photon counting module was used to determine the fluorescence lifetime from single spots and to record lifetime images. The fluorescence lifetime of mTHPC decreased from 7.5 to 5.5 ns during incubation from 1 to 6 h. This decrease was probably attributed to enhanced formation of aggregates during incubation. Fluorescence lifetime imaging showed that longer lifetimes were correlated with accumulation in the cytoplasm in the neighborhood of the cell nucleus, whereas shorter lifetimes were found in the outer cytoplasm. For cells that were incubated with 5-ALA, a fluorescence lifetime of 7.4 ns was found for PPIX; a shorter lifetime at 3.6 ns was probably attributed to photoproducts and aggregates of PPIX. In contrast from fluorescence intensity images alone, different fluorescence species could not be distinguished. However, in the lifetime image a structured fluorescence distribution in the cytoplasm was correlated with the longer lifetime and probably coincides with mitochondria. In conclusion, picosecond diode lasers coupled to a laser scanning microscope equipped with appropriate detection units allows time-resolved spectroscopy and lifetime imaging

  2. Excited state dynamics of 9,9'-bianthryl in room temperature ionic liquids as revealed by picosecond time-resolved fluorescence study

    Indian Academy of Sciences (India)

    Dinesh Chandra Khara; Aniruddha Paul; Kotni Santhosh; Anunay Samanta

    2009-05-01

    Picosecond time-resolved fluorescence measurements have been carried out on 9,9'-bianthryl in three imidazolium ionic liquids to probe the excited state dynamics. In the early time-scale, the fluorescence spectra of bianthryl have been found to consist of emission from both locally excited (LE) and charge transfer (CT) states. The LE → CT relaxation time, as estimated from the decay of the fluorescence intensity of the LE emission, is found to vary between 230 and 390 ps, while the average solvent relaxation time, as estimated from the analysis of time-dependent fluorescence Stokes shift, is found to vary between 620 ps and 1840 ps, depending on the viscosity of the ionic liquids. The results confirm that while in conventional less viscous solvents the CT formation kinetics of bianthryl occurs simultaneously with the solvation dynamics, in ionic liquids the two processes mostly occur in different time scales.

  3. Nonphotochemical quenching of excitation energy in photosystem II. A picosecond time-resolved study of the low yield of chlorophyll a fluorescence induced by single-turnover flash in isolated spinach thylakoids.

    Science.gov (United States)

    Vasil'ev, S; Bruce, D

    1998-08-04

    Chlorophyll a fluorescence emission is widely used as a noninvasive measure of a number of parameters related to photosynthetic efficiency in oxygenic photosynthetic organisms. The most important component for the estimation of photochemistry is the relative increase in fluorescence yield between dark-adapted samples which have a maximal capacity for photochemistry and a minimal fluorescence yield (F0) and light-saturated samples where photochemistry is saturated and fluorescence yield is maximal (Fm). However, when photosynthesis is saturated with a short (less than 50 micro(s)) flash of light, which induces only one photochemical turnover of photosystem II, the maximal fluorescence yield is significantly lower (Fsat) than when saturation is achieved with a millisecond duration multiturnover flash (Fm). To investigate the origins of the difference in fluorescence yield between these two conditions, our time-resolved fluorescence apparatus was modified to allow collection of picosecond time-resolved decay kinetics over a short time window immediately following a saturating single-turnover flash (Fsat) as well as after a multiturnover saturating pulse (Fm). Our data were analyzed with a global kinetic model based on an exciton radical pair equilibrium model for photosystem II. The difference between Fm and Fsat was modeled well by changing only the rate constant for quenching of excitation energy in the antenna of photosystem II. An antenna-based origin for the quenching was verified experimentally by the observation that addition of the antenna quencher 5-hydroxy-1,4-naphthoquinone to thylakoids under Fm conditions resulted in decay kinetics and modeled kinetic parameters very similar to those observed under Fsat conditions in the absence of added quinone. Our data strongly support the origin of low fluorescence yield at Fsat to be an antenna-based nonphotochemical quenching of excitation energy in photosystem II which has not usually been considered explicitly in

  4. The Self-Injected Laser for Picosecond Time-Resolved Spectroscopy

    OpenAIRE

    Armani, F.; Martini, F; Mataloni, P.

    1983-01-01

    The principles of operation and the characteristics of the self-injected picosecond laser are presented. We show that in spite of its simple design our device is able to generate very high power pulses in the picosecond domain. This warrants the use of this laser for time resolved spectroscopy in the picosecond domain.

  5. Toward picosecond time-resolved X-ray absorption studies of interfacial photochemistry

    Science.gov (United States)

    Gessner, Oliver; Mahl, Johannes; Neppl, Stefan

    2016-05-01

    We report on the progress toward developing a novel picosecond time-resolved transient X-ray absorption spectroscopy (TRXAS) capability for time-domain studies of interfacial photochemistry. The technique is based on the combination of a high repetition rate picosecond laser system with a time-resolved X-ray fluorescent yield setup that may be used for the study of radiation sensitive materials and X-ray spectroscopy compatible photoelectrochemical (PEC) cells. The mobile system is currently deployed at the Advanced Light Source (ALS) and may be used in all operating modes (two-bunch and multi-bunch) of the synchrotron. The use of a time-stamping technique enables the simultaneous recording of TRXAS spectra with delays between the exciting laser pulses and the probing X-ray pulses spanning picosecond to nanosecond temporal scales. First results are discussed that demonstrate the viability of the method to study photoinduced dynamics in transition metal-oxide semiconductor (SC) samples under high vacuum conditions and at SC-liquid electrolyte interfaces during photoelectrochemical water splitting. Opportunities and challenges are outlined to capture crucial short-lived intermediates of photochemical processes with the technique. This work was supported by the Department of Energy Office of Science Early Career Research Program.

  6. Picosecond time resolved conductance measurements of redox molecular junctions

    Science.gov (United States)

    Arielly, Rani; Nachman, Nirit; Zelinskyy, Yaroslav; May, Volkhard; Selzer, Yoram

    2017-03-01

    Due to bandwidth limitations of state of the art electronics, the transient transport properties of molecular junctions are experimentally a terra incognita, which can only be explored if novel picosecond current-probing techniques are developed. Here we demonstrate one such approach: the laser pulse-pair sequence scheme. The method is used to monitor in picosecond resolution the oxidation state of a redox molecule, 6-ferrocenyl-1-hexanethiol, within a junction and to quantify its redox rate constant, which is found to be (80 ps)-1.

  7. Picosecond time-resolved imaging using SPAD cameras

    Science.gov (United States)

    Gariepy, Genevieve; Leach, Jonathan; Warburton, Ryan; Chan, Susan; Henderson, Robert; Faccio, Daniele

    2016-10-01

    The recent development of 2D arrays of single-photon avalanche diodes (SPAD) has driven the development of applications based on the ability to capture light in motion. Such arrays are composed typically of 32x32 SPAD detectors, each having the ability to detect single photons and measure their time of arrival with a resolution of about 100 ps. Thanks to the single-photon sensitivity and the high temporal resolution of these detectors, it is now possible to image light as it is travelling on a centimetre scale. This opens the door for the direct observation and study of dynamics evolving over picoseconds and nanoseconds timescales such as laser propagation in air, laser-induced plasma and laser propagation in optical fibres. Another interesting application enabled by the ability to image light in motion is the detection of objects hidden from view, based on the recording of scattered waves originating from objects hidden by an obstacle. Similarly to LIDAR systems, the temporal information acquired at every pixel of a SPAD array, combined with the spatial information it provides, allows to pinpoint the position of an object located outside the line-of-sight of the detector. A non-line-of-sight tracking can be a valuable asset in many scenarios, including for search and rescue mission and safer autonomous driving.

  8. Time resolved fluorescence of naproxen in organogel medium

    Science.gov (United States)

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

    2008-07-01

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

  9. Semiconductors Investigated by Time Resolved Raman Absorption and Photoluminescence Spectroscopy Using Femtosecond and Picosecond Laser Techniques.

    Science.gov (United States)

    1983-05-05

    This report summarizes the research progress achieved in the period 1979-1982 in the research effort supported by AFOSR 80-0079. Two main areas of research are: picosecond and subpicosecond laser development and application and time-resolved studies of semiconductors. In the subpicosecond laser development program we investigated a variety of cavities of different physical parameters. A stable and reliable oscillator, which produces 200 fsec pulses, has been developed using

  10. Singlet Exciton Migration in a Conjugated Polymer by Picosecond Time-Resolved Photoluminescence

    Institute of Scientific and Technical Information of China (English)

    马国宏; 钱士雄; 雷洪; 汪河洲; 王荣秋; 李永舫

    2001-01-01

    The transient photoluminescence (PL) of DO-PPV (poly-(2,5-dioctyloxy-1,4-phenylene vinylene)) solution in chloroform was investigated by picosecond time-resolved PL spectroscopy. An ultrafast rise of PL and the following single exponential decay with a time constant of about 400ps were assigned to the formation of the intrachain exciton and its decay process, respectively. The redshift of the PL emission spectrum with time was caused by the subsequent exciton migration among the different conjugated segments in the DO-PPV polymer.

  11. 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.

  12. Time resolved multiphoton excited fluorescence probes in model membranes

    CERN Document Server

    Bai, Y

    2000-01-01

    Using the time-correlated single-photon counting technique, this thesis reports on a time-resolved fluorescence study of several fluorescent probes successfully employed in membrane research. Concentration and temperature effects on fluorescence anisotropy parameters are demonstrated by DPH, p-terphenyl, alpha-NPO and PPO in DPPC lipid bilayers. Fluorescence anisotropy has shown that trans-stilbene and Rhd 800 have a two-site location in membranes. Multiphoton induced fluorescence of DPH, p-terphenyl, alpha-NPO and v-biphenyl in liposomes was measured using 800nm excitation with a femtosecond Ti:Sapphire laser. P-terphenyl, alpha-NPO and v-biphenyl are new probes for membranes. Comparison of one and multiphoton excitation results has demonstrated higher initial anisotropy with multiphoton excitation than with one-photon excitation. The rotational times were identical for one and multiphoton excitation, indicating the absence of significant local heating or sample perturbation. Excimer formation of alpha-NPO w...

  13. Study on time-resolved fluorescence dynamics of cyanine dye sensitizing AgBr

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    The fluorescence spectra of three different dyes adsorbed on the tabular and cubic AgBr microcrystals are obtained by the picosecond time-resolved streak camera technique. The dependence of the ultrafast electron transferring from dye-aggre-gates to the conduction band of AgBr and the efficiency of spectral sensitization on different kinds of dyes with different concentrations is analyzed. Further more,the microcosmic mechanism of the sensitization process is discussed. It is found that the fluorescence decay curves are fitted very well by the double exponential func-tion,consisting of a slow component and a fast one with large amplitude. We con-sider this fast one mainly attributable to the electron transfer from dye J-aggre-gates to the conduction band of AgBr.

  14. Capturing interfacial photoelectrochemical dynamics with picosecond time-resolved X-ray photoelectron spectroscopy.

    Science.gov (United States)

    Neppl, Stefan; Shavorskiy, Andrey; Zegkinoglou, Ioannis; Fraund, Matthew; Slaughter, Daniel S; Troy, Tyler; Ziemkiewicz, Michael P; Ahmed, Musahid; Gul, Sheraz; Rude, Bruce; Zhang, Jin Z; Tremsin, Anton S; Glans, Per-Anders; Liu, Yi-Sheng; Wu, Cheng Hao; Guo, Jinghua; Salmeron, Miquel; Bluhm, Hendrik; Gessner, Oliver

    2014-01-01

    Time-resolved core-level spectroscopy using laser pulses to initiate and short X-ray pulses to trace photoinduced processes has the unique potential to provide electronic state- and atomic site-specific insight into fundamental electron dynamics in complex systems. Time-domain studies using transient X-ray absorption and emission techniques have proven extremely valuable to investigate electronic and structural dynamics in isolated and solvated molecules. Here, we describe the implementation of a picosecond time-resolved X-ray photoelectron spectroscopy (TRXPS) technique at the Advanced Light Source (ALS) and its application to monitor photoinduced electron dynamics at the technologically pertinent interface formed by N3 dye molecules anchored to nanoporous ZnO. Indications for a dynamical chemical shift of the Ru3d photoemission line originating from the N3 metal centre are observed ∼30 ps after resonant HOMO-LUMO excitation with a visible laser pump pulse. The transient changes in the TRXPS spectra are accompanied by a characteristic surface photovoltage (SPV) response of the ZnO substrate on a pico- to nanosecond time scale. The interplay between the two phenomena is discussed in the context of possible electronic relaxation and recombination pathways that lead to the neutralisation of the transiently oxidised dye after ultrafast electron injection. A detailed account of the experimental technique is given including an analysis of the chemical modification of the nano-structured ZnO substrate during extended periods of solution-based dye sensitisation and its relevance for studies using surface-sensitive spectroscopy techniques.

  15. Time-resolved fluorescence analysis of the mobile flavin cofactor in -hydroxybenzoate hydroxylase

    Indian Academy of Sciences (India)

    Petra A W Van Den Berg; Koert Grever; Arie Van Hoek; Willem J H Van Berkel; Antonie J W G Visser

    2007-03-01

    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; the `in’ conformation with the isoalloxazine ring located in the active site, and the `out’ conformation with the isoalloxazine ring disposed towards the protein surface. Fluorescence-lifetime analysis of these complexes revealed similar lifetime distributions for the `in’ and `out’ conformations. The reason for this is twofold. First, the active site of PHBH contains various potential fluorescence-quenching sites close to the flavin. Fluorescence analysis of uncomplexed PHBH Y222V and Y222A showed that Tyr222 is responsible for picosecond fluorescence quenching free enzyme. In addition, other potential quenching sites, including a tryptophan and two tyrosines involved in substrate binding, are located nearby. Since the shortest distance between these quenching sites and the isoalloxazine ring differs only little on average, these aromatic residues are likely to contribute to fluorescence quenching. Second, the effect of flavin conformation on the fluorescence lifetime distribution is blurred by binding of the aromatic substrates: saturation with aromatic substrates induces highly efficient fluorescence quenching. The flavin conformation is therefore only reflected in the small relative contributions of the longer lifetimes.

  16. Time-resolved spectroscopy of the fluorescence quenching of a donor — acceptor pair by halothane

    Science.gov (United States)

    Sharma, A.; Draxler, S.; Lippitsch, M. E.

    1992-04-01

    Donor (anthracene) sensitized acceptor (perylene) fluorescence is quenched more efficiently by halothane than is intrinsic perylene fluorescence. The underlying process of dynamic fluorescence quenching is investigated by time-resolved fluorescence spectroscopy.

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

    Science.gov (United States)

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

    2010-02-01

    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.

  18. Time-resolved chlorophyll fluorescence in forest decline research

    Energy Technology Data Exchange (ETDEWEB)

    Schneckenburger, H.; Schmidt, W. [Fachhochschule Aalen (Germany). Fachbereich Optoelektronik

    1997-12-01

    Aiming at clues of forest decline we studied prompt and delayed luminescence of spruce needles from the picosecond to the second time range using various self fabricated kinetic equipments including self written software. Both kinetics in the picosecond and in the seconds time range could be fitted by three exponentially decaying components yielding three amplitudes and three reaction constants each. Basically, all components showed a typical annual time course, independent of the degree of damage or air pollution. In addition, it turned out that on one hand the `slow` component of picosecond decay kinetics (decay time {tau}=2.0-3.5 ns) reflects some damage of the photosynthetic apparatus. Similarly, in long term delayed luminescence in the seconds time range the `fast` component (decay time {tau}=0.13 s) obviously carries some information on the spruces` vitality. Interestingly, all other components are scarcely affected. In the present report we present results obtained from gas exclusion experiments performed within so-called Open Top Chambers (OTC`s) at Edelmannshof, Welzheimer Wald. In general, all spruces showed the highest photosynthetic efficiencies but also the most pronounced stress symptoms during the summer period - probably due to high irradiance, drought and increased ozone concentrations. (orig.)

  19. 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.

  20. Expansion dynamics of supercritical water probed by picosecond time-resolved photoelectron spectroscopy.

    Science.gov (United States)

    Gladytz, Thomas; Abel, Bernd; Siefermann, Katrin R

    2015-02-21

    Vibrational excitation of liquid water with femtosecond laser pulses can create extreme states of water. Yet, the dynamics directly after initial sub-picosecond delocalization of molecular vibrations remain largely unclear. We study the ultrafast expansion dynamics of an accordingly prepared supercritical water phase with a picosecond time resolution. Our experimental setup combines vacuum-compatible liquid micro-jet technology and a table top High Harmonic light source driven by a femtosecond laser system. An ultrashort laser pulse centered at a wavelength of 2900 nm excites the OH-stretch vibration of water molecules in the liquid. The deposited energy corresponds to a supercritical phase with a temperature of about 1000 K and a pressure of more than 1 GPa. We use a time-delayed extreme ultraviolet pulse centered at 38.6 eV, and obtained via High Harmonic generation (HHG), to record valence band photoelectron spectra of the expanding water sample. The series of photoelectron spectra is analyzed with noise-corrected target transform fitting (cTTF), a specifically developed multivariate method. Together with a simple fluid dynamics simulation, the following picture emerges: when a supercritical phase of water expands into vacuum, temperature and density of the first few nanometers of the expanding phase drop below the critical values within a few picoseconds. This results in a supersaturated phase, in which condensation seeds form and grow from small clusters to large clusters on a 100 picosecond timescale.

  1. Polar plot representation of time-resolved fluorescence.

    Science.gov (United States)

    Eichorst, John Paul; Wen Teng, Kai; Clegg, Robert M

    2014-01-01

    Measuring changes in a molecule's fluorescence emission is a common technique to study complex biological systems such as cells and tissues. Although the steady-state fluorescence intensity is frequently used, measuring the average amount of time that a molecule spends in the excited state (the fluorescence lifetime) reveals more detailed information about its local environment. The lifetime is measured in the time domain by detecting directly the decay of fluorescence following excitation by short pulse of light. The lifetime can also be measured in the frequency domain by recording the phase and amplitude of oscillation in the emitted fluorescence of the sample in response to repetitively modulated excitation light. In either the time or frequency domain, the analysis of data to extract lifetimes can be computationally intensive. For example, a variety of iterative fitting algorithms already exist to determine lifetimes from samples that contain multiple fluorescing species. However, recently a method of analysis referred to as the polar plot (or phasor plot) is a graphical tool that projects the time-dependent features of the sample's fluorescence in either the time or frequency domain into the Cartesian plane to characterize the sample's lifetime. The coordinate transformations of the polar plot require only the raw data, and hence, there are no uncertainties from extensive corrections or time-consuming fitting in this analysis. In this chapter, the history and mathematical background of the polar plot will be presented along with examples that highlight how it can be used in both cuvette-based and imaging applications.

  2. Time-resolved fluorescence spectroscopy for chemical sensors

    Science.gov (United States)

    Draxler, Sonja; Lippitsch, Max E.

    1996-07-01

    A family of sensors is presented with fluorescence decay-time measurements used as the sensing technique. The concept is to take a single fluorophore with a suitably long fluorescence decay time as the basic building block for numerous different sensors. Analyte recognition can be performed by different functional groups that are necessary for selective interaction with the analyte. To achieve this, the principle of excited-state electron transfer is applied with pyrene as the fluorophore. Therefore the same instrumentation based on a small, ambient air-nitrogen laser and solid-state electronics can be used to measure different analytes, for example, oxygen, pH, carbon dioxide, potassium, ammonium, lead, cadmium, zinc, and phosphate.

  3. Time-resolved fluorescence spectroscopy of oil spill detected by ocean lidar

    Science.gov (United States)

    Li, Xiao-long; Chen, Yong-hua; Li, Jie; Jiang, Jingbo; Ni, Zuotao; Liu, Zhi-shen

    2016-10-01

    Based on time-resolved fluorescence of oils, an oceanographic fluorescence Lidar was designed to identify oil pollutions. A third harmonic (at 355nm) of Nd:YAG laser is used as the excitation source, and the fluorescence intensities and lifetimes of oil fluorescence at wavelength from 380 nm to 580 nm are measured by an intensified CCD (ICCD). In the experiments, time-resolved fluorescence spectra of 20 oil samples, including crude oils, fuel oils, lubricating oil, diesel oils and gasoline, are analyzed to discuss fluorescence spectral characteristics of samples for oil classification. The spectral characteristics of oil fluorescence obtained by ICCD with delay time of 2 ns, 4 ns, and 6 ns were studied by using the principal component analysis (PCA) method. Moreover, an efficient method is used to improve the recognition rate of the oil spill types, through enlarging spectral differences of oil fluorescence at different delay times. Experimental analysis shows that the optimization method can discriminate between crude oil and fuel oil, and a more accurate classification of oils is obtained by time-resolved fluorescence spectroscopy. As the result, comparing to traditional fluorescence spectroscopy, a higher recognition rate of oil spill types is achieved by time-resolved fluorescence spectroscopy which is also a feasibility technology for Ocean Lidar.

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

    Science.gov (United States)

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

    2009-11-15

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

  5. Steady-state and time-resolved fluorometry of fluorescent pollutants and heavy metal complexes

    Science.gov (United States)

    Resch, Ute; Rurack, Knut

    1997-05-01

    Time-resolved laser-induced fluorescence spectroscopy is one of the most sensitive optical methods which is well suited for on-line in situ analysis. Here, three examples for the steady- state and time-resolved fluorescence analysis of environmentally important analytes, the fluorescent monoaromatic hydrocarbons benzene, toluene, and xylene as well as non fluorescent heavy metal ions forming a fluorescent complex with a cation coordinating fluorescence probe, are presented and the potential of both methods is discussed. For BTX, various mixtures of the spectrally similar compounds B, T, and X showing different fluorescence lifetimes were studied with both methods. As an example for fluorometric metal ion analysis, the fluorescence probe BP(OH)2 (2,2'-bipyridyl- 3,3'-diol) was employed for the determination of d10 metal ions in water and the newly developed fluorescence probe APTA for the detection of Cu(II). Cation complexation of BP(OH2 yields spectrally very similar complexes which differ in their fluorescence lifetimes. Complexation of APTA to Cu(II) leads to small spectral changes and a strong increase in fluorescence quantum yield and lifetime. For the analytes studied, a comparison of the detection limits, standard deviations, and linear dynamic range of both methods clearly demonstrates the analytical potential of time-resolved fluorometry.

  6. Fluorescence-suppressed time-resolved Raman spectroscopy of pharmaceuticals using complementary metal-oxide semiconductor (CMOS) single-photon avalanche diode (SPAD) detector.

    Science.gov (United States)

    Rojalin, Tatu; Kurki, Lauri; Laaksonen, Timo; Viitala, Tapani; Kostamovaara, Juha; Gordon, Keith C; Galvis, Leonardo; Wachsmann-Hogiu, Sebastian; Strachan, Clare J; Yliperttula, Marjo

    2016-01-01

    In this work, we utilize a short-wavelength, 532-nm picosecond pulsed laser coupled with a time-gated complementary metal-oxide semiconductor (CMOS) single-photon avalanche diode (SPAD) detector to acquire Raman spectra of several drugs of interest. With this approach, we are able to reveal previously unseen Raman features and suppress the fluorescence background of these drugs. Compared to traditional Raman setups, the present time-resolved technique has two major improvements. First, it is possible to overcome the strong fluorescence background that usually interferes with the much weaker Raman spectra. Second, using the high photon energy excitation light source, we are able to generate a stronger Raman signal compared to traditional instruments. In addition, observations in the time domain can be performed, thus enabling new capabilities in the field of Raman and fluorescence spectroscopy. With this system, we demonstrate for the first time the possibility of recording fluorescence-suppressed Raman spectra of solid, amorphous and crystalline, and non-photoluminescent and photoluminescent drugs such as caffeine, ranitidine hydrochloride, and indomethacin (amorphous and crystalline forms). The raw data acquired by utilizing only the picosecond pulsed laser and a CMOS SPAD detector could be used for identifying the compounds directly without any data processing. Moreover, to validate the accuracy of this time-resolved technique, we present density functional theory (DFT) calculations for a widely used gastric acid inhibitor, ranitidine hydrochloride. The obtained time-resolved Raman peaks were identified based on the calculations and existing literature. Raman spectra using non-time-resolved setups with continuous-wave 785- and 532-nm excitation lasers were used as reference data. Overall, this demonstration of time-resolved Raman and fluorescence measurements with a CMOS SPAD detector shows promise in diverse areas, including fundamental chemical research, the

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

    Science.gov (United States)

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

    1991-06-01

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

  8. Intracellular Monitoring of AS1411 Aptamer by Time-Resolved Microspectrofluorimetry and Fluorescence Imaging.

    Science.gov (United States)

    Kočišová, Eva; Praus, Petr; Bok, Jiří; Bonneau, Stéphanie; Sureau, Franck

    2015-09-01

    Time-resolved microspectrofluorimetry and fluorescence microscopy imaging-two complementary fluorescence techniques-provide important information about the intracellular distribution, level of uptake and binding/interactions inside living cell of the labeled molecule of interest. They were employed to monitor the "fate" of AS1411 aptamer labeled by ATTO 425 in human living cells. Confocal microspectrofluorimeter adapted for time-resolved intracellular fluorescence measurements by using a phase-modulation principle with homodyne data acquisition was employed to obtain emission spectra and to determine fluorescence lifetimes in U-87 MG tumor brain cells and Hs68 non-tumor foreskin cells. Acquired spectra from both the intracellular space and the reference solutions were treated to observe the aptamer localization and its interaction with biological structures inside the living cell. The emission spectra and the maximum emission wavelengths coming from the cells are practically identical, however significant lifetime lengthening was observed for tumor cell line in comparison to non-tumor one.

  9. Use of Time-Resolved Fluorescence to Monitor Bioactive Compounds in Plant Based Foodstuffs

    Directory of Open Access Journals (Sweden)

    M. Adília Lemos

    2015-06-01

    Full Text Available The study of compounds that exhibit antioxidant activity has recently received much interest in the food industry because of their potential health benefits. Most of these compounds are plant based, such as polyphenolics and carotenoids, and there is a need to monitor them from the field through processing and into the body. Ideally, a monitoring technique should be non-invasive with the potential for remote capabilities. The application of the phenomenon of fluorescence has proved to be well suited, as many plant associated compounds exhibit fluorescence. The photophysical behaviour of fluorescent molecules is also highly dependent on their microenvironment, making them suitable probes to monitor changes in pH, viscosity and polarity, for example. Time-resolved fluorescence techniques have recently come to the fore, as they offer the ability to obtain more information, coupled with the fact that the fluorescence lifetime is an absolute measure, while steady state just provides relative and average information. In this work, we will present illustrative time-resolved measurements, rather than a comprehensive review, to show the potential of time-resolved fluorescence applied to the study of bioactive substances. The aim is to help assess if any changes occur in their form, going from extraction via storage and cooking to the interaction with serum albumin, a principal blood transport protein.

  10. Advances in ultrafast time resolved fluorescence physics for cancer detection in optical biopsy

    Directory of Open Access Journals (Sweden)

    R. R. Alfano

    2012-03-01

    Full Text Available We discuss the use of time resolved fluorescence spectroscopy to extract fundamental kinetic information on molecular species in tissues. The temporal profiles reveal the lifetime and amplitudes associated with key active molecules distinguishing the local spectral environment of tissues. The femtosecond laser pulses at 310 nm excite the tissue. The emission profile at 340 nm from tryptophan is non-exponential due to the micro-environment. The slow and fast amplitudes and lifetimes of emission profiles reveal that cancer and normal states can be distinguished. Time resolved optical methods offer a new cancer diagnostic modality for the medical community.

  11. Locating and classifying fluorescent tags behind turbid layers using time-resolved inversion.

    Science.gov (United States)

    Satat, Guy; Heshmat, Barmak; Barsi, Christopher; Raviv, Dan; Chen, Ou; Bawendi, Moungi G; Raskar, Ramesh

    2015-04-13

    The use of fluorescent probes and the recovery of their lifetimes allow for significant advances in many imaging systems, in particular, medical imaging systems. Here we propose and experimentally demonstrate reconstructing the locations and lifetimes of fluorescent markers hidden behind a turbid layer. This opens the door to various applications for non-invasive diagnosis, analysis, flowmetry and inspection. The method is based on a time-resolved measurement that captures information about both fluorescence lifetime and spatial position of the probes. To reconstruct the scene, the method relies on a sparse optimization framework to invert time-resolved measurements. This wide-angle technique does not rely on coherence, and does not require the probes to be directly in line of sight of the camera, making it potentially suitable for long-range imaging.

  12. Halide (Cl(super -)) Quenching of Quinine Sulfate Fluorescence: A Time-Resolved Fluorescence Experiment for Physical Chemistry

    Science.gov (United States)

    Gutow, Jonathan H.

    2005-01-01

    The time-resolved fluorescence experiment investigating the halide quenching of fluorescence from quinine sulfate in water is described. The objectives of the experiment include reinforcing student understanding of the kinetics of competing pathways, making connections with microscopic theories of kinetics through comparison of experimental and…

  13. CMOS time-resolved, contact, and multispectral fluorescence imaging for DNA molecular diagnostics.

    Science.gov (United States)

    Guo, Nan; Cheung, Kawai; Wong, Hiu Tong; Ho, Derek

    2014-10-31

    Instrumental limitations such as bulkiness and high cost prevent the fluorescence technique from becoming ubiquitous for point-of-care deoxyribonucleic acid (DNA) detection and other in-field molecular diagnostics applications. The complimentary metal-oxide-semiconductor (CMOS) technology, as benefited from process scaling, provides several advanced capabilities such as high integration density, high-resolution signal processing, and low power consumption, enabling sensitive, integrated, and low-cost fluorescence analytical platforms. In this paper, CMOS time-resolved, contact, and multispectral imaging are reviewed. Recently reported CMOS fluorescence analysis microsystem prototypes are surveyed to highlight the present state of the art.

  14. CMOS Time-Resolved, Contact, and Multispectral Fluorescence Imaging for DNA Molecular Diagnostics

    Directory of Open Access Journals (Sweden)

    Nan Guo

    2014-10-01

    Full Text Available Instrumental limitations such as bulkiness and high cost prevent the fluorescence technique from becoming ubiquitous for point-of-care deoxyribonucleic acid (DNA detection and other in-field molecular diagnostics applications. The complimentary metal-oxide-semiconductor (CMOS technology, as benefited from process scaling, provides several advanced capabilities such as high integration density, high-resolution signal processing, and low power consumption, enabling sensitive, integrated, and low-cost fluorescence analytical platforms. In this paper, CMOS time-resolved, contact, and multispectral imaging are reviewed. Recently reported CMOS fluorescence analysis microsystem prototypes are surveyed to highlight the present state of the art.

  15. Photophysical behavior and fluorescence quenching by halides of quinidine dication: Steady state and time resolved study

    Energy Technology Data Exchange (ETDEWEB)

    Joshi, Neeraj Kumar; Tewari, Neeraj; Arora, Priyanka; Rautela, Ranjana; Pant, Sanjay [Photophysics Laboratory, Department of Physics, DSB Campus, Kumaun University, Nainital 263002, Uttarakhand (India); Joshi, Hem Chandra, E-mail: hem_sup@yahoo.co.uk [Institute for Plasma Research, Laser Diagnostics Division, Bhat, Near Indira Bridge, Gandhinagar 382428, Gujarat (India)

    2015-02-15

    The fluorescence quenching of quinidine in acidified aqueous solution by various halides (Cl{sup −}, Br{sup −} and I{sup −}) was studied using steady state and time resolved fluorescence techniques. The quenching process was characterized by Stern–Volmer (S–V) plots. Possibility of conformers (one is not quenched by halide and the other is quenched) is invoked to explain the observed results. - Highlights: • Fluorescence quenching of quinidine in acidified aqueous solution by halides. • Various quenching parameters have been estimated. • Possibility of conformers is invoked to explain the observed results.

  16. Assembling Tunable Time-Resolved Fluorescence Layer onto Nano-Gold

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    The assembling of a coating of time-resolved fluorescent chelator BSPDA (abbreviated for 4,7-bis(sulfhydrylphenyl)-1,10-phenanthroline-2,9-dicarboxylic acid) onto a nano-gold layer was demonstrated. First, BSPDA was synthesized by simple procedures, and then an approach was developed to immobilize BSPDA onto the nano-gold layer deposited on a silane modified glass substrate, whereby europium ion (Ⅲ, Eu3+) was captured and released owing to the interactive process of complexation and dissociation between BSPDA functionalized coating and Eu3+ solution. The fluorescence spectra and related lifetimes were determined. Also, the BSPDA functionalized coating's specific complexation with Eu3+ on the BSPDA assembly layer and the nonspecific adsorption of Eu3+ on the nano-gold layer were compared. These results allowed a selective complexation of Eu3+ by assembling a BSPDA chelating layer on the nano-gold layer;thus, a tunable time-resolved fluorescent layer was covalently attached. The results of the nanoparticle assembling and probing (or labeling) processes to specific bio-systems were very interesting and had significant implications to time-resolved-fluorescence-based detection on biosensor surfaces such as DNA chip and to arrayed light display devices.

  17. Feasibility analysis of an epidermal glucose sensor based on time-resolved fluorescence

    Science.gov (United States)

    Katika, Kamal M.; Pilon, Laurent

    2007-06-01

    The goal of this study is to test the feasibility of using an embedded time-resolved fluorescence sensor for monitoring glucose concentration. Skin is modeled as a multilayer medium with each layer having its own optical properties and fluorophore absorption coefficients, lifetimes, and quantum yields obtained from the literature. It is assumed that the two main fluorophores contributing to the fluorescence at these excitation and emission wavelengths are nicotinamide adenine dinucleotide (NAD)H and collagen. The intensity distributions of excitation and fluorescent light in skin are determined by solving the transient radiative transfer equation by using the modified method of characteristics. The fluorophore lifetimes are then recovered from the simulated fluorescence decays and compared with the actual lifetimes used in the simulations. Furthermore, the effect of adding Poissonian noise to the simulated decays on recovering the lifetimes was studied. For all cases, it was found that the fluorescence lifetime of NADH could not be recovered because of its negligible contribution to the overall fluorescence signal. The other lifetimes could be recovered to within 1.3% of input values. Finally, the glucose concentrations within the skin were recovered to within 13.5% of their actual values, indicating a possibility of measuring glucose concentrations by using a time-resolved fluorescence sensor.

  18. Time-Resolved Fluorescence in Lipid Bilayers: Selected Applications and Advantages over Steady State

    Science.gov (United States)

    Amaro, Mariana; Šachl, Radek; Jurkiewicz, Piotr; Coutinho, Ana; Prieto, Manuel; Hof, Martin

    2014-01-01

    Fluorescence methods are versatile tools for obtaining dynamic and topological information about biomembranes because the molecular interactions taking place in lipid membranes frequently occur on the same timescale as fluorescence emission. The fluorescence intensity decay, in particular, is a powerful reporter of the molecular environment of a fluorophore. The fluorescence lifetime can be sensitive to the local polarity, hydration, viscosity, and/or presence of fluorescence quenchers/energy acceptors within several nanometers of the vicinity of a fluorophore. Illustrative examples of how time-resolved fluorescence measurements can provide more valuable and detailed information about a system than the time-integrated (steady-state) approach will be presented in this review: 1), determination of membrane polarity and mobility using time-dependent spectral shifts; 2), identification of submicroscopic domains by fluorescence lifetime imaging microscopy; 3), elucidation of membrane leakage mechanisms from dye self-quenching assays; and 4), evaluation of nanodomain sizes by time-resolved Förster resonance energy transfer measurements. PMID:25517142

  19. Spectra-resolved technique of a sensitive time-resolved fluorescence immunoassay instrument

    Science.gov (United States)

    Guo, Zhouyi; Tian, Zhen; Jia, Yali

    2004-07-01

    The lanthanide trivalence ion and its chelates are used for marking substance in time-resolved fluorescence immunoassay (TRFIA), marking the protein, hormone, antibody, nucleic acid probe or biologica alive cell, to measure the concentration of the analysis substance inside the reaction system with time-resolved fluorometry after the reaction system occurred, and attain the quantitative analysis's purpose. TRFIA has been become a kind of new and more sensitive measure method after radioisotope marking, enzymatic marking, chemiluminescence, electrochemiluminescence, it primarily is decided by the special physics and chemistry characteristic of lanthanide trivalence ion and its chelates. In this paper, the result of spectroscopic evaluation of europium trivalence ion and its chelate, and the principle of spectra-resolved technology and a sensitive time-resolved fluorescence immunoassay instrument made by ourselves are reported. In the set, a high frequency Xenon pulsed-light was adopted as exciting light, and two special filters was utilized according to spectra-resolved technique. Thus the influence of scattering light and short-lifetime fluorescence was removed. And the sensitivity is 10-12mol/L (when Eu3+ was used for marking substance), examination repeat is CV = 95% (p < 0.01).

  20. Fluorescence imaging and time-resolved spectroscopy of steroid using confocal synchrotron radiation microscopy

    Science.gov (United States)

    Gerritsen, Hans C.; van der Oord, C. J. R.; Levine, Yehudi K.; Munro, Ian H.; Jones, Gareth R.; Shaw, D. A.; Rommerts, Fokko F.

    1994-08-01

    The Confocal Synchrotron Radiation Microscope at Daresbury was used in a study of the transport and distribution of the steroid Coumestrol in single Leydig cells. The broad spectrum of synchrotron radiation in combination with UV compatible microscope optics affords the extension of confocal microscopy from the visible to the UV region down to about 200 nm. Consequently fluorescent molecules with absorption bands in the UV can be imaged. In addition the pulsed nature of the light source allows us to perform time-resolved fluorescence spectroscopy experiments on microscopic volumes. Coumestrol is a naturally fluorescing plant steroid exhibiting estrogenic activity. In physiological environments it has an absorption peak in the UV at 340 nm and it emits around 440 nm. First results indicate that the Coumestrol transport through the cell membrane is diffusion limited. The weak fluorescence observed in the nuclei of the Leydig cells may be due to fluorescence quenching arising from the interaction of the Coumesterol with nuclear components. However, micro-volume time-resolved fluorescence spectroscopy experiments on cell nuclei have revealed the same decay behavior for Coumesterol in both the cytoplasm and nucleus of the cells.

  1. Time-Resolved Fluorescence Immunoassay for C-Reactive Protein Using Colloidal Semiconducting Nanoparticles

    Directory of Open Access Journals (Sweden)

    Pekka Hänninen

    2011-11-01

    Full Text Available Besides the typical short-lived fluorescence with decay times in the nanosecond range, colloidal II/VI semiconductor nanoparticles dispersed in buffer also possess a long-lived fluorescence component with decay times in the microsecond range. Here, the signal intensity of the long-lived luminescence at microsecond range is shown to increase 1,000-fold for CdTe nanoparticles in PBS buffer. This long-lived fluorescence can be conveniently employed for time-gated fluorescence detection, which allows for improved signal-to-noise ratio and thus the use of low concentrations of nanoparticles. The detection principle is demonstrated with a time-resolved fluorescence immunoassay for the detection of C-reactive protein (CRP using CdSe-ZnS nanoparticles and green light excitation.

  2. Development of time-resolved laser-induced fluorescence spectroscopic technique for the analysis of biomolecules

    Directory of Open Access Journals (Sweden)

    Terzić M.

    2008-01-01

    Full Text Available Our developments of the time-resolved laser-induced fluorescence (TR-LIF detection system for biomolecules are presented. This system is based on the tunable (320 nm to 475 nm Nd:YAG laser pulses used to excite various biomolecules. The detection part is the Streak System for Fluorescence Lifetime Spectroscopy (Hamamatsu, Japan. The system consists of a C4334-01 streakscope, as a detector, DG 535 digital pulse/delay generator, C5094-S Spectrograph and HPD-TA System, as a temporal analyzer. The TR-LIF spectrometer is designed primarily to study the temperature and pressure effects on fluorescence behavior of biomolecules upon excitation with a single nanosecond pulse. The design of this system has capability to combine laser-induced breakdown (LIB with fluorescence, as well to study optodynamic behavior of fluorescence biomolecules.

  3. Characterization of powellite-based solid solutions by site-selective time resolved laser fluorescence spectroscopy

    OpenAIRE

    Schmidt, Moritz; Heck, Stephanie; Bosbach, Dirk; Ganschow, Steffen; Walther, Clemens; Stumpf, Thorsten

    2013-01-01

    We present a comprehensive study of the solid solution system Ca-2(MoO4)(2)-NaGd(MoO4)(2) on the molecular scale, by means of site-selective time resolved laser fluorescence spectroscopy (TRLFS). Eu3+ is used as a trace fluorescent probe, homogeneously substituting for Gd3+ in the solid solution crystal structure. Site-selective TRLFS of a series of polycrystalline samples covering the whole composition range of the solid solution series from 10% substitution of Ca2+ to the NaGd end-member re...

  4. Local structures in ionic liquids probed and characterized by microscopic thermal diffusion monitored with picosecond time-resolved Raman spectroscopy.

    Science.gov (United States)

    Yoshida, Kyousuke; Iwata, Koichi; Nishiyama, Yoshio; Kimura, Yoshifumi; Hamaguchi, Hiro-o

    2012-03-14

    Vibrational cooling rate of the first excited singlet (S(1)) state of trans-stilbene and bulk thermal diffusivity are measured for seven room temperature ionic liquids, C(2)mimTf(2)N, C(4)mimTf(2)N, C(4)mimPF(6), C(5)mimTf(2)N, C(6)mimTf(2)N, C(8)mimTf(2)N, and bmpyTf(2)N. Vibrational cooling rate measured with picosecond time-resolved Raman spectroscopy reflects solute-solvent and solvent-solvent energy transfer in a microscopic solvent environment. Thermal diffusivity measured with the transient grating method indicates macroscopic heat conduction capability. Vibrational cooling rate of S(1) trans-stilbene is known to have a good correlation with bulk thermal diffusivity in ordinary molecular liquids. In the seven ionic liquids studied, however, vibrational cooling rate shows no correlation with thermal diffusivity; the observed rates are similar (0.082 to 0.12 ps(-1) in the seven ionic liquids and 0.08 to 0.14 ps(-1) in molecular liquids) despite large differences in thermal diffusivity (5.4-7.5 × 10(-8) m(2) s(-1) in ionic liquids and 8.0-10 × 10(-8) m(2) s(-1) in molecular liquids). This finding is consistent with our working hypothesis that there are local structures characteristically formed in ionic liquids. Vibrational cooling rate is determined by energy transfer among solvent ions in a local structure, while macroscopic thermal diffusion is controlled by heat transfer over boundaries of local structures. By using "local" thermal diffusivity, we are able to simulate the vibrational cooling kinetics observed in ionic liquids with a model assuming thermal diffusion in continuous media. The lower limit of the size of local structure is estimated with vibrational cooling process observed with and without the excess energy. A quantitative discussion with a numerical simulation shows that the diameter of local structure is larger than 10 nm. If we combine this lower limit, 10 nm, with the upper limit, 100 nm, which is estimated from the transparency (no light

  5. Design and evaluation of a device for fast multispectral time-resolved fluorescence spectroscopy and imaging.

    Science.gov (United States)

    Yankelevich, Diego R; Ma, Dinglong; Liu, Jing; Sun, Yang; Sun, Yinghua; Bec, Julien; Elson, Daniel S; Marcu, Laura

    2014-03-01

    The application of time-resolved fluorescence spectroscopy (TRFS) to in vivo tissue diagnosis requires a method for fast acquisition of fluorescence decay profiles in multiple spectral bands. This study focusses on development of a clinically compatible fiber-optic based multispectral TRFS (ms-TRFS) system together with validation of its accuracy and precision for fluorescence lifetime measurements. It also presents the expansion of this technique into an imaging spectroscopy method. A tandem array of dichroic beamsplitters and filters was used to record TRFS decay profiles at four distinct spectral bands where biological tissue typically presents fluorescence emission maxima, namely, 390, 452, 542, and 629 nm. Each emission channel was temporally separated by using transmission delays through 200 μm diameter multimode optical fibers of 1, 10, 19, and 28 m lengths. A Laguerre-expansion deconvolution algorithm was used to compensate for modal dispersion inherent to large diameter optical fibers and the finite bandwidth of detectors and digitizers. The system was found to be highly efficient and fast requiring a few nano-Joule of laser pulse energy and time-resolved fluorescence lifetime measurements of low quantum efficiency sub-nanosecond fluorophores.

  6. [Discrimination of Crude Oil Samples Using Laser-Induced Time-Resolved Fluorescence Spectroscopy].

    Science.gov (United States)

    Han, Xiao-shuang; Liu, De-qing; Luan, Xiao-ning; Guo, Jin-jia; Liu, Yong-xin; Zheng, Rong-er

    2016-02-01

    The Laser-induced fluorescence spectra combined with pattern recognition method has been widely applied in discrimination of different spilled oil, such as diesel, gasoline, and crude oil. However, traditional three-dimension fluorescence analysis method, which is not adapted to requirement of field detection, is limited to laboratory investigatio ns. The development of oil identification method for field detection is significant to quick response and operation of oil spill. In this paper, a new method based on laser-induced time-resolved fluorescence combined with support vector machine (SVM) model was introduced to discriminate crude oil samples. In this method, time-resolved spectra data was descended into two dimensions with selecting appropriate range in time and wavelength domains respectively to form a SVM data base. It is found that the classification accurate rate increased with an appropriate selection. With a selected range from 54 to 74 ns in time domain, the classification accurate rate has been increased from 83.3% (without selection) to 88.1%. With a selected wavelength range of 387.00~608.87 nm, the classification accurate rate of suspect oil was improved from 84% (without selection) to 100%. Since the detection delay of fluorescence lidar fluctuates due to wave and platform swing, the identification method with optimizing in both time and wavelength domains could offer a better flexibility for field applications. It is hoped that the developed method could provide some useful reference with data reduction for classification of suspect crude oil in the future development.

  7. Fluorescence properties of dyes adsorbed to silver islands, investigated by picosecond techniques

    Science.gov (United States)

    Leitner, A.; Lippitsch, M. E.; Draxler, S.; Riegler, M.; Aussenegg, F. R.

    1985-02-01

    The fluorescence properties of dye molecules (rhodamine 6G and erythrosin) adsorbed on pure glass surfaces and on silver islands films are investigated by cw and picosecond time-resolved methods. On pure glass surfaces we observe concentration quenching below a critical intermolecular distance (reduction of the fluorescence power per molecule as well as shortened and non-exponential fluorescence decay). On silver islands films the shortening in fluorescence lifetime is more drastic and is nearly independent of the intermolecular distance. This behavior suggests an electrodynamic interaction between dye monomers and plasmons in the metal particles, modified by a damping influence of dye dimers.

  8. Diffuse optical fluorescence tomography using time-resolved data acquired in transmission

    Science.gov (United States)

    Leblond, Frederic; Fortier, Simon; Friedlander, Michael P.

    2007-02-01

    We present an algorithm using data acquired with a time-resolved system with the goal of reconstructing sources of fluorescence emanating from the deep interior of highly scattering biological tissues. A novelty in our tomography algorithm is the integration of a light transport model adapted to rodent geometries. For small volumes, our analysis suggest that neglecting the index of refraction mismatch between diffusive and non-diffusive regions, as well as the curved nature of the boundary, can have a profound impact on fluorescent images and spectroscopic applications relying on diffusion curve fitting. Moreover, we introduce a new least-squares solver with bound constraints adapted for optical problems where a physical non-negative constraint can be imposed. Finally, we find that maximizing the time-related information content of the data in the reconstruction process significantly enhances the quality of fluorescence images. Preliminary noise propagation and detector placement optimization analysis are also presented.

  9. Efficient signal processing for time-resolved fluorescence detection of nitrogen-vacancy spins in diamond

    Science.gov (United States)

    Gupta, A.; Hacquebard, L.; Childress, L.

    2016-03-01

    Room-temperature fluorescence detection of the nitrogen-vacancy center electronic spin typically has low signal to noise, requiring long experiments to reveal an averaged signal. Here, we present a simple approach to analysis of time-resolved fluorescence data that permits an improvement in measurement precision through signal processing alone. Applying our technique to experimental data reveals an improvement in signal to noise equivalent to a 14% increase in photon collection efficiency. We further explore the dependence of the signal to noise ratio on excitation power, and analyze our results using a rate equation model. Our results provide a rubric for optimizing fluorescence spin detection, which has direct implications for improving precision of nitrogen-vacancy-based sensors.

  10. Drug/protein interactions studied by time-resolved fluorescence spectroscopy

    Science.gov (United States)

    Gustavsson, Thomas; Markovitsi, Dimitra; Vayá, Ignacio; Bonancía, Paula; Jiménez, M. C.; Miranda, Miguel A.

    2014-09-01

    We report here on a recent time-resolved fluorescence study [1] of the interaction between flurbiprofen (FBP), a chiral non-steroidal anti-inflammatory drug, and human serum albumin (HSA), the main transport protein in the human body. We compare the results obtained for the drug-protein complex with those of various covalently linked flurbiprofentryptophan dyads having well-defined geometries. In all cases stereoselective dynamic fluorescence quenching is observed, varying greatly from one system to another. In addition, the fluorescence anisotropy decays also display a clear stereoselectivity. For the drug-protein complexes, this can be interpreted in terms of the protein microenvironment playing a significant role in the conformational relaxation of FBP, which is more restricted in the case of the (R)- enantiomer.

  11. Advanced Time-Resolved Fluorescence Microscopy Techniques for the Investigation of Peptide Self-Assembly

    Science.gov (United States)

    Anthony, Neil R.

    The ubiquitous cross beta sheet peptide motif is implicated in numerous neurodegenerative diseases while at the same time offers remarkable potential for constructing isomorphic high-performance bionanomaterials. Despite an emerging understanding of the complex folding landscape of cross beta structures in determining disease etiology and final structure, we lack knowledge of the critical initial stages of nucleation and growth. In this dissertation, I advance our understanding of these key stages in the cross-beta nucleation and growth pathways using cutting-edge microscopy techniques. In addition, I present a new combined time-resolved fluorescence analysis technique with the potential to advance our current understanding of subtle molecular level interactions that play a pivotal role in peptide self-assembly. Using the central nucleating core of Alzheimer's Amyloid-beta protein, Abeta(16 22), as a model system, utilizing electron, time-resolved, and non-linear microscopy, I capture the initial and transient nucleation stages of peptide assembly into the cross beta motif. In addition, I have characterized the nucleation pathway, from monomer to paracrystalline nanotubes in terms of morphology and fluorescence lifetime, corroborating the predicted desolvation process that occurs prior to cross-beta nucleation. Concurrently, I have identified unique heterogeneous cross beta domains contained within individual nanotube structures, which have potential bionanomaterials applications. Finally, I describe a combined fluorescence theory and analysis technique that dramatically increases the sensitivity of current time-resolved techniques. Together these studies demonstrate the potential for advanced microscopy techniques in the identification and characterization of the cross-beta folding pathway, which will further our understanding of both amyloidogenesis and bionanomaterials.

  12. A CTRW-based model of time-resolved fluorescence lifetime imaging in a turbid medium.

    Science.gov (United States)

    Chernomordik, Victor; Gandjbakhche, Amir H; Hassan, Moinuddin; Pajevic, Sinisa; Weiss, George H

    2010-12-01

    We develop an analytic model of time-resolved fluorescent imaging of photons migrating through a semi-infinite turbid medium bounded by an infinite plane in the presence of a single stationary point fluorophore embedded in the medium. In contrast to earlier models of fluorescent imaging in which photon motion is assumed to be some form of continuous diffusion process, the present analysis is based on a continuous-time random walk (CTRW) on a simple cubic lattice, the object being to estimate the position and lifetime of the fluorophore. Such information can provide information related to local variations in pH and temperature with potential medical significance. Aspects of the theory were tested using time-resolved measurements of the fluorescence from small inclusions inside tissue-like phantoms. The experimental results were found to be in good agreement with theoretical predictions provided that the fluorophore was not located too close to the planar boundary, a common problem in many diffusive systems.

  13. Time-resolved fluorescence studies of nucleotide flipping by restriction enzymes.

    Science.gov (United States)

    Neely, Robert K; Tamulaitis, Gintautas; Chen, Kai; Kubala, Marta; Siksnys, Virginijus; Jones, Anita C

    2009-11-01

    Restriction enzymes Ecl18kI, PspGI and EcoRII-C, specific for interrupted 5-bp target sequences, flip the central base pair of these sequences into their protein pockets to facilitate sequence recognition and adjust the DNA cleavage pattern. We have used time-resolved fluorescence spectroscopy of 2-aminopurine-labelled DNA in complex with each of these enzymes in solution to explore the nucleotide flipping mechanism and to obtain a detailed picture of the molecular environment of the extrahelical bases. We also report the first study of the 7-bp cutter, PfoI, whose recognition sequence (T/CCNGGA) overlaps with that of the Ecl18kI-type enzymes, and for which the crystal structure is unknown. The time-resolved fluorescence experiments reveal that PfoI also uses base flipping as part of its DNA recognition mechanism and that the extrahelical bases are captured by PfoI in binding pockets whose structures are quite different to those of the structurally characterized enzymes Ecl18kI, PspGI and EcoRII-C. The fluorescence decay parameters of all the enzyme-DNA complexes are interpreted to provide insight into the mechanisms used by these four restriction enzymes to flip and recognize bases and the relationship between nucleotide flipping and DNA cleavage.

  14. Use of time-resolved fluorescence spectroscopy to evaluate diagnostic value of collagen degradation products.

    Science.gov (United States)

    Sikora, Joanna; Cyrankiewicz, Michał; Wybranowski, Tomasz; Ziomkowska, Blanka; Ośmiałowski, Borys; Obońska, Ewa; Augustyńska, Beata; Kruszewski, Stefan; Kubica, Jacek

    2015-05-01

    The concentration of collagen degradation products (CDPs) may reflect the process of left ventricular remodeling (LVR). The aim of this study was to evaluate the potential diagnostic usefulness of time-resolved fluorescence spectroscopy (TRFS) in assessment of CDPs. The preliminary experiment was designed to establish if CDPs’ characteristics might be visible by mean fluorescence lifetime (FLT) in determined conditions. The in vitro model of CDPs was prepared by conducting the hydrolysis of type III collagen. The FLT of samples was measured by the time-resolved spectrometer Life Spec II with the subnanosecond pulsed 360-nm EPLED diode. The FLTs were obtained by deconvolution analysis of the data using a multiexponential model of fluorescence decay. In order to determine the limit of traceability of CDPs, a comparison of different collagen/plasma ratio in samples was performed. The results of our study showed that the increase of added plasma to hydrolyzed collagen extended the mean FLT. Thus, the diagnosis of LVR based on measurements using TRFS is possible. However, it is important to point out the experiment was preliminary and further investigation in this field of research is crucial.

  15. Adaptation of light-harvesting systems of Arthrospira platensis to light conditions, probed by time-resolved fluorescence spectroscopy.

    Science.gov (United States)

    Akimoto, Seiji; Yokono, Makio; Hamada, Fumiya; Teshigahara, Ayaka; Aikawa, Shimpei; Kondo, Akihiko

    2012-08-01

    Cyanobacteria change the quantity and/or quality of their pigment-protein complexes in response to light conditions. In the present study, we analyzed excitation relaxation dynamics in the cyanobacterium, Arthrospira (Spirulina) platensis, grown under lights exhibiting different spectral profiles, by means of steady-state absorption and picosecond time-resolved fluorescence spectroscopies. It was found that F760, which is the PSI red-chlorophyll characteristic of A. platensis, contributes to slower energy-transfer phase in the PSI of A. platensis. Excitation energy transfers in phycobilisome and those from PSII to PSI were modified depending on the light quality. Existence of quencher was suggested in PSI of the blue-light grown cells. Phycobilisomes in the green-light grown cells and the far-red-light grown cells transferred excitation energy from phycobilisome to chlorophyll without loss of energy. In these cells, excitation energy was shared between two photosystems. Fast energy transfer was established in phycobilisome under the yellow-light condition where only the phycobilisome can absorb the cultivation light. Differences in light-harvesting and energy-transfer processes under different cultivation-light conditions are discussed. This article is part of a Special Issue entitled: Photosynthesis Research for Sustainability: from Natural to Artificial.

  16. Real time optical Biopsy: Time-resolved Fluorescence Spectroscopy instrumentation and validation

    Science.gov (United States)

    Kittle, David S.; Vasefi, Fartash; Patil, Chirag G.; Mamelak, Adam; Black, Keith L.; Butte, Pramod V.

    2016-12-01

    The Time-resolved fluorescence spectroscopy (TR-FS) has the potential to differentiate tumor and normal tissue in real time during surgical excision. In this manuscript, we describe the design of a novel TR-FS device, along with preliminary data on detection accuracy for fluorophores in a mixture. The instrument is capable of near real-time fluorescence lifetime acquisition in multiple spectral bands and analysis. It is also able to recover fluorescence lifetime with sub-20ps accuracy as validated with individual organic fluorescence dyes and dye mixtures yielding lifetime values for standard fluorescence dyes that closely match with published data. We also show that TR-FS is able to quantify the relative concentration of fluorescence dyes in a mixture by the unmixing of lifetime decays. We show that the TR-FS prototype is able to identify in near-real time the concentrations of dyes in a complex mixture based on previously trained data. As a result, we demonstrate that in complex mixtures of fluorophores, the relative concentration information is encoded in the fluorescence lifetime across multiple spectral bands. We show for the first time the temporal and spectral measurements of a mixture of fluorochromes and the ability to differentiate relative concentrations of each fluorochrome mixture in real time.

  17. Design and evaluation of a device for fast multispectral time-resolved fluorescence spectroscopy and imaging

    Energy Technology Data Exchange (ETDEWEB)

    Yankelevich, Diego R. [Department of Electrical and Computer Engineering, University of California, 3101 Kemper Hall, Davis, California 95616 (United States); Department of Biomedical Engineering, University of California, 451 Health Sciences Drive, Davis, California 95616 (United States); Ma, Dinglong; Liu, Jing; Sun, Yang; Sun, Yinghua; Bec, Julien; Marcu, Laura, E-mail: lmarcu@ucdavis.edu [Department of Biomedical Engineering, University of California, 451 Health Sciences Drive, Davis, California 95616 (United States); Elson, Daniel S. [Hamlyn Centre for Robotic Surgery, Department of Surgery and Cancer, Imperial College London, Exhibition Road, London SW7 2AZ (United Kingdom)

    2014-03-15

    The application of time-resolved fluorescence spectroscopy (TRFS) to in vivo tissue diagnosis requires a method for fast acquisition of fluorescence decay profiles in multiple spectral bands. This study focusses on development of a clinically compatible fiber-optic based multispectral TRFS (ms-TRFS) system together with validation of its accuracy and precision for fluorescence lifetime measurements. It also presents the expansion of this technique into an imaging spectroscopy method. A tandem array of dichroic beamsplitters and filters was used to record TRFS decay profiles at four distinct spectral bands where biological tissue typically presents fluorescence emission maxima, namely, 390, 452, 542, and 629 nm. Each emission channel was temporally separated by using transmission delays through 200 μm diameter multimode optical fibers of 1, 10, 19, and 28 m lengths. A Laguerre-expansion deconvolution algorithm was used to compensate for modal dispersion inherent to large diameter optical fibers and the finite bandwidth of detectors and digitizers. The system was found to be highly efficient and fast requiring a few nano-Joule of laser pulse energy and <1 ms per point measurement, respectively, for the detection of tissue autofluorescent components. Organic and biological chromophores with lifetimes that spanned a 0.8–7 ns range were used for system validation, and the measured lifetimes from the organic fluorophores deviated by less than 10% from values reported in the literature. Multi-spectral lifetime images of organic dye solutions contained in glass capillary tubes were recorded by raster scanning the single fiber probe in a 2D plane to validate the system as an imaging tool. The lifetime measurement variability was measured indicating that the system provides reproducible results with a standard deviation smaller than 50 ps. The ms-TRFS is a compact apparatus that makes possible the fast, accurate, and precise multispectral time-resolved fluorescence

  18. Picosecond kinetic measurements of the metalloporphyrin fluorescence

    Energy Technology Data Exchange (ETDEWEB)

    Aaviskoq, Y.Y.; Freiburg, A.M.; Savikhin, S.F.; Stel' makh, G.F.

    1986-08-01

    The authors attempt to directly measure the deactivation kinetics of the short-lived excited S/sub 2/ and S/sub 1/ states of metalloporphyrins and compare the results with those obtained by other (either direct or indirect) methods. The studies were carried out on diamagnetic metallocomplexes of tetrabenzoporphyrin (MeTBP) exhibiting measurable fluorescence from the S/sub 1/ and S/sub 2/ states. The complexes with Lu, Cd, and Zn in dilute solutions were studied at room temperature. The results of direct kinetic experiments confirm the previously obtained data on picosecond deactivation processes in photoexcited metalloporphyrins.

  19. Development of a High-Speed Digitizer to Time Resolve Nanosecond Fluorescence Pulses

    Directory of Open Access Journals (Sweden)

    E. Moreno-García

    2012-04-01

    Full Text Available The development of a high-speed digitizer system to measure time-domain voltage pulses in nanoseconds range is presented in this work. The digitizer design includes a high performance digital signal processor, a high-bandwidth analog-to-digital converter of flash-type, a set of delay lines, and a computer to achieve the time-domain measurements. A program running on the processor applies a time-equivalent sampling technique to acquire the input pulse. The processor communicates with the computer via a serial port RS-232 to receive commands and to transmit data. A control program written in LabVIEW 7.1 starts an acquisition routine in the processor. The program reads data from processor point by point in each occurrence of the signal, and plots each point to recover the time-resolved input pulse after n occurrences. The developed prototype is applied to measure fluorescence pulses from a homemade spectrometer. For this application, the LabVIEW program was improved to control the spectrometer, and to register and plot time-resolved fluorescence pulses produced by a substance. The developed digitizer has 750 MHz of analog input bandwidth, and it is able to resolve 2 ns rise-time pulses with 150 ps of resolution and a temporal error of 2.6 percent.

  20. Compressive hyperspectral time-resolved wide-field fluorescence lifetime imaging

    Science.gov (United States)

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

    2017-07-01

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

  1. Simultaneous quantitation of diphtheria and tetanus antibodies by double antigen, time-resolved fluorescence immunoassay.

    Science.gov (United States)

    Aggerbeck, H; Nørgaard-Pedersen, B; Heron, I

    1996-04-19

    A dual, double antigen, time-resolved fluorescence immunoassay (DELFIA) for the simultaneous detection and quantitation of diphtheria (D) and tetanus (T) antibodies in sera has been developed. In the double antigen format one arm of the antibody binds to antigen coated microtitre wells and the other arm binds to labelled antigen to provide a fluorescent signal. This assay was found to be functionally specific for IgG antibodies and showed a good correlation with established toxin neutralization assays. Furthermore, the double antigen set-up was species independent, permitting the direct use of existing international references of animal origin to measure protective antibody levels in humans in international units (IU/ml). The detection limit corresponded to 0.0003 IU/ml with Eu(3+)-labelled toxoids and to 0.0035 IU/ml using Sm(3+)-labelled toxoids. The assay was fast with a high capacity making it a suitable method for serological surveillance studies.

  2. A Novel Europium Chelate Coated Nanosphere for Time-Resolved Fluorescence Immunoassay.

    Directory of Open Access Journals (Sweden)

    Yifeng Shen

    Full Text Available A novel europium ligand 2,2',2'',2'''-(4,7-diphenyl-1,10-phenanthroline-2,9-diyl bis (methylene bis (azanetriyl tetra acetic acid (BC-EDTA was synthesized and characterized. It shows an emission spectrum peak at 610 nm when it is excited at 360 nm, with a large Stock shift (250 nm. It is covalently coated on the surface of a bare silica nanosphere containi free amino groups, using 1-ethyl-3-(3-dimethylaminopropyl carbodiimide hydrochloride and N-Hydroxysuccinimide. We also observed an interesting phenomenon that when BC-EDTA is labeled with a silica nanosphere, the chelate shows different excitation spectrum peaks of about 295 nm. We speculate that the carboxyl has a significant influence on its excitation spectrum. The BC-EDTA/Eu3+coated nanosphere could be used as a fluorescent probe for time-resolved fluorescence immunoassay. We labeled the antibody with the fluorescent nanosphere to develop a nanosphere based hepatitis B surface antigen as a time-resolved fluorescence immunoassay reagent, which is very easy to operate and eliminates potential contamination of Eu3+ contained in the environment. The analytical and functional sensitivities are 0.0037 μg/L and 0.08 μg/L (S/N≥2.0 respectively. The detection range is 0.08-166.67 μg/L, which is much wider than that of ELISA (0.2-5 μg/L. It is comparable to the commercial dissociation-enhanced lanthanide fluoro-immunoassay system (DELFIA reagents (0.2-145 μg/L. We propose that it can fulfill clinical applications.

  3. Time-resolved remote Raman and fluorescence spectrometers for planetary exploration

    Science.gov (United States)

    Sharma, Shiv K.; Misra, Anupam K.; Acosta, Tayro E.; Lucey, Paul G.

    2012-06-01

    At the University of Hawaii, we have developed compact time-resolved (TR) Raman, and fluorescence spectrometers suitable for planetary exploration under NASA's Mars Instrument Development Program. The compact Raman and fluorescence spectrometers consist of custom miniature spectrographs based on volume holographic gratings, and custom miniature intensified CCD cameras. These spectrographs have been interfaced with a regular 50 mm camera lens as well as with a three and a half inch diameter telescope for remotely interrogating minerals, water, water-ice and dry ice. Using a small frequency-doubled Nd:YAG pulsed laser (35 mJ/pulse, 20 Hz) and 50 mm camera lens, TRRaman and LINF spectra of minerals, and bio-minerals can be measured within 30 s under super-critical CO2, and with 3.5-inch telescope these samples can be interrogated to 50 m radial distance during day time and nighttime. The fluorescence spectrograph is capable of measuring TR- laser-induced fluorescence excited with 355 nm laser in the spectral range 400-800 nm spectral range. The TR-fluorescence spectra allow measurement of LINF from rare-earths and transition-metal ions in time domain, and also assist in differentiating between abiogenic minerals from organic and biogenic materials based on the fluorescence lifetime. Biological materials are also identified from their characteristic short-lived (<10 ns) laser-induced fluorescence lifetime. These instruments will play important role in planetary exploration especially in NASA's future Mars Sample Return Mission, and lander and rover missions.

  4. Fluorescence Dynamics in the Endoplasmic Reticulum of a Live Cell: Time-Resolved Confocal Microscopy.

    Science.gov (United States)

    Ghosh, Shirsendu; Nandi, Somen; Ghosh, Catherine; Bhattacharyya, Kankan

    2016-09-19

    Fluorescence dynamics in the endoplasmic reticulum (ER) of a live non-cancer lung cell (WI38) and a lung cancer cell (A549) are studied by using time-resolved confocal microscopy. To selectively study the organelle, ER, we have used an ER-Tracker dye. From the emission maximum (λmaxem) of the ER-Tracker dye, polarity (i.e. dielectric constant, ϵ) in the ER region of the cells (≈500 nm in WI38 and ≈510 nm in A549) is estimated to be similar to that of chloroform (λmaxem =506 nm, ϵ≈5). The red shift by 10 nm in λmaxem in the cancer cell (A549) suggests a slightly higher polarity compared to the non-cancer cell (WI38). The fluorescence intensity of the ER-Tracker dye exhibits prolonged intermittent oscillations on a timescale of 2-6 seconds for the cancer cell (A549). For the non-cancer cell (WI38), such fluorescence oscillations are much less prominent. The marked fluorescence intensity oscillations in the cancer cell are attributed to enhanced calcium oscillations. The average solvent relaxation time () of the ER region in the lung cancer cell (A549, 250±50 ps) is about four times faster than that in the non-cancer cell (WI38, 1000±50 ps).

  5. Time-resolved laser fluorescence spectroscopy of UO2(CO3)3(4-).

    Science.gov (United States)

    Jung, E C; Cho, H-R; Baik, M H; Kim, H; Cha, W

    2015-11-21

    The objective of the present study is to examine the luminescence characteristics of UO2(CO3)3(4-) in detail using time-resolved laser fluorescence spectroscopy. The peak wavelengths and lifetime of UO2(CO3)3(4-) were determined at room temperature using the two excitation laser wavelengths of 266 and 448 nm. The peak wavelengths in the luminescence spectrum exhibited hypsochromic shifts compared with those of UO2(2+). The lifetime determined from several samples containing various uranium concentrations was 8.9 ± 0.8 ns. Explanations for the hindrance to the observation of the luminescence spectrum of UO2(CO3)3(4-) in previous investigations are discussed. The representative experimental parameters, which might interrupt the measurement of weak luminescence, are the insertion delay time of the detection device, the overlapped luminescence of the background materials and the primary inner filter effect in the sample solution.

  6. Time-resolved fluorescence spectroscopy for clinical diagnosis of actinic cheilitis

    Science.gov (United States)

    Cosci, Alessandro; Nogueira, Marcelo Saito; Pratavieira, Sebastião; Takahama, Ademar; Azevedo, Rebeca de Souza; Kurachi, Cristina

    2016-01-01

    Actinic cheilitis is a potentially malignant disorder of the lips. Its first cause is believed to be UV sun radiation. The lesion is highly heterogeneous, making the choice of area to be biopsied difficult. This study exploits the capabilities of time-resolved fluorescence spectroscopy for the identification of the most representative area to be biopsied. A preliminary study was performed on fourteen patients. A classification algorithm was used on data acquired on nine different biopsies. The algorithm discriminated between absent, mild, and moderate dysplasia with a sensitivity of 92.9%, 90.0%, and 80.0%, respectively. The false positive rate for healthy tissue (specificity) was 88.8%. PMID:27867726

  7. 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.

  8. Experimental station for laser-based picosecond time-resolved x-ray absorption near-edge spectroscopy

    Science.gov (United States)

    Dorchies, F.; Fedorov, N.; Lecherbourg, L.

    2015-07-01

    We present an experimental station designed for time-resolved X-ray Absorption Near-Edge Spectroscopy (XANES). It is based on ultrashort laser-plasma x-ray pulses generated from a table-top 100 mJ-class laser at 10 Hz repetition rate. A high transmission (10%-20%) x-ray beam line transport using polycapillary optics allows us to set the sample in an independent vacuum chamber, providing high flexibility over a wide spectral range from 0.5 up to 4 keV. Some XANES spectra are presented, demonstrating 1% noise level in only ˜1 mn and ˜100 cumulated laser shots. Time-resolved measurements are reported, indicating that the time resolution of the entire experimental station is 3.3 ± 0.6 ps rms.

  9. Experimental station for laser-based picosecond time-resolved x-ray absorption near-edge spectroscopy.

    Science.gov (United States)

    Dorchies, F; Fedorov, N; Lecherbourg, L

    2015-07-01

    We present an experimental station designed for time-resolved X-ray Absorption Near-Edge Spectroscopy (XANES). It is based on ultrashort laser-plasma x-ray pulses generated from a table-top 100 mJ-class laser at 10 Hz repetition rate. A high transmission (10%-20%) x-ray beam line transport using polycapillary optics allows us to set the sample in an independent vacuum chamber, providing high flexibility over a wide spectral range from 0.5 up to 4 keV. Some XANES spectra are presented, demonstrating 1% noise level in only ∼1 mn and ∼100 cumulated laser shots. Time-resolved measurements are reported, indicating that the time resolution of the entire experimental station is 3.3 ± 0.6 ps rms.

  10. Experimental station for laser-based picosecond time-resolved x-ray absorption near-edge spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Dorchies, F., E-mail: dorchies@celia.u-bordeaux1.fr; Fedorov, N.; Lecherbourg, L. [Université Bordeaux, CNRS, CEA, CELIA (Centre Lasers Intenses et Applications), UMR 5107, Talence F-33405 (France)

    2015-07-15

    We present an experimental station designed for time-resolved X-ray Absorption Near-Edge Spectroscopy (XANES). It is based on ultrashort laser-plasma x-ray pulses generated from a table-top 100 mJ-class laser at 10 Hz repetition rate. A high transmission (10%–20%) x-ray beam line transport using polycapillary optics allows us to set the sample in an independent vacuum chamber, providing high flexibility over a wide spectral range from 0.5 up to 4 keV. Some XANES spectra are presented, demonstrating 1% noise level in only ∼1 mn and ∼100 cumulated laser shots. Time-resolved measurements are reported, indicating that the time resolution of the entire experimental station is 3.3 ± 0.6 ps rms.

  11. Steady state and time resolved fluorescence studies of azadioxatriangulenium (ADOTA) fluorophore in silica and PVA thin films

    DEFF Research Database (Denmark)

    Chib, Rahul; Raut, Sangram; Shah, Sunil

    2015-01-01

    in silica thin films and PVA films were studied by means of steady-state and time resolved fluorescence techniques. We have found that the azadioxatriangulenium entrapped in silica thin film has a wider fluorescence lifetime distribution (Lorentzian distribution), lower fluorescence efficiencies, shorter....... In contrast to the PVA matrices, the porous silica films allow restricted rotations of Azadioxatriangulenium molecules, which result in faster and complex fluorescence anisotropy decays suggesting energy migration among dye molecules....

  12. Time-resolved fluorescence quenching studies of sodium lauryl ether sulfate micelles

    Energy Technology Data Exchange (ETDEWEB)

    Friedrich, Leidi C.; Silva, Volnir O.; Quina, Frank H., E-mail: quina@usp.br [Universidade de Sao Paulo (USP), Sao Paulo, SP (Brazil). Instituto de Quimica; Moreira Junior, Paulo F. [Universidade de Sao Paulo (USP), Sao Paulo, SP (Brazil). Escola Politecnica. Departamento de Engenharia Quimica; Tcacenco, Celize M. [Fundacao Instituto de Ensino para Osasco (FIEO/UNIFIEO), SP (Brazil). Centro Universitario FIEO. Centro de Estudos Quimicos

    2013-02-15

    Aggregation numbers (N{sub Ag}) of micelles of the commercial anionic detergent sodium lauryl ether sulfate (SLES), with an average of two ethylene oxide subunits, were determined at 30 and 40 deg C by the time-resolved fluorescence quenching method with pyrene as the fluorescent probe and the N-hexadecylpyridinium ion as the quencher. The added-salt dependent growth of SLES micelles ({gamma} = 0.11-0.15, where {gamma} is the slope of a plot of log aggregation number vs. log [Y{sub aq}] and [Y{sub aq}] is the sodium counterion concentration free in the intermicellar aqueous phase) is found to be significantly lower than that of sodium alkyl sulfate micelles ({gamma} ca. 0.25), a difference attributed to the larger headgroup size of SLES. The I{sub 1}/I{sub 3} vibronic intensity ratio and the rate constant for intramicellar quenching of pyrene show that the pyrene solubilization microenvironment and the intramicellar microviscosity are insensitive to micelle size or the presence of added salt. (author)

  13. Time-resolved fluorescence quenching studies of sodium lauryl ether sulfate micelles

    Energy Technology Data Exchange (ETDEWEB)

    Friedrich, Leidi C.; Silva, Volnir O.; Quina, Frank H., E-mail: quina@usp.br [Universidade de Sao Paulo (USP), Sao Paulo, SP (Brazil). Instituto de Quimica; Moreira Junior, Paulo F. [Universidade de Sao Paulo (USP), Sao Paulo, SP (Brazil). Escola Politecnica. Departamento de Engenharia Quimica; Tcacenco, Celize M. [Fundacao Instituto de Ensino para Osasco (FIEO/UNIFIEO), SP (Brazil). Centro Universitario FIEO. Centro de Estudos Quimicos

    2013-02-15

    Aggregation numbers (N{sub Ag}) of micelles of the commercial anionic detergent sodium lauryl ether sulfate (SLES), with an average of two ethylene oxide subunits, were determined at 30 and 40 deg C by the time-resolved fluorescence quenching method with pyrene as the fluorescent probe and the N-hexadecylpyridinium ion as the quencher. The added-salt dependent growth of SLES micelles ({gamma} = 0.11-0.15, where {gamma} is the slope of a plot of log aggregation number vs. log [Y{sub aq}] and [Y{sub aq}] is the sodium counterion concentration free in the intermicellar aqueous phase) is found to be significantly lower than that of sodium alkyl sulfate micelles ({gamma} ca. 0.25), a difference attributed to the larger headgroup size of SLES. The I{sub 1}/I{sub 3} vibronic intensity ratio and the rate constant for intramicellar quenching of pyrene show that the pyrene solubilization microenvironment and the intramicellar microviscosity are insensitive to micelle size or the presence of added salt. (author)

  14. Solvent sorting in (mixed solvent + electrolyte) systems: Time-resolved fluorescence measurements and theory

    Indian Academy of Sciences (India)

    Harun Al Rasidgazi; Hemant K Kashyap; Ranjit Biswas

    2015-01-01

    In this manuscriptwe explore electrolyte-induced modification of preferential solvation of a dipolar solute dissolved in a binary mixture of polar solvents. Composition dependence of solvation characteristics at a fixed electrolyte concentration has been followed. Binary mixtures of two different polarities have been employed to understand the competition between solute-ion and solute-solvent interactions. Time-resolved fluorescence Stokes shift and anisotropy have been measured for coumarin 153 (C153) in moderately polar (ethyl acetate + 1-propanol) and strongly polar (acetonitrile + propylene carbonate) binary mixtures at various mixture compositions, and in the corresponding 1.0M solutions of LiClO4. Both the mixtures show red shifts in C153 absorption and fluorescence emission upon increase of mole fraction of the less polar solvent component in presence of the electrolyte. In addition, measured average solvation times become slower and rotation times faster for the above change in the mixture composition. A semi-molecular theory based on solution density fluctuations has been developed and found to successfully capture the essential features of the measured Stokes shift dynamics of these complex multi-component mixtures. Dynamic anisotropy results have been analyzed by using both Stokes-Einstein-Debye (SED) and Dote-Kivelson-Schwartz (DKS) theories. The importance of local solvent structure around the dissolved solute has been stressed.

  15. Observation of Ultrafast Bond-length Expansion at the Initial Stage of Laser Ablation by Picosecond Time-resolved EXAFS

    Science.gov (United States)

    Oguri, Katsuya; Okano, Yasuaki; Nishikawa, Tadashi; Nakano, Hidetoshi

    We have demonstrated a time-resolved extended X-ray absorption fine structure (EXAFS) technique by using a femtosecond laser produced plasma soft X-ray source. By applying this technique to the measurement of the initial stage of the laser ablation in Si foil, we were able to observe a slight shortening of the EXAFS oscillation period. This result suggests that the Si-Si atomic bond length expands as a result of the solid-liquid phase transition in Si. The realization of this technique is the first step toward understanding atomic structural dynamics during a chemical reaction.

  16. 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.

  17. Picosecond time-resolved laser pump/X-ray probe experiments using a gated single-photon-counting area detector

    DEFF Research Database (Denmark)

    Ejdrup, T.; Lemke, H.T.; Haldrup, Martin Kristoffer

    2009-01-01

    . The capability of the gated PILATUS detector to selectively detect the signal from a given X-ray pulse in 24 bunch mode at the APS storage ring is demonstrated. A test experiment performed on polycrystalline organic thin films of [alpha]-perylene illustrates the possibility of reaching an X-ray pulse duration......The recent developments in X-ray detectors have opened new possibilities in the area of time-resolved pump/probe X-ray experiments; this article presents the novel use of a PILATUS detector to achieve X-ray pulse duration limited time-resolution at the Advanced Photon Source (APS), USA...... limited time-resolution of 60 ps using the gated PILATUS detector. This is the first demonstration of X-ray pulse duration limited data recorded using an area detector without the use of a mechanical chopper array at the beamline....

  18. Investigation of Prolactin Receptor Activation and Blockade Using Time-Resolved Fluorescence Resonance Energy Transfer

    Directory of Open Access Journals (Sweden)

    Estelle eTallet

    2011-09-01

    Full Text Available The prolactin receptor (PRLR is emerging as a therapeutic target in oncology. Knowledge-based drug design led to the development of a pure PRLR antagonist (Del1-9-G129R-hPRL that was recently shown to prevent PRL-induced mouse prostate tumorogenesis. In humans, the first gain-of-function mutation of the PRLR (PRLRI146L was recently identified in breast tumor patients. At the molecular level, the actual mechanism of action of these two novel players in the PRL system remains elusive. In this study, we addressed whether constitutive PRLR activation (PRLRI146L or PRLR blockade (antagonist involved alteration of receptor oligomerization and/or of inter-chain distances compared to unstimulated and PRL-stimulated PRLR. Using a combination of various biochemical and spectroscopic approaches (co-IP, blue-native electrophoresis, BRET1, we demonstrated that preformed PRLR homodimers are altered neither by PRL- or I146L-induced receptor triggering, nor by antagonist-mediated blockade. These findings were confirmed using a novel time-resolved fluorescence resonance energy transfer (TR-FRET technology that allows monitoring distance changes between cell-surface tagged receptors. This technology revealed that PRLR blockade or activation did not involve detectable distance changes between extracellular domains of receptor chains within the dimer. This study merges with our previous structural investigations suggesting that the mechanism of PRLR activation solely involves intermolecular contact adaptations leading to subtle intramolecular rearrangements.

  19. Rapid homogenous time-resolved fluorescence (HTRF) immunoassay for anthrax detection.

    Science.gov (United States)

    Cohen, Noam; Mechaly, Adva; Mazor, Ohad; Fisher, Morly; Zahavy, Eran

    2014-05-01

    Infection with Bacillus anthracsis spores induces an acute anthrax disease that can cause casualties and death in untreated cases. Thus rapid diagnosis of anthrax at early stage of the disease is essential to allow an effective treatment. Here we present the development of rapid and sensitive homogenous time-resolved fluorescence (HTRF) immunoassays based on the energy transfer process of europium cryptate (EuK) donor to AlexaFluor647 acceptor. The energy transfer process is limited to d bacteremia in infected hosts, using two monoclonal anti-PA antibodies that specifically recognize two different epitopes on the PA molecule. The assay was sensitive enabling detection of 2 ng/ml PA in the serum of B. anthracsis-infected rabbits in only 15 min assay. Additionally, HTRF assay was developed for the detection of bacterial spores using polyclonal anti-spore antibodies that recognize many epitopes on the bacterial surface. The assay enabled the detection of 2 × 10(6) spores/ml in 30 min assay and was specific, showing no cross reactivity with closely related non-virulent bacillus cereus strain. This study describes the use of the HTRF assay for the detection of both singled-epitope (proteins) and multi-epitope (particles) as rapid, simple and sensitive method that can be used at the time that fast results are needed to allow an effective medical care.

  20. A chloride ion nanosensor for time-resolved fluorimetry and fluorescence lifetime imaging.

    Science.gov (United States)

    Ruedas-Rama, Maria J; Orte, Angel; Hall, Elizabeth A H; Alvarez-Pez, Jose M; Talavera, Eva M

    2012-03-21

    In this work, the first CdSe/ZnS quantum dot (QD) photoluminescence lifetime based chloride ion nanosensor is reported. The acridinium dication lucigenin was self-assembled on the surface of negatively charged mercaptopropionic acid capped QDs to achieve QD-lucigenin conjugates. Upon attachment, a drastic decrease of the photoluminescence lifetime of both QD nanoparticles and lucigenin is observed by virtue of a charge transfer mechanism. Since lucigenin is a chloride-sensitive indicator dye, the photoluminescence decay of QD-lucigenin conjugates changes by adding chloride ion. The photoluminescence lifetime of the QDs in the conjugate increases after reacting with Cl(-), but also shows a concomitant decrease in the lucigenin lifetime immobilized on the surface. The photoluminescence lifetime of QD-lucigenin nanosensors shows a linear response in the Cl(-) concentration range between 0.5 and 50 mM. Moreover, the ratio τ(ave)(QD)/τ(ave)(luc) can be used as an analytical signal since the lifetime ratio presents a linear response in the same Cl(-) concentration range. The system also shows good selectivity towards most of the main anions and molecules that can be found in biological fluids. These nanosensors have been satisfactorily applied for Cl(-) determination in simulated intracellular media with high sensitivity and high selectivity. Finally, we demonstrate the potential application of the proposed nanosensor in confocal fluorescence lifetime imaging (FLIM). These results show the promising application of the QD-lucigenin nanosensors in FLIM, particularly for intracellular sensing, with the invaluable advantages of the time-resolved fluorescence techniques.

  1. Assessment of lifetime resolution limits in time-resolved photoacoustic calorimetry vs. transducer frequencies: setting the stage for picosecond resolution.

    Science.gov (United States)

    Schaberle, Fábio A; Rego Filho, Francisco de Assis M G; Reis, Luís A; Arnaut, Luis G

    2016-02-01

    Time-resolved photoacoustic calorimetry (PAC) gives access to lifetimes and energy fractions of reaction intermediates by deconvolution of the photoacoustic wave of a sample (E-wave) with that of the instrumental response (T-wave). The ability to discriminate between short lifetimes increases with transducer frequencies employed to detect the PAC waves. We investigate the lifetime resolution limits of PAC as a function of the transducer frequencies using the instrumental response obtained with the photoacoustic reference 2-hydroxybenzophenone in toluene or acetonitrile. The instrumental response was obtained for a set of transducers with central frequencies ranging from 0.5 MHz up to 225 MHz. The simulated dependence of the lifetime resolution with the transducer frequencies was anchored on experimental data obtained for the singlet state of naphthalene with a 2.25 MHz transducer. The shortest lifetime resolved with the 2.25 MHz transducer was 19 ns and our modelling of the transducer responses indicates that sub-nanosecond lifetimes of photoacoustic transients can be resolved with transducers of central frequencies above 100 MHz.

  2. Steady-State and Time-Resolved Studies into the Origin of the Intrinsic Fluorescence of G-Quadruplexes.

    Science.gov (United States)

    Sherlock, Madeline E; Rumble, Christopher A; Kwok, Chun Kit; Breffke, Jens; Maroncelli, Mark; Bevilacqua, Philip C

    2016-06-16

    Stretches of guanines in DNA and RNA can fold into guanine quadruplex structures (GQSs). These structures protect telomeres in DNA and regulate gene expression in RNA. GQSs have an intrinsic fluorescence that is sensitive to different parameters, including loop sequence and length. However, the dependence of GQS fluorescence on solution and sequence parameters and the origin of this fluorescence are poorly understood. Herein we examine effects of dangling nucleotides and cosolute conditions on GQS fluorescence using both steady-state and time-resolved fluorescence spectroscopy. The quantum yield of dGGGTGGGTGGGTGGG, termed "dG3T", is found to be modest at ∼2 × 10(-3). Nevertheless, dG3T and its variants are significantly brighter than the common nucleic acid fluorophore 2-aminopurine (2AP) largely due to their sizable extinction coefficients. Dangling 5'-end nucleotides generally reduce emission and blue-shift the resultant spectrum, whereas dangling 3'-end nucleotides slightly enhance fluorescence, particularly on the red side of the emission band. Time-resolved fluorescence decays are broadly distributed in time and require three exponential components for accurate fits. Time-resolved emission spectra suggest the presence of two emitting populations centered at ∼330 and ∼390 nm, with the redder component being a well-defined long-lived (∼1 ns) entity. Insights into GQS fluorescence obtained here should be useful in designing brighter intrinsic RNA and DNA quadruplexes for use in label-free biotechnological applications.

  3. 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

  4. Time-Resolved Fluorescent Immunochromatography of Aflatoxin B1 in Soybean Sauce: A Rapid and Sensitive Quantitative Analysis

    Science.gov (United States)

    Wang, Du; Zhang, Zhaowei; Li, Peiwu; Zhang, Qi; Zhang, Wen

    2016-01-01

    Rapid and quantitative sensing of aflatoxin B1 with high sensitivity and specificity has drawn increased attention of studies investigating soybean sauce. A sensitive and rapid quantitative immunochromatographic sensing method was developed for the detection of aflatoxin B1 based on time-resolved fluorescence. It combines the advantages of time-resolved fluorescent sensing and immunochromatography. The dynamic range of a competitive and portable immunoassay was 0.3–10.0 µg·kg−1, with a limit of detection (LOD) of 0.1 µg·kg−1 and recoveries of 87.2%–114.3%, within 10 min. The results showed good correlation (R2 > 0.99) between time-resolved fluorescent immunochromatographic strip test and high performance liquid chromatography (HPLC). Soybean sauce samples analyzed using time-resolved fluorescent immunochromatographic strip test revealed that 64.2% of samples contained aflatoxin B1 at levels ranging from 0.31 to 12.5 µg·kg−1. The strip test is a rapid, sensitive, quantitative, and cost-effective on-site screening technique in food safety analysis. PMID:27428975

  5. Dynamics and flexibility of human aromatase probed by FTIR and time resolved fluorescence spectroscopy.

    Directory of Open Access Journals (Sweden)

    Giovanna Di Nardo

    Full Text Available Human aromatase (CYP19A1 is a steroidogenic cytochrome P450 converting androgens into estrogens. No ligand-free crystal structure of the enzyme is available to date. The crystal structure in complex with the substrate androstenedione and the steroidal inhibitor exemestane shows a very compact conformation of the enzyme, leaving unanswered questions on the conformational changes that must occur to allow access of the ligand to the active site. As H/D exchange kinetics followed by FTIR spectroscopy can provide information on the conformational changes in proteins where solvent accessibility is affected, here the amide I region was used to measure the exchange rates of the different elements of the secondary structure for aromatase in the ligand-free form and in the presence of the substrate androstenedione and the inhibitor anastrozole. Biphasic exponential functions were found to fit the H/D exchange data collected as a function of time. Two exchange rates were assigned to two populations of protons present in different flexible regions of the protein. The addition of the substrate androstenedione and the inhibitor anastrozole lowers the H/D exchange rates of the α-helices of the enzyme when compared to the ligand-free form. Furthermore, the presence of the inhibitor anastrozole lowers exchange rate constant (k1 for β-sheets from 0.22±0.06 min(-1 for the inhibitor-bound enzyme to 0.12±0.02 min(-1 for the free protein. Dynamics effects localised in helix F were studied by time resolved fluorescence. The data demonstrate that the fluorescence lifetime component associated to Trp224 emission undergoes a shift toward longer lifetimes (from ≈5.0 to ≈5.5 ns when the substrate or the inhibitor are present, suggesting slower dynamics in the presence of ligands. Together the results are consistent with different degrees of flexibility of the access channel and therefore different conformations adopted by the enzyme in the free, substrate- and

  6. Dynamics and flexibility of human aromatase probed by FTIR and time resolved fluorescence spectroscopy.

    Science.gov (United States)

    Di Nardo, Giovanna; Breitner, Maximilian; Sadeghi, Sheila J; Castrignanò, Silvia; Mei, Giampiero; Di Venere, Almerinda; Nicolai, Eleonora; Allegra, Paola; Gilardi, Gianfranco

    2013-01-01

    Human aromatase (CYP19A1) is a steroidogenic cytochrome P450 converting androgens into estrogens. No ligand-free crystal structure of the enzyme is available to date. The crystal structure in complex with the substrate androstenedione and the steroidal inhibitor exemestane shows a very compact conformation of the enzyme, leaving unanswered questions on the conformational changes that must occur to allow access of the ligand to the active site. As H/D exchange kinetics followed by FTIR spectroscopy can provide information on the conformational changes in proteins where solvent accessibility is affected, here the amide I region was used to measure the exchange rates of the different elements of the secondary structure for aromatase in the ligand-free form and in the presence of the substrate androstenedione and the inhibitor anastrozole. Biphasic exponential functions were found to fit the H/D exchange data collected as a function of time. Two exchange rates were assigned to two populations of protons present in different flexible regions of the protein. The addition of the substrate androstenedione and the inhibitor anastrozole lowers the H/D exchange rates of the α-helices of the enzyme when compared to the ligand-free form. Furthermore, the presence of the inhibitor anastrozole lowers exchange rate constant (k1) for β-sheets from 0.22±0.06 min(-1) for the inhibitor-bound enzyme to 0.12±0.02 min(-1) for the free protein. Dynamics effects localised in helix F were studied by time resolved fluorescence. The data demonstrate that the fluorescence lifetime component associated to Trp224 emission undergoes a shift toward longer lifetimes (from ≈5.0 to ≈5.5 ns) when the substrate or the inhibitor are present, suggesting slower dynamics in the presence of ligands. Together the results are consistent with different degrees of flexibility of the access channel and therefore different conformations adopted by the enzyme in the free, substrate- and inhibitor

  7. Hyperspectral time-resolved wide-field fluorescence molecular tomography based on structured light and single-pixel detection.

    Science.gov (United States)

    Pian, Qi; Yao, Ruoyang; Zhao, Lingling; Intes, Xavier

    2015-02-01

    We present a time-resolved fluorescence diffuse optical tomography platform that is based on wide-field structured illumination, single-pixel detection, and hyperspectral acquisition. Two spatial light modulators (digital micro-mirror devices) are employed to generate independently wide-field illumination and detection patterns, coupled with a 16-channel spectrophotometer detection module to capture hyperspectral time-resolved tomographic data sets. The main system characteristics are reported, and we demonstrate the feasibility of acquiring dense 4D tomographic data sets (space, time, spectra) for time domain 3D quantitative multiplexed fluorophore concentration mapping in turbid media.

  8. 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.

  9. Metal-like heat conduction in laser-excited InSb probed by picosecond time-resolved x-ray diffraction

    Science.gov (United States)

    Sondhauss, P.; Synnergren, O.; Hansen, T. N.; Canton, S. E.; Enquist, H.; Srivastava, A.; Larsson, J.

    2008-09-01

    A semiconductor (InSb) showed transient metal-like heat conduction after excitation of a dense electron-hole plasma via short and intense light pulses. A related ultrafast strain relaxation was detected using picosecond time-resolved x-ray diffraction. The deduced heat conduction was, by a factor of 30, larger than the lattice contribution. The anomalously high heat conduction can be explained once the contribution from the degenerate photocarrier plasma is taken into account. The magnitude of the effect could provide the means for guiding heat in semiconductor nanostructures. In the course of this work, a quantitative model for the carrier dynamics in laser-irradiated semiconductors has been developed, which does not rely on any adjustable parameters or ad hoc assumptions. The model includes various light absorption processes (interband, free carrier, two photon, and dynamical Burstein-Moss shifts), ambipolar diffusion, energy transport (heat and chemical potential), electrothermal effects, Auger recombination, collisional excitation, and scattering (elastic and inelastic). The model accounts for arbitrary degrees of degeneracy.

  10. 340 nm pulsed UV LED system for europium-based time-resolved fluorescence detection of immunoassays

    DEFF Research Database (Denmark)

    Rodenko, Olga; Fodgaard, Henrik; Tidemand-Lichtenberg, Peter

    2016-01-01

    We report on the design, development and investigation of an optical system based on UV light emitting diode (LED) excitation at 340 nm for time-resolved fluorescence detection of immunoassays. The system was tested to measure cardiac marker Troponin I with a concentration of 200 ng/L in immunoas......We report on the design, development and investigation of an optical system based on UV light emitting diode (LED) excitation at 340 nm for time-resolved fluorescence detection of immunoassays. The system was tested to measure cardiac marker Troponin I with a concentration of 200 ng....../L in immunoassay. The signal-to-noise ratio was comparable to state-of-the-art Xenon flash lamp based unit with equal excitation energy and without overdriving the LED. We performed a comparative study of the flash lamp and the LED based system and discussed temporal, spatial, and spectral features of the LED...

  11. Energy transfer in Anabaena variabilis filaments adapted to nitrogen-depleted and nitrogen-enriched conditions studied by time-resolved fluorescence.

    Science.gov (United States)

    Onishi, Aya; Aikawa, Shimpei; Kondo, Akihiko; Akimoto, Seiji

    2017-02-16

    Nitrogen is among the most important nutritious elements for photosynthetic organisms such as plants, algae, and cyanobacteria. Therefore, nitrogen depletion severely compromises the growth, development, and photosynthesis of these organisms. To preserve their integrity under nitrogen-depleted conditions, filamentous nitrogen-fixing cyanobacteria reduce atmospheric nitrogen to ammonia, and self-adapt by regulating their light-harvesting and excitation energy-transfer processes. To investigate the changes in the primary processes of photosynthesis, we measured the steady-state absorption and fluorescence spectra and time-resolved fluorescence spectra (TRFS) of whole filaments of the nitrogen-fixing cyanobacterium Anabaena variabilis at 77 K. The filaments were grown in standard and nitrogen-free media for 6 months. The TRFS were measured with a picosecond time-correlated single photon counting system. Despite the phycobilisome degradation, the energy-transfer paths within phycobilisome and from phycobilisome to both photosystems were maintained. However, the energy transfer from photosystem II to photosystem I was suppressed and a specific red chlorophyll band appeared under the nitrogen-depleted condition.

  12. Computational modeling of time-resolved fluorescence transport in turbid media for non-invasive clinical diagnostics

    Science.gov (United States)

    Vishwanath, Karthik

    Fluorescence spectroscopy and imaging methods, including fluorescence lifetime sensing, are being developed for a variety of non-invasive clinical diagnostic procedures, including applications to early cancer diagnosis. Here, both the theoretical developments and experimental validations of a versatile, numerical Monte Carlo code that models photon migration in turbid media to include simulations of time-resolved fluorescence transport are presented. The developed numerical model was used to study, for the first time, the dependence of time-resolved fluorescence signals emanating from turbid media on the optical transport coefficients, fluorophore properties and source-detector configurations in single-layered turbid media as well as more complex multi-layered turbid media. The numerical codes presented here can be adapted to model a wide range of experimental techniques measuring the optical responses of biological tissues to laser irradiation and are demonstrated here for two specific applications (a) to model time-resolved fluorescence dynamics in human colon tissues and (b) to extract the frequency-dependent optical responses of a model adult human head to an incident laser-source whose intensity was harmonically modulated i.e. simulating frequency-domain measurements. Specifically, measurements of time-resolved fluorescence decays from a previous clinical study aimed toward detecting differences in tissue pathologies in patients undergoing gastro-intestinal endoscopy were simulated using the Monte Carlo model and results demonstrated that variations in tissue optical transport coefficients (absorption and scattering) alone could not account for the fluorescence decay differences detected between tissue pathologies in vivo. However, variations in fluorescence decay time as large as those detected clinically between normal and pre-malignant tissues (of 2 ns) could be accounted for by simulated variations in tissue morphology or biochemistry while intrinsic

  13. Persistent luminescence nanoprobe for biosensing and lifetime imaging of cell apoptosis via time-resolved fluorescence resonance energy transfer.

    Science.gov (United States)

    Zhang, Lei; Lei, Jianping; Liu, Jintong; Ma, Fengjiao; Ju, Huangxian

    2015-10-01

    Time-resolved fluorescence technique can reduce the short-lived background luminescence and auto-fluorescence interference from cells and tissues by exerting the delay time between pulsed excitation light and signal acquisition. Here, we prepared persistent luminescence nanoparticles (PLNPs) to design a universal time-resolved fluorescence resonance energy transfer (TR-FRET) platform for biosensing, lifetime imaging of cell apoptosis and in situ lifetime quantification of intracellular caspase-3. Three kinds of PLNPs-based nanoprobes are assembled by covalently binding dye-labeled peptides or DNA to carboxyl-functionalized PLNPs for the efficient detection of caspase-3, microRNA and protein. The peptides-functionalized nanoprobe is also employed for fluorescence lifetime imaging to monitor cell apoptosis, which shows a dependence of cellular fluorescence lifetime on caspase-3 activity and thus leads to an in situ quantification method. This work provides a proof-of-concept for PLNPs-based TR-FRET analysis and demonstrates its potential in exploring dynamical information of life process. Copyright © 2015 Elsevier Ltd. All rights reserved.

  14. Photoionization-induced π↔ H site switching dynamics in phenol(+)-Rg (Rg = Ar, Kr) dimers probed by picosecond time-resolved infrared spectroscopy.

    Science.gov (United States)

    Miyazaki, Mitsuhiko; Sakata, Yuri; Schütz, Markus; Dopfer, Otto; Fujii, Masaaki

    2016-09-21

    The ionization-induced π↔ H site switching reaction in phenol(+)-Rg (PhOH(+)-Rg) dimers with Rg = Ar and Kr is traced in real time by picosecond time-resolved infrared (ps-TRIR) spectroscopy. The ps-TRIR spectra show the prompt appearance of the non-vanishing free OH stretching band upon resonant photoionization of the π-bound neutral clusters, and the delayed appearance of the hydrogen-bonded (H-bonded) OH stretching band. This result directly proves that the Rg ligand switches from the π-bound site on the aromatic ring to the H-bonded site at the OH group by ionization. The subsequent H →π back reaction converges the dimer to a π↔ H equilibrium. This result is in sharp contrast to the single-step π→ H forward reaction in the PhOH(+)-Ar2 trimer with 100% yield. The reaction mechanism and yield strongly depend on intracluster vibrational energy redistribution. A classical rate equation analysis for the time evolutions of the band intensities of the two vibrations results in similar estimates for the time constants of the π→ H forward reaction of τ+ = 122 and 73 ps and the H →π back reaction of τ- = 155 and 188 ps for PhOH(+)-Ar and PhOH(+)-Kr, respectively. The one order of magnitude slower time constant in comparison to the PhOH(+)-Ar2 trimer (τ+ = 7 ps) is attributed to the decrease in density of states due to the absence of the second Ar in the dimer. The similar time constants for both PhOH(+)-Rg dimers are well rationalized by a classical interpretation based on the comparable potential energy surfaces, reaction pathways, and density of states arising from their similar intermolecular vibrational frequencies.

  15. 340 nm pulsed UV LED system for europium-based time-resolved fluorescence detection of immunoassays.

    Science.gov (United States)

    Rodenko, Olga; Fodgaard, Henrik; Tidemand-Lichtenberg, Peter; Petersen, Paul Michael; Pedersen, Christian

    2016-09-19

    We report on the design, development and investigation of an optical system based on UV light emitting diode (LED) excitation at 340 nm for time-resolved fluorescence detection of immunoassays. The system was tested to measure cardiac marker Troponin I with a concentration of 200 ng/L in immunoassay. The signal-to-noise ratio was comparable to state-of-the-art Xenon flash lamp based unit with equal excitation energy and without overdriving the LED. We performed a comparative study of the flash lamp and the LED based system and discussed temporal, spatial, and spectral features of the LED excitation for time-resolved fluorimetry. Optimization of the suggested key parameters of the LED promises significant increase of the signal-to-noise ratio and hence of the sensitivity of immunoassay systems.

  16. Ns-scale time-resolved laser induced fluorescence imaging for detection of fecal contamination on apples

    Science.gov (United States)

    Kim, Moon S.; Lefcourt, Alan M.; Chen, Yud-Ren

    2004-11-01

    Our laboratory has been utilizing fluorescence techniques as a potential means for detection of quality and wholesomeness of food products. A system with a short pulse light source such as a laser coupled with a gated detector can be used to harvest fluorescence in ambient light conditions from biological samples with relatively low fluorescence yields. We present a versatile multispectral laser-induced fluorescence (LIF) imaging system capable of ns-scale time resolved fluorescence. The system is equipped with a tunable pulse laser system that emits in the visible range from 410 nm to 690 nm. Ns-scale, time-dependent multispectral fluorescence emissions of apples contaminated with a range of diluted cow feces were acquired. Four spectral bands, F670, F680, F685 and F730, centered near the emission peak wavelengths of the major constituents responsible for the red fluorescence emissions from apples artificially contaminated with cow feces were examined to determine a suitable single red fluorescence band and optimal ns-gate window for detection of fecal contamination on apples. The results based on the ns decay curves showed that 670 nm with 10 nm full width at half maximum (FWHM) at a gate-delay of 4 ns from the laser excitation peak provided the greatest differences in time-dependent fluorescence responses between feces contaminated spots and apples surfaces.

  17. Time-resolved fluorescence spectra of cis-stilbene in hexane and acetonitrile

    Science.gov (United States)

    Sajadi, M.; Dobryakov, A. L.; Garbin, E.; Ernsting, N. P.; Kovalenko, S. A.

    2010-04-01

    Transient fluorescence spectra from cis-stilbene in solution are recorded with 0.24 ps instrument response by a Kerr-Shutter upon excitation at 283 and 267 nm. The fluorescence decay shows no dependence on the excitation wavelength and proceeds monoexponentially with 0.21 ps in acetonitrile and 0.75 ps in hexane. No spectral shift or distortion of the fluorescence band is observed during the decay. Fluorescence contribution from 4a,4b-dihydrophenanthrene (DHP), produced in a competing reaction channel, was not detectable. From comparison with trans-fluorescence, the emission oscillator strength of cis-stilbene is determined to be 0.19 in hexane and 0.21 in acetonitrile.

  18. Cellular uptake of modified oligonucleotides enhanced by porphyrins studied by time-resolved microspectrofluorimetry and fluorescence imaging techniques

    Science.gov (United States)

    Praus, P.; Kočišová, E.; Mojzeš, P.; Štěpánek, J.; Turpin, P.-Y.; Sureau, F.

    2011-05-01

    Fluorescence microimaging and homodyne phase-resolved confocal microspectrofluorimetry were used to monitor the transport of antisense oligonucleotide into 3T3 living cells and its subsequent intracellular distribution. Phosphorothioate analog of 15-mer oligothymidylate labeled by ATTO 425 was complexed with 5,10,15,20-tetrakis (1-methyl-4-pyridyl) porphyrin (H 2TMPyP4) as an uptake-mediating agent. High frequency (up to 180 MHz) analog modulation of both exciting diode laser and the detector image intensifier gain was used to record time-resolved fluorescence spectra. Fluorescence lifetime data within a broad spectral range have revealed preservation of oligonucleotide/porphyrin complex integrity and binding properties of both components inside the cell.

  19. A homogeneous europium cryptate-based assay for the diagnosis of mutations by time-resolved fluorescence resonance energy transfer.

    Science.gov (United States)

    Lopez-Crapez, E; Bazin, H; Andre, E; Noletti, J; Grenier, J; Mathis, G

    2001-07-15

    Oligonucleotide ligation assay (OLA) is considered to be a very useful methodology for the detection and characterization of mutations, particularly for clinical purposes. The fluorescence resonance energy transfer between a fluorescent donor and a suitable fluorophore as acceptor has been applied in the past to several scientific fields. This technique is well adapted to nucleic acid analysis such as DNA sequencing, DNA hybridization and polymerase chain reaction. We describe here a homogeneous format based on the use of a rare earth cryptate label as donor: tris-bipyridine-Eu(3+). The long-lived fluorescence of this label makes it possible to reach a high sensitivity by using a time-resolved detection mode. A non-radiative energy transfer technology, known as time-resolved amplification of cryptate emission (TRACE((R))) characterized by a temporal and spectral selectivity has been developed. The TRACE((R)) detection of characterized single nucleotide polymorphism using the OLA for allelic discrimination is proposed. We demonstrate the potentialities of this OLA-TRACE((R)) methodology through the analysis of K-ras oncogene point mutations.

  20. Strongly nonexponential time-resolved fluorescence of quantum-dot ensembles in three-dimensional photonic crystals

    DEFF Research Database (Denmark)

    Nikolaev, Ivan S.; Lodahl, Peter; van Driel, A. Floris

    2007-01-01

    We observe experimentally that ensembles of quantum dots in three-dimensional 3D photonic crystals reveal strongly nonexponential time-resolved emission. These complex emission decay curves are analyzed with a continuous distribution of decay rates. The log-normal distribution describes the decays...... parameter. This interpretation qualitatively agrees with the calculations of the 3D projected local density of states. We therefore conclude that fluorescence decay of ensembles of quantum dots is highly nonexponential to an extent that is controlled by photonic crystals....

  1. 340 nm pulsed UV LED system for europium-based time-resolved fluorescence detection of immunoassays

    DEFF Research Database (Denmark)

    Rodenko, Olga; Fodgaard, Henrik; Tidemand-Lichtenberg, Peter

    2016-01-01

    We report on the design, development and investigation of an optical system based on UV light emitting diode (LED) excitation at 340 nm for time-resolved fluorescence detection of immunoassays. The system was tested to measure cardiac marker Troponin I with a concentration of 200 ng....../L in immunoassay. The signal-to-noise ratio was comparable to state-of-the-art Xenon flash lamp based unit with equal excitation energy and without overdriving the LED. We performed a comparative study of the flash lamp and the LED based system and discussed temporal, spatial, and spectral features of the LED...

  2. Time-resolved fluorescence study of electron transfer in a model peptide system

    Science.gov (United States)

    Donald, Fiona; Hungerford, Graham; Moore, Barry D.; Birch, David J. S.

    1994-08-01

    At present there is a great deal of interest in the study of the transference of energy in biological systems. For example, electron transfer is of major importance in many synthetic and biological processes and in nature is mediated by proteins. Information regarding this process is therefore useful in leading to a greater understanding of phenomena such as photosynthesis and respiration. Previous work on protein systems has shown the electron transfer process to be complex to analyze because of the presence of competing pathways. This has led to the use of model systems to simplify the kinetics. We have synthesized novel model systems using peptides containing both a fluorescent methoxy- naphthalene donor and a dicyanoethylene group as a potential electron acceptor and observed fluorescence quenching for both dipeptide and oligopeptide systems. Biexponential fluorescence decay behavior was observed for all donor acceptor systems, with an increase in the amount of the shorter fluorescence decay component on increasing temperature.

  3. Time-resolved fluorescence-based assay for rapid detection of Escherichia coli.

    Science.gov (United States)

    Kulpakko, Janne; Kopra, Kari; Hänninen, Pekka

    2015-02-01

    Fast and simple detection of pathogens is of utmost importance in health care and the food industry. In this article, a novel technology for the detection of pathogenic bacteria is presented. The technology uses lytic-specific bacteriophages and a nonspecific interaction of cellular components with a luminescent lanthanide chelate. As a proof of principle, Escherichia coli-specific T4 bacteriophage was used to infect the bacteria, and the cell lysis was detected. In the absence of E. coli, luminescent Eu(3+)-chelate complex cannot be formed and low time-resolved luminescence signal is monitored. In the presence of E. coli, increased luminescence signal is observed as the cellular contents are leached to the surrounding medium. The luminescence signal is observed as a function of the number of bacteria in the sample. The homogeneous assay can detect living E. coli in bacterial cultures and simulated urine samples within 25 min with a detection limit of 1000 or 10,000 bacterial cells/ml in buffer or urine, respectively. The detection limit is at the clinically relevant level, which indicates that the method could also be applicable to clinical settings for fast detection of urine bacteria.

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

    Science.gov (United States)

    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 optically initiated by pulsed (< 3 ps, 1.75 nJ) excitation. Although K-590 remains structurally unchanged throughout the 50-ps to 1-ns time interval, distinct structural changes do appear over the 1-ns to 260-ns period. Specifically, comparisons of the 50-ps PTR/CARS spectra with those recorded with time delays of 1 ns to 260 ns reveal 1) three types of changes in the hydrogen-out-of-plane (HOOP) region: the appearance of a strong, new feature at 984 cm-1; intensity decreases for the bands at 957 cm-1, 952 cm-1, and 939 cm-1; and small changes intensity and/or frequency of bands at 855 cm-1 and 805 cm-1; and 2) two types of changes in the C-C stretching region: the intensity increase in the band at 1196 cm-1 and small intensity changes and/or frequency shifts for bands at 1300 cm-1 and 1362 cm-1. No changes are observed in the C = C stretching region, and no bands assignable to the Schiff base stretching mode (C = NH+) mode are found in any of the PTR/CARS spectra assignable to K-590. These PTR/CARS data are used, together with vibrational mode assignments derived from previous work, to characterize the retinal structural changes in K-590 as it evolves from its 3.5-ps formation (ps/K-590) through the nanosecond time regime (ns/K-590) that precedes the formation of L-550. The PTR/CARS data suggest that changes in the torsional modes near the C14-C15 = N bonds are directly associated with the appearance of ns/K-590, and perhaps with the KL intermediate proposed in earlier studies. These

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

    Science.gov (United States)

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

    2016-12-01

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

  6. Direct Detection of Time-Resolved Rabi Oscillationsin a Single Quantum Dot via Resonance Fluorescence

    Science.gov (United States)

    2013-03-19

    Schaibley, A. Burgers, G. McCracken , D. Steel, A. Bracker, D. Gammon, and I. Sham 5d. PROJECT NUMBER QEST 5e. TASK NUMBER MI 5f. WORK UNIT...fluorescence J. R. Schaibley, A. P. Burgers, G. A. McCracken , and D. G. Steel* The H. M. Randall Laboratory of Physics, The University of Michigan, Ann Arbor

  7. Preparation and time-resolved fluorescence study of RGB organic crystals

    NARCIS (Netherlands)

    Fang, Hong-Hua; Lu, Shi-Yang; Wang, Lei; Ding, Ran; Wang, Hai-Yu; Feng, Jing; Chen, Qi-Dai; Sun, Hong-Bo; Fang, Honghua

    In this work, large-size tetracene- and pentacene-doped 1,4-Bis(4-methylstyryl)-benzene (BSB-Me) crystals were prepared with physical vapor transfer technique. The photoluminescence emission can be adjusted from blue to green and even to red by changing the doping. Their fluorescence features are

  8. Preparation and time-resolved fluorescence study of RGB organic crystals

    NARCIS (Netherlands)

    Fang, Hong-Hua; Lu, Shi-Yang; Wang, Lei; Ding, Ran; Wang, Hai-Yu; Feng, Jing; Chen, Qi-Dai; Sun, Hong-Bo; Fang, Honghua

    2013-01-01

    In this work, large-size tetracene- and pentacene-doped 1,4-Bis(4-methylstyryl)-benzene (BSB-Me) crystals were prepared with physical vapor transfer technique. The photoluminescence emission can be adjusted from blue to green and even to red by changing the doping. Their fluorescence features are in

  9. A dissociative fluorescence enhancement technique for one-step time-resolved immunoassays

    Energy Technology Data Exchange (ETDEWEB)

    Blomberg, Kaj R.; Mukkala, Veli-Matti; Hakala, Harri H.O.; Maekinen, Pauliina H.; Suonpaeae, Mikko U.; Hemmilae, Ilkka A. [PerkinElmer Inc, Wallac Oy, P.O. Box 10, Turku (Finland)

    2011-02-15

    The limitation of current dissociative fluorescence enhancement techniques is that the lanthanide chelate structures used as molecular probes are not stable enough in one-step assays with high concentrations of complexones or metal ions in the reaction mixture since these substances interfere with lanthanide chelate conjugated to the detector molecule. Lanthanide chelates of diethylenetriaminepentaacetic acid (DTPA) are extremely stable, and we used EuDTPA derivatives conjugated to antibodies as tracers in one-step immunoassays containing high concentrations of complexones or metal ions. Enhancement solutions based on different {beta}-diketones were developed and tested for their fluorescence-enhancing capability in immunoassays with EuDTPA-labelled antibodies. Characteristics tested were fluorescence intensity, analytical sensitivity, kinetics of complex formation and signal stability. Formation of fluorescent complexes is fast (5 min) in the presented enhancement solution with EuDTPA probes withstanding strong complexones (ethylenediaminetetra acetate (EDTA) up to 100 mM) or metal ions (up to 200 {mu}M) in the reaction mixture, the signal is intensive, stable for 4 h and the analytical sensitivity with Eu is 40 fmol/L, Tb 130 fmol/L, Sm 2.1 pmol/L and Dy 8.5 pmol/L. With the improved fluorescence enhancement technique, EDTA and citrate plasma samples as well as samples containing relatively high concentrations of metal ions can be analysed using a one-step immunoassay format also at elevated temperatures. It facilitates four-plexing, is based on one chelate structure for detector molecule labelling and is suitable for immunoassays due to the wide dynamic range and the analytical sensitivity. (orig.)

  10. Solvation dynamics of coumarin 153 embedded in AOT + phenol organogels studied by time-resolved fluorescence spectroscopy

    Science.gov (United States)

    Nishiyama, Katsura; Takata, Kei; Watanabe, Keiichi; Shigematsu, Hirotake

    2012-03-01

    We investigate solvation dynamics of organogel utilizing ps-ns fluorescence spectroscopy. The organogel studied in this Letter comprises bis(2-ethylhexyl) sulfosuccinate (AOT) and p-chlorophenol in the m-xylene solvent, that produce an organogel architecture with self-assembly. Within the organogel, an emitting probe, coumarin 153 (C153), is embedded. We then obtain dynamic response functions of solvation derived from the time-resolved fluorescence spectra of C153. We propose that total energy of the C153-organogel system relaxes with a relaxation time of 3.9 ns, whereas the entire rearrangement of the organogel structure around C153 is achieved with that of 6.1 ns, respectively.

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

    Science.gov (United States)

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

    2017-02-01

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

  12. 340nm UV LED excitation in time-resolved fluorescence system for europium-based immunoassays detection

    DEFF Research Database (Denmark)

    Rodenko, Olga; Fodgaard, Henrik; Tidemand-Lichtenberg, Peter

    2017-01-01

    In immunoassay analyzers for in-vitro diagnostics, Xenon flash lamps have been widely used as excitation light sources. Recent advancements in UV LED technology and its advantages over the flash lamps such as smaller footprint, better wall-plug efficiency, narrow emission spectrum...... by 39% compared to that of the Xenon flash lamp based unit, due to the LEDs narrower emission spectrum and longer pulse width. Key parameters of the LED system are discussed to further optimize the signal-to-noise ratio and signal-to-background, and hence the sensitivity of the instrument......, and no significant afterglow, have made them attractive light sources for gated detection systems. In this paper, we report on the implementation of a 340 nm UV LED based time-resolved fluorescence system based on europium chelate as a fluorescent marker. The system performance was tested with the immunoassay based...

  13. Short-pulsed diode lasers as an excitation source for time-resolved fluorescence applications and confocal laser scanning microscopy in PDT

    Science.gov (United States)

    Kress, Matthias; Meier, Thomas H.; El-Tayeb, Tarek A. A.; Kemkemer, Ralf; Steiner, Rudolf W.; Rueck, Angelika C.

    2001-11-01

    This article describes a setup for subcellular time-resolved fluorescence spectroscopy and fluorescence lifetime measurements using a confocal laser scanning microscope in combination with a short pulsed diode laser for fluorescence excitation and specimen illumination. The diode laser emits pulses at 398 nm wavelength with 70 ps full width at half maximum (FWHM) duration. The diode laser can be run at a pulse repetition rate of 40 MHz down to single shot mode. For time resolved spectroscopy a spectrometer setup consisting of an Czerny Turner spectrometer and a MCP-gated and -intensified CCD camera was used. Subcellular fluorescence lifetime measurements were achieved using a time-correlated single photon counting (TCSPC) module instead of the spectrometer setup. The capability of the short pulsed diode laser for fluorescence imaging, fluorescence lifetime measurements and time-resolved spectroscopy in combination with laser scanning microscopy is demonstrated by fluorescence analysis of several photosensitizers on a single cell level.

  14. Time resolved fluorescence anisotropy of basic dyes bound to poly(methacrylic acid in solution

    Directory of Open Access Journals (Sweden)

    Oliveira Hueder Paulo M. de

    2003-01-01

    Full Text Available Solutions of atactic poly(methacrylic acid, PMAA, with molecular weights in the range of (1.6 to 3.4 x 10(5 g mol-1, and labeled with the fluorescent dyes 9-aminoacridine or Nile blue were studied by photophysical measurements as a function of solvent viscosity and polarity. The conformational behavior of the PMAA chain segments around the fluorescent probe was reported by the change in the rotational diffusion of the dyes. Ethylene glycol swells the polymer chain compared with the more contracted conformation of PMAA in 50% water/ethylene glycol. The change in the rotational relaxation time of the dye bound to PMAA with the decrease of water content in the solvent mixture indicates a progressive expansion of polymer chain to a more open coil form in solution.

  15. A Theoretical Distinction Between Time-Resolved Resonance Raman andResonance Fluorescence

    Institute of Scientific and Technical Information of China (English)

    LU Jing; DU Si-De; FAN Kang-Nian; Lee Soo-Ying

    2000-01-01

    Based on the time-dependent theory, an analysis of the distinction between resonance Raman (RR) and resonance fluorescence (RF) with pulse excitation was presented. The real population of the intermediate state gives two optical components-the independent time evolution of intermediate ket and bra states generates RR while RF originates from the phase coherent between ket and bra states. In cw limit, the transition probability of spontaneous emission with pulse excitation can be reduced to the classical theory.

  16. A space- and time-resolved single photon counting detector for fluorescence microscopy and spectroscopy

    Science.gov (United States)

    Michalet, X.; Siegmund, O. H. W.; Vallerga, J. V.; Jelinsky, P.; Millaud, J. E.; Weiss, S.

    2006-02-01

    We have recently developed a wide-field photon-counting detector having high-temporal and high-spatial resolutions and capable of high-throughput (the H33D detector). Its design is based on a 25 mm diameter multi-alkali photocathode producing one photo electron per detected photon, which are then multiplied up to 10 7 times by a 3-microchannel plate stack. The resulting electron cloud is proximity focused on a cross delay line anode, which allows determining the incident photon position with high accuracy. The imaging and fluorescence lifetime measurement performances of the H33D detector installed on a standard epifluorescence microscope will be presented. We compare them to those of standard single-molecule detectors such as single-photon avalanche photodiode (SPAD) or electron-multiplying camera using model samples (fluorescent beads, quantum dots and live cells). Finally, we discuss the design and applications of future generation of H33D detectors for single-molecule imaging and high-throughput study of biomolecular interactions.

  17. Architecture of polyglutamine-containing fibrils from time-resolved fluorescence decay.

    Science.gov (United States)

    Röthlein, Christoph; Miettinen, Markus S; Borwankar, Tejas; Bürger, Jörg; Mielke, Thorsten; Kumke, Michael U; Ignatova, Zoya

    2014-09-26

    The disease risk and age of onset of Huntington disease (HD) and nine other repeat disorders strongly depend on the expansion of CAG repeats encoding consecutive polyglutamines (polyQ) in the corresponding disease protein. PolyQ length-dependent misfolding and aggregation are the hallmarks of CAG pathologies. Despite intense effort, the overall structure of these aggregates remains poorly understood. Here, we used sensitive time-dependent fluorescent decay measurements to assess the architecture of mature fibrils of huntingtin (Htt) exon 1 implicated in HD pathology. Varying the position of the fluorescent labels in the Htt monomer with expanded 51Q (Htt51Q) and using structural models of putative fibril structures, we generated distance distributions between donors and acceptors covering all possible distances between the monomers or monomer dimensions within the polyQ amyloid fibril. Using Monte Carlo simulations, we systematically scanned all possible monomer conformations that fit the experimentally measured decay times. Monomers with four-stranded 51Q stretches organized into five-layered β-sheets with alternating N termini of the monomers perpendicular to the fibril axis gave the best fit to our data. Alternatively, the core structure of the polyQ fibrils might also be a zipper layer with antiparallel four-stranded stretches as this structure showed the next best fit. All other remaining arrangements are clearly excluded by the data. Furthermore, the assessed dimensions of the polyQ stretch of each monomer provide structural evidence for the observed polyQ length threshold in HD pathology. Our approach can be used to validate the effect of pharmacological substances that inhibit or alter amyloid growth and structure.

  18. Photosynthetic membrane development studied using picosecond fluorescence kinetics

    Energy Technology Data Exchange (ETDEWEB)

    Karukstis, K.K.; Sauer, K.

    1983-01-01

    Using measurements of the kinetics of chlorophyll a fluorescence emission, the development of the photosynthetic membrane during etioplast-to-chloroplast differentiation was investigated. Tthe chlorophyll fluorescence decay kinetics of pea chloroplasts from plants grown under intermittent (2 min light-118 min dark) and continuous light regimes were monitored with a single-proton timing system with picosecond resolution. The changes in the fluorescence yields and decay kinetics were associated with known structural and organizational developmental phenomena in the chloroplast. This correlation provides a more detailed assignment of the origins of the fluorescence decay components than has been previously obtained by studying only mature chloroplasts. In particular, the analysis of the variable kinetics and multiexponential character of the fluorescence emission during thylakoid development focuses on the organization of photosynthetic units and the degree of communication between reaction centers in the same photosystem. These results further demonstrate that the age of etiolated tissue is critical to plastid development.

  19. Global and Time-Resolved Monitoring of Crop Photosynthesis with Chlorophyll Fluorescence

    Science.gov (United States)

    Guanter, Luis; Zhang, Yongguang; Jung, Martin; Joiner, Joanna; Voigt, Maximilian; Berry, Joseph A.; Frankenberg, Christian; Huete, Alfredo R.; Zarco-Tejada, Pablo; Lee, Jung-Eun; Moran, M. Susan; Ponce-Campos, Guillermo; Beer, Christian; Camps-Valls, Gustavo; Buchmann, Nina; Gianelle, Damiano; Klumpp, Katja; Cescatti, Alessandro; Baker, John M.; Griffis, Timothy J.

    2014-01-01

    Photosynthesis is the process by which plants harvest sunlight to produce sugars from carbon dioxide and water. It is the primary source of energy for all life on Earth; hence it is important to understand how this process responds to climate change and human impact. However, model-based estimates of gross primary production (GPP, output from photosynthesis) are highly uncertain, in particular over heavily managed agricultural areas. Recent advances in spectroscopy enable the space-based monitoring of sun-induced chlorophyll fluorescence (SIF) from terrestrial plants. Here we demonstrate that spaceborne SIF retrievals provide a direct measure of the GPP of cropland and grassland ecosystems. Such a strong link with crop photosynthesis is not evident for traditional remotely sensed vegetation indices, nor for more complex carbon cycle models. We use SIF observations to provide a global perspective on agricultural productivity. Our SIF-based crop GPP estimates are 50-75% higher than results from state-of-the-art carbon cycle models over, for example, the US Corn Belt and the Indo-Gangetic Plain, implying that current models severely underestimate the role of management. Our results indicate that SIF data can help us improve our global models for more accurate projections of agricultural productivity and climate impact on crop yields. Extension of our approach to other ecosystems, along with increased observational capabilities for SIF in the near future, holds the prospect of reducing uncertainties in the modeling of the current and future carbon cycle.

  20. Monoclonal antibody-based time-resolved fluorescence immunoassays for daidzein, genistein and equol in blood and urine

    DEFF Research Database (Denmark)

    Talbot, Duncan C.S.; Ogborne, Richard M.; Dadd, Tony

    2007-01-01

    isoflavones in reducing the risk of coronary heart disease in postmenopaususal women. Methods: We estalished murine monoclonal TR-FIA methods for daidzein, genistein and equol. The assays could be perfomed manually or adapted to an automated analyzer for the high throughput and increased accuracy. Analysis....... Conclusions: The validated monoclonal TR-FIA methods are applicable for use in large-scale human phytoestrogen intervention studies and can be used to monitor cokpliance, demonstrate bioavailability and assess equol producer status.......Background: Time-resolved fluorescence immunoessays (TR-FIAs) for phytoestrogens in biological samples are an alternative to mass spectrometric methods. These immunoessays were used to test urne and plasma samples from individuals in a dietary trial aimed at determining the efficacy of dietary...

  1. Using time-resolved fluorescence to measure serum venom-specific IgE and IgG.

    Directory of Open Access Journals (Sweden)

    Pauline E van Eeden

    Full Text Available We adapted DELFIA™ (dissociation-enhanced lanthanide fluoroimmunoassay, a time resolved fluorescence method, to quantitate whole venom specific and allergenic peptide-specific IgE (sIgE, sIgG(1 and sIgG(4 in serum from people clinically allergic to Australian native ant venoms, of which the predominant cause of allergy is jack jumper ant venom (JJAV. Intra-assay CV was 6.3% and inter-assay CV was 13.7% for JJAV sIgE. DELFIA and Phadia CAP JJAV sIgE results correlated well and had similar sensitivity and specificity for the detection of JJAV sIgE against intradermal skin testing as the gold standard. DELFIA was easily adapted for detecting sIgE to a panel of other native ant venoms.

  2. Temperature-dependent loop formation kinetics in flexible peptides studied by time-resolved fluorescence spectroscopy

    Directory of Open Access Journals (Sweden)

    Harekrushna Sahoo

    2006-01-01

    Full Text Available Looping rates in short polypeptides can be determined by intramolecular fluorescence quenching of a 2,3-diazabicyclo[2.2.2]oct-2-ene-labeled asparagine (Dbo by tryptophan. By this methodology, the looping rates in glycine-serine peptides with the structure Trp-(Gly-Sern-Dbo-NH2 of different lengths (n = 0–10 were determined in dependence on temperature in D2O and the activation parameters were derived. In general, the looping rate increases with decreasing peptide length, but the shortest peptide (n=0 shows exceptional behavior because its looping rate is slower than that for the next longer ones (n=1,2. The activation energies increase from 17.5 kJ mol−1 for the longest peptide (n=10 to 20.5 kJ mol−1 for the shortest one (n=0, while the pre-exponential factors (log⁡(A/s−1 range from 10.20 to 11.38. The data are interpreted in terms of an interplay between internal friction (stiffness of the biopolymer backbone and steric hindrance effects and solvent friction (viscosity-limited diffusion. For the longest peptides, the activation energies resemble more and more the value expected for solvent viscous flow. Internal friction is most important for the shortest peptides, causing a negative curvature and a smaller than ideal slope (ca. –1.1 of the double-logarithmic plots of the looping rates versus the number of peptide chain segments (N. Interestingly, the corresponding plot for the pre-exponential factors (logA versus logN shows the ideal slope (–1.5. While the looping rates can be used to assess the flexibility of peptides in a global way, it is suggested that the activation energies provide a measure of the “thermodynamic” flexibility of a peptide, while the pre-exponential factors reflect the “dynamic” flexibility.

  3. Interactions of a lytic peptide with supported lipid bilayers investigated by time-resolved evanescent wave-induced fluorescence spectroscopy

    Science.gov (United States)

    Rapson, Andrew C.; Gee, Michelle L.; Clayton, Andrew H. A.; Smith, Trevor A.

    2016-12-01

    We report investigations, using time-resolved and polarised evanescent wave-induced fluorescence methods, into the location, orientation and mobility of a fluorescently labelled form of the antimicrobial peptide, melittin, when it interacts with vesicles and supported lipid bilayers (SLBs). This melittin analogue, termed MK14-A430, was found to penetrate the lipid headgroup structure in pure, ordered-phase DPPC membranes but was located near the headgroup-water region when cholesterol was included. MK14-A430 formed lytic pores in SLBs, and an increase in pore formation with incubation time was observed through an increase in polarity and mobility of the probe. When associated with the Cholesterol-containing SLB, the probe displayed polarity and mobility that indicated a population distributed near the lipid headgroup-water interface with MK14-A430 arranged predominantly in a surface-aligned state. This study indicates that the lytic activity of MK14-A430 occurred through a pore-forming mechanism. The lipid headgroup environment experienced by the fluorescent label, where MK14-A430 displayed pore information, indicated that pore formation was best described by the toroidal pore model.

  4. Development of a dual-modal tissue diagnostic system combining time-resolved fluorescence spectroscopy and ultrasonic backscatter microscopy

    Science.gov (United States)

    Sun, Yang; Park, Jesung; Stephens, Douglas N.; Jo, Javier A.; Sun, Lei; Cannata, Jonathan M.; Saroufeem, Ramez M. G.; Shung, K. Kirk; Marcu, Laura

    2009-06-01

    We report a tissue diagnostic system which combines two complementary techniques of time-resolved laser-induced fluorescence spectroscopy (TR-LIFS) and ultrasonic backscatter microscopy (UBM). TR-LIFS evaluates the biochemical composition of tissue, while UBM provides tissue microanatomy and enables localization of the region of diagnostic interest. The TR-LIFS component consists of an optical fiber-based time-domain apparatus including a spectrometer, gated multichannel plate photomultiplier, and fast digitizer. It records the fluorescence with high sensitivity (nM concentration range) and time resolution as low as 300 ps. The UBM system consists of a transducer, pulser, receiving circuit, and positioning stage. The transducer used here is 45 MHz, unfocused, with axial and lateral resolutions 38 and 200 μm. Validation of the hybrid system and ultrasonic and spectroscopic data coregistration were conducted both in vitro (tissue phantom) and ex vivo (atherosclerotic tissue specimens of human aorta). Standard histopathological analysis of tissue samples was used to validate the UBM-TRLIFS data. Current results have demonstrated that spatially correlated UBM and TR-LIFS data provide complementary characterization of both morphology (necrotic core and calcium deposits) and biochemistry (collagen, elastin, and lipid features) of the atherosclerotic plaques at the same location. Thus, a combination of fluorescence spectroscopy with ultrasound imaging would allow for better identification of features associated with tissue pathologies. Current design and performance of the hybrid system suggests potential applications in clinical diagnosis of atherosclerotic plaque.

  5. Full genotyping of a highly polymorphic human gene trait by time-resolved fluorescence resonance energy transfer.

    Directory of Open Access Journals (Sweden)

    Edoardo Totè

    Full Text Available The ability of detecting the subtle variations occurring, among different individuals, within specific DNA sequences encompassed in highly polymorphic genes discloses new applications in genomics and diagnostics. DQB1 is a gene of the HLA-II DQ locus of the Human Leukocyte Antigens (HLA system. The polymorphisms of the trait of the DQB1 gene including codons 52-57 modulate the susceptibility to a number of severe pathologies. Moreover, the donor-receiver tissue compatibility in bone marrow transplantations is routinely assessed through crossed genotyping of DQB and DQA. For the above reasons, the development of rapid, reliable and cost-effective typing technologies of DQB1 in general, and more specifically of the codons 52-57, is a relevant although challenging task. Quantitative assessment of the fluorescence resonance energy transfer (FRET efficiency between chromophores labelling the opposite ends of gene-specific oligonucleotide probes has proven to be a powerful tool to type DNA polymorphisms with single-nucleotide resolution. The FRET efficiency can be most conveniently quantified by applying a time-resolved fluorescence analysis methodology, i.e. time-correlated single-photon counting, which allows working on very diluted template specimens and in the presence of fluorescent contaminants. Here we present a full in-vitro characterization of the fluorescence responses of two probes when hybridized to oligonucleotide mixtures mimicking all the possible genotypes of the codons 52-57 trait of DQB1 (8 homozygous and 28 heterozygous. We show that each genotype can be effectively tagged by the combination of the fluorescence decay constants extrapolated from the data obtained with such probes.

  6. Translational and rotational motions of albumin sensed by a non-covalent associated porphyrin under physiological and acidic conditions: a fluorescence correlation spectroscopy and time resolved anisotropy study.

    NARCIS (Netherlands)

    Andrade, S.M.; Costa, S.M.; Borst, J.W.; Hoek, van A.; Visser, A.J.W.G.

    2008-01-01

    The interaction between a free-base, anionic water-soluble porphyrin, TSPP, and the drug carrier protein, bovine serum albumin (BSA) has been studied by time-resolved fluorescence anisotropy (TRFA) and fluorescence correlation spectroscopy (FCS) at two different pH-values. Both rotational correlatio

  7. 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.

  8. 340nm UV LED excitation in time-resolved fluorescence system for europium-based immunoassays detection

    Science.gov (United States)

    Rodenko, Olga; Fodgaard, Henrik; Tidemand-Lichtenberg, Peter; Pedersen, Christian

    2017-02-01

    In immunoassay analyzers for in-vitro diagnostics, Xenon flash lamps have been widely used as excitation light sources. Recent advancements in UV LED technology and its advantages over the flash lamps such as smaller footprint, better wall-plug efficiency, narrow emission spectrum, and no significant afterglow, have made them attractive light sources for gated detection systems. In this paper, we report on the implementation of a 340 nm UV LED based time-resolved fluorescence system based on europium chelate as a fluorescent marker. The system performance was tested with the immunoassay based on the cardiac marker, TnI. The same signal-to-noise ratio as for the flash lamp based system was obtained, operating the LED below specified maximum current. The background counts of the system and its main contributors were measured and analyzed. The background of the system of the LED based unit was improved by 39% compared to that of the Xenon flash lamp based unit, due to the LEDs narrower emission spectrum and longer pulse width. Key parameters of the LED system are discussed to further optimize the signal-to-noise ratio and signal-to-background, and hence the sensitivity of the instrument.

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

    Energy Technology Data Exchange (ETDEWEB)

    Mao, Pengcheng; Wang, Zhuan; Dang, Wei; Weng, Yuxiang, E-mail: yxweng@aphy.iphy.ac.cn [Key Laboratory of Soft Matter Physics, Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190 (China)

    2015-12-15

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

  10. 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 to t...

  11. 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...

  12. Flexibility of Enzymes Suspended in Organic Solvents Probed by Time-Resolved Fluorescence Anisotropy. Evidence That Enzyme Activity and Enantioselectivity Are Directly Related to Enzyme Flexibility

    NARCIS (Netherlands)

    Broos, Jaap; Visser, Antonie J.W.G.; Engbersen, Johan F.J.; Verboom, Willem; Hoek, Arie van; Reinhoudt, David N.

    1995-01-01

    A time-resolved fluorescence anisotropy study on the molecular flexibility of active-site labeled anthraniloyl-α-chymotrypsin, dansylsubtilisin Carlsberg, and native subtilisin Carlsberg, suspended in organic solvents, is described. The internal rotational mobility of the fluorophore in the

  13. Detection of anthrax protective antigen (PA) using europium labeled anti-PA monoclonal antibody and time-resolved fluorescence.

    Science.gov (United States)

    Stoddard, Robyn A; Quinn, Conrad P; Schiffer, Jarad M; Boyer, Anne E; Goldstein, Jason; Bagarozzi, Dennis A; Soroka, Stephen D; Dauphin, Leslie A; Hoffmaster, Alex R

    2014-06-01

    Inhalation anthrax is a rare but acute infectious disease following adsorption of Bacillus anthracis spores through the lungs. The disease has a high fatality rate if untreated, but early and correct diagnosis has a significant impact on case patient recovery. The early symptoms of inhalation anthrax are, however, non-specific and current anthrax diagnostics are primarily dependent upon culture and confirmatory real-time PCR. Consequently, there may be a significant delay in diagnosis and targeted treatment. Rapid, culture-independent diagnostic tests are therefore needed, particularly in the context of a large scale emergency response. The aim of this study was to evaluate the ability of monoclonal antibodies to detect anthrax toxin proteins that are secreted early in the course of B. anthracis infection using a time-resolved fluorescence (TRF) immunoassay. We selected monoclonal antibodies that could detect protective antigen (PA), as PA83 and also PA63 and LF in the lethal toxin complex. The assay reliable detection limit (RDL) was 6.63×10(-6)μM (0.551ng/ml) for PA83 and 2.51×10(-5)μM (1.58ng/ml) for PA63. Despite variable precision and accuracy of the assay, PA was detected in 9 out of 10 sera samples from anthrax confirmed case patients with cutaneous (n=7), inhalation (n=2), and gastrointestinal (n=1) disease. Anthrax Immune Globulin (AIG), which has been used in treatment of clinical anthrax, interfered with detection of PA. This study demonstrates a culture-independent method of diagnosing anthrax through the use of monoclonal antibodies to detect PA and LF in the lethal toxin complex.

  14. Detection of anthrax protective antigen (PA) using europium labeled anti-PA monoclonal antibody and time-resolved fluorescence

    Science.gov (United States)

    Stoddard, Robyn A.; Quinn, Conrad P.; Schiffer, Jarad M.; Boyer, Anne E.; Goldstein, Jason; Bagarozzi, Dennis A.; Soroka, Stephen D.; Dauphin, Leslie A.; Hoffmaster, Alex R.

    2015-01-01

    Inhalation anthrax is a rare but acute infectious disease following adsorption of Bacillus anthracis spores through the lungs. The disease has a high fatality rate if untreated, but early and correct diagnosis has a significant impact on case patient recovery. The early symptoms of inhalation anthrax are, however, non-specific and current anthrax diagnostics are primarily dependent upon culture and confirmatory real-time PCR. Consequently, there may be a significant delay in diagnosis and targeted treatment. Rapid, culture-independent diagnostic tests are therefore needed, particularly in the context of a large scale emergency response. The aim of this study was to evaluate the ability of monoclonal antibodies to detect anthrax toxin proteins that are secreted early in the course of B. anthracis infection using a time-resolved fluorescence (TRF) immunoassay. We selected monoclonal antibodies that could detect protective antigen (PA), as PA83 and also PA63 and LF in the lethal toxin complex. The assay reliable detection limit (RDL) was 6.63 × 10−6 μM (0.551 ng/ml) for PA83 and 2.51 × 10−5 μM (1.58 ng/ml) for PA63. Despite variable precision and accuracy of the assay, PA was detected in 9 out of 10 sera samples from anthrax confirmed case patients with cutaneous (n=7), inhalation (n=2), and gastrointestinal (n=1) disease. Anthrax Immune Globulin (AIG), which has been used in treatment of clinical anthrax, interfered with detection of PA. This study demonstrates a culture-independent method of diagnosing anthrax through use of monoclonal antibodies to detect PA and LF in the lethal toxin complex. PMID:24857756

  15. Picosecond spectroscopy of dihydro biliverdin

    Science.gov (United States)

    Ditto, Manfred; Brunner, Harald; Lippitsch, Max E.

    1991-10-01

    Picosecond time-resolved fluorescence and absorption spectroscopy was performed on dihydro biliverdin, a model for the chromophore in the plant pigment phytochrome, a chromoprotein governing plant growth. Close agreement between the model compound and the native chromophore proves the importance of the saturated pyrrol ring for the decay kinetics and renders chromophore protonation in phytochrome unlikely.

  16. Demonstration of single-shot picosecond time-resolved MeV electron imaging using a compact permanent magnet quadrupole based lens

    CERN Document Server

    Cesar, D; Musumeci, P; Sun, Y; Harrison, J; Frigola, P; O'Shea, F H; To, H; Alesini, D; Li, R K

    2016-01-01

    We present the results of an experiment where a short focal length (~ 1.3 cm) permanent magnet electron lens is used to image micron-size features of a metal sample in a single shot, using an ultra- high brightness ps-long 4 MeV electron beam from a radiofrequency photoinjector. Magnifcation ratios in excess of 30x were obtained using a triplet of compact, small gap (3.5 mm), Halbach-style permanent magnet quadrupoles with nearly 600 T/m field gradients. These results pave the way to- wards single shot time-resolved electron microscopy and open new opportunities in the applications of high brightness electron beams.

  17. Strongly nonexponential time-resolved fluorescence of quantum-dot ensembles in three-dimensional photonic crystals

    NARCIS (Netherlands)

    Nikolaev, I.; Lodahl, P.; van Driel, A. Floris; Koenderink, A.F.; Vos, Willem L.

    2007-01-01

    We observe experimentally that ensembles of quantum dots in three-dimensional (3D) photonic crystals reveal strongly nonexponential time-resolved emission. These complex emission decay curves are analyzed with a continuous distribution of decay rates. The log-normal distribution describes the decays

  18. Picosecond Fluorescence Dynamics of Tryptophan and 5-Fluorotryptophan in Monellin : Slow Water-Protein Relaxation Unmasked

    NARCIS (Netherlands)

    Xu, Jianhua; Chen, Binbin; Callis, Patrik Robert; Muiño, Pedro L; Rozeboom, Henriette J; Broos, Jaap; Toptygin, Dmitri; Brand, Ludwig; Knutson, Jay R

    2015-01-01

    Time Dependent Fluorescence Stokes (emission wavelength) Shifts (TDFSS) from tryptophan (Trp) following sub-picosecond excitation are increasingly used to investigate protein dynamics, most recently enabling active research interest into water dynamics near the surface of proteins. Unlike many fluor

  19. Picosecond Fluorescence Dynamics of Tryptophan and 5-Fluorotryptophan in Monellin : Slow Water-Protein Relaxation Unmasked

    NARCIS (Netherlands)

    Xu, Jianhua; Chen, Binbin; Callis, Patrik Robert; Muiño, Pedro L; Rozeboom, Henriette J; Broos, Jaap; Toptygin, Dmitri; Brand, Ludwig; Knutson, Jay R

    2015-01-01

    Time Dependent Fluorescence Stokes (emission wavelength) Shifts (TDFSS) from tryptophan (Trp) following sub-picosecond excitation are increasingly used to investigate protein dynamics, most recently enabling active research interest into water dynamics near the surface of proteins. Unlike many

  20. A time-resolved fluorescence immunoassay for the measurement of testosterone in saliva: Monitoring of testosterone replacement therapy with testosterone buciclate

    OpenAIRE

    Tschöp, Matthias; Behre, Hermann M.; Nieschlag, Eberhard; Dressendorfer, Regina A.; Strasburger, Christian J.

    1998-01-01

    Monitoring of testosterone replacement therapy requires a reliable method for testosterone measurement. Determination of salivary testosterone, which reflects the hormone's biologically active plasma fraction, is a superior technique for this purpose. The aim of the present study was to establish a new sensitive time-resolved fluorescence immunoassay for the accurate measurement of testosterone levels in saliva and to validate it by monitoring testosterone replacement therapy in eight hypogon...

  1. Monitoring changes of cellular metabolism and microviscosity in vitro based on time-resolved endogenous fluorescence and its anisotropy decay dynamics

    Science.gov (United States)

    Zheng, Wei; Li, Dong; Qu, Jianan Y.

    2010-05-01

    Reduced nicotinamide adenine dinucleotide (NADH) is a well-known metabolic coenzyme and endogenous fluorophore. In this study, we develop a system that simultaneously measures time- and wavelength-resolved fluorescence to extract free and protein-bound NADH signals from total cellular fluorescence. We analyze temporal characteristics of NADH fluorescence in a mixture of NADH and lactate dehydrogenase (LDH) as well as in living cell samples. The results show that in both the NADH/LDH mixture and cell samples, a fraction of free NADH and protein-bound components can be identified. The extracted free and bound NADH signals are confirmed by time-resolved measurement of anisotropy decay of NADH fluorescence, based on the fact that free NADH is a small fluorescent molecule with much shorter rotational diffusion time than bound NADH. The ratio of free NADH signal to bound NADH signal is very different between normal and cancer cervical epithelial cells. In addition, the ratio changes significantly when the cell samples are treated with a mitochondrial inhibitor or uncoupler, demonstrating that the method is sensitive to monitor cellular metabolic activity. Finally, we demonstrate that the microviscosity for relatively small molecules such as NADH in cells could be extracted from wavelength- and time-resolved NADH fluorescence of living cell samples.

  2. Time-resolved study of the UV fluorescence of chlorine under synchrotron radiation excitation of Cl/sub 2//rare-gas mixtures

    Energy Technology Data Exchange (ETDEWEB)

    Le Calve, J. (CEA Centre d' Etudes Nucleaires de Saclay, 91 - Gif-sur-Yvette (France)); Castex, M.C. (Paris-13 Univ., 93 - Villetaneuse (France)); Haaks, D. (Gesamthochschule Wuppertal (Germany, F.R.). Inst. fuer Physikalische Chemie); Jordan, B.; Zimmerer, G. (Hamburg Univ. (Germany, F.R.). 2. Inst. fuer Experimentalphysik)

    1981-05-11

    UV fluorescence of pure Cl/sub 2/ and Cl/sub 2//rare-gas mixtures has been investigated under selective, pulsed VUV excitation. In pure Cl/sub 2/, a strong fluorescence between 1350 and 2000 A is found with typical radiative lifetimes of 3 ns. Addition of Kr(Ar) to Cl/sub 2/ strongly quenches this fluorescence and let show up Kr(Ar)Cl* emissions as well as the Cl/sub 2/ ''laser'' emission at 2580 A. The radiative lifetime of the Cl/sub 2/ laser state is found to be 16 ns. Absorptions and emissions observed in this work are discussed in view of the results of time-resolved fluorescence spectroscopy and of recent theoretical results on the excited-potential curves of Cl/sub 2/.

  3. A novel cell-based duplex high-throughput screening assay combining fluorescent Ca(2+) measurement with homogeneous time-resolved fluorescence technology.

    Science.gov (United States)

    Kiss, László; Cselenyák, Attila; Varga, Ágnes; Visegrády, András

    2016-08-15

    Cell-based assays for G-protein-coupled receptor (GPCR) activation applied in high-throughput screening (HTS) monitor various readouts for second messengers or intracellular effectors. Recently, our understanding of diverging signaling pathways downstream of receptor activation and the capability of small molecules to selectively modulate signaling routes has increased substantially, underlining the importance of selecting appropriate readouts in cellular functional screens. To minimize the rate of false negatives in large-scale screening campaigns, it is crucial to maximize the chance of a ligand being detected, and generally applicable methods for detecting multiple analytes from a single well might serve this purpose. The few assays developed so far based on multiplexed GPCR readouts are limited to only certain applications and usually rely on genetic manipulations hindering screening in native or native-like cellular systems. Here we describe a more generally applicable and HTS-compatible homogeneous assay based on the combination of fluorometric detection of [Ca(2+)] with subsequent homogeneous time-resolved fluorescence (HTRF) cAMP readout in the same well. Besides describing development and validation of the assay, using a cell line recombinantly expressing the human PTH1 receptor screening of a small library is also presented, demonstrating the robustness and HTS compatibility of the novel paradigm.

  4. Time-Resolved Fluorescence Anisotropy Study of the Interaction Between DNA and a Peptide Truncated from the p53 Protein Core Domain.

    Science.gov (United States)

    Liu, Chengxuan; Liang, Gaiting; Liu, Zhen; Zu, Lily

    2014-03-01

    Time-resolved fluorescence anisotropy spectroscopy was applied to study the interaction between a peptide truncated from the binding site of tumor suppressor p53 protein and the DNAs covalently labeled with 6-carboxyfluorescein (FAM) dye. Fluorescence intensity quenching and changes of anisotropy decay lifetime were monitored when FAM labeled DNA formed complex with the peptide. The results demonstrated that the sequence of DNA could not define the binding specificity between the peptide and DNA. But the anisotropy decay of FAM can be used to examine the binding affinity of the peptide to DNA. The fluorescent dynamics of FAM can also be used to represent the rigidity of the complex formed between the peptide and DNA.

  5. Time-resolved study of the UV fluorescence of chlorine under synchrotron radiation excitation of Cl/sub 2//rare-gas mixtures

    Energy Technology Data Exchange (ETDEWEB)

    le Calve, J. (CEA Centre d' Etudes Nucleaires de Saclay, 91 - Gif-sur-Yvette (France)); Castex, M.C. (Centre National de la Recherche Scientifique, 93 - Villetaneuse (France). Lab. des Interactions Moleculaires et des Hautes Pressions); Haaks, D. (Gesamthochschule Wuppertal (Germany, F.R.). Inst. fuer Physikalische Chemie); Jordan, B.; Zimmerer, G. (Hamburg Univ. (Germany, F.R.). 2. Inst. fuer Experimentalphysik)

    1981-05-11

    UV fluroescence of pure Cl/sub 2/ and Cl/sub 2//rare-gas mixtures has been investigated under selective, pulsed VUV excitation. In pure Cl/sub 2/, a strong fluorescence between 135 and 200 nm is found with typical radiative lifetimes of 3 ns. Addition of Kr(Ar) to Cl/sub 2/ strongly quenches this fluorescence and let Kr(Ar)Clsup(*) emissions show up as well as the Cl/sub 2/ laser emission at 258 nm. The radiative lifetime of the Cl/sub 2/ laser state is found to be 16 ns. Absorptions and emissions observed in this work are discussed in view of the results of time-resolved fluorescence spectroscopy and the recent theoretical results on the excited-potential curves of Cl/sub 2/.

  6. The open, the closed, and the empty: time-resolved fluorescence spectroscopy and computational analysis of RC-LH1 complexes from Rhodopseudomonas palustris.

    Science.gov (United States)

    Beyer, Sebastian R; Müller, Lars; Southall, June; Cogdell, Richard J; Ullmann, G Matthias; Köhler, Jürgen

    2015-01-29

    We studied the time-resolved fluorescence of isolated RC-LH1 complexes from Rhodopseudomonas palustris as a function of the photon fluence and the repetition rate of the excitation laser. Both parameters were varied systematically over 3 orders of magnitude. On the basis of a microstate description we developed a quantitative model for RC-LH1 and obtained very good agreement between experiments and elaborate simulations based on a global master equation approach. The model allows us to predict the relative population of RC-LH1 complexes with the special pair in the neutral state or in the oxidized state P(+) and those complexes that lack a reaction center.

  7. Selective nonpeptidic fluorescent ligands for oxytocin receptor: design, synthesis, and application to time-resolved FRET binding assay.

    Science.gov (United States)

    Karpenko, Iuliia A; Margathe, Jean-François; Rodriguez, Thiéric; Pflimlin, Elsa; Dupuis, Elodie; Hibert, Marcel; Durroux, Thierry; Bonnet, Dominique

    2015-03-12

    The design and the synthesis of the first high-affinity fluorescent ligands for oxytocin receptor (OTR) are described. These compounds enabled the development of a TR-FRET based assay for OTR, readily amenable to high throughput screening. The validation of the assay was achieved by competition experiments with both peptide and nonpeptide OTR ligands as competitors. These probes represent the first selective fluorescent ligands for the oxytocin G protein-coupled receptor.

  8. Time-resolved detection of aromatic compounds on planetary surfaces by ultraviolet laser induced fluorescence and Raman spectroscopy

    Science.gov (United States)

    Eshelman, E.; Daly, M. G.; Slater, G.; Cloutis, E.

    2015-12-01

    Raman spectroscopic instruments are highly capable in the search for organics on Mars due to the potential to perform rapid and nondestructive measurements on unprepared samples. Upcoming and future Raman instruments are likely to also incorporate laser-induced fluorescence (LIF) capabilities, which can be added for modest cost and complexity. We demonstrate that it is possible to obtain sub-ns fluorescence lifetime measurements of Mars-relevant organics and minerals if a fast time-gating capability is used with an intensified detector and a short ultraviolet laser pulse. This serves a primary purpose of discriminating mineral from short-lived (less than 10 ns) organic fluorescence, considered a potential biosignature. Additionally, lifetime measurements may assist in determining if more than one fluorescing species is present and provide information concerning the molecular structure as well as the local environment. Fast time-gating is also useful at longer visible or near-IR wavelengths, as this approach increases the sensitivity of the instrument to organic material by removing the majority of the fluorescence background from the Raman signal and reducing the effect of ambient light.

  9. Simultaneous determination of nabumetone and its principal metabolite in medicines and human urine by time-resolved fluorescence.

    Science.gov (United States)

    Murillo Pulgarín, José Antonio; Alañón Molina, Aurelia; Martínez Ferreras, Fernando

    2012-11-07

    A simple fluorescent methodology for the simultaneous determination of nabumetone and its main metabolite, 6-methoxy-2-naphthylacetic acid (6-MNA), in pharmaceutical preparations and human urine is proposed. Due to the strong overlapping between the fluorescence spectra of both analytes, the use of fluorescence decay curves to resolve their mixture is proposed, since these curves are more selective. Values of dependent instrumental variables affecting the signal-to-noise ratio were fixed using a simplex optimization procedure. A factorial design with three levels per factor coupled to a central composite design was selected to obtain a calibration matrix of thirteen standards plus one blank sample that was processed using a partial least-squares (PLS) analysis. In order to assess the goodness of the proposed method, a prediction set of ten synthetic samples was analyzed, obtaining recovery percentages between 97 and 105%. Limits of detection, calculated by means of a new criterion, were 0.96 μg L(-1) and 0.88 μg L(-1) for nabumetone and 6-MNA, respectively. The method was also tested in the pharmaceutical preparation Relif, which contains nabumetone, obtaining recovery percentages close to 100%. Finally, the simultaneous determination of both analytes in human urine samples was successfully carried out by the PLS-analysis of a matrix of fifteen standards plus four analyte blanks and the use of the standard addition technique. Although urine shows native fluorescence, no extraction method or prior separation of the analytes was needed.

  10. Excitation relaxation dynamics and energy transfer in fucoxanthin-chlorophyll a/c-protein complexes, probed by time-resolved fluorescence.

    Science.gov (United States)

    Akimoto, Seiji; Teshigahara, Ayaka; Yokono, Makio; Mimuro, Mamoru; Nagao, Ryo; Tomo, Tatsuya

    2014-09-01

    In algae, light-harvesting complexes contain specific chlorophylls (Chls) and keto-carotenoids; Chl a, Chl c, and fucoxanthin (Fx) in diatoms and brown algae; Chl a, Chl c, and peridinin in photosynthetic dinoflagellates; and Chl a, Chl b, and siphonaxanthin in green algae. The Fx-Chl a/c-protein (FCP) complex from the diatom Chaetoceros gracilis contains Chl c1, Chl c2, and the keto-carotenoid, Fx, as antenna pigments, in addition to Chl a. In the present study, we investigated energy transfer in the FCP complex associated with photosystem II (FCPII) of C. gracilis. For these investigations, we analyzed time-resolved fluorescence spectra, fluorescence rise and decay curves, and time-resolved fluorescence anisotropy data. Chl a exhibited different energy forms with fluorescence peaks ranging from 677 nm to 688 nm. Fx transferred excitation energy to lower-energy Chl a with a time constant of 300fs. Chl c transferred excitation energy to Chl a with time constants of 500-600fs (intra-complex transfer), 600-700fs (intra-complex transfer), and 4-6ps (inter-complex transfer). The latter process made a greater contribution to total Chl c-to-Chl a transfer in intact cells of C. gracilis than in the isolated FCPII complexes. The lower-energy Chl a received excitation energy from Fx and transferred the energy to higher-energy Chl a. This article is part of a special issue entitled: photosynthesis research for sustainability: keys to produce clean energy.

  11. Time-resolved fluorescence of cationic dyes covalently bound to poly(methacrylic acid) in rigid media

    Energy Technology Data Exchange (ETDEWEB)

    Paulo Moises de Oliveira, Hueder [Instituto de Quimica de Sao Carlos, Universidade de Sao Paulo, Sao Carlos, SP (Brazil); Gehlen, Marcelo Henrique [Instituto de Quimica de Sao Carlos, Universidade de Sao Paulo, Sao Carlos, SP (Brazil)]. E-mail: marcelog@iqsc.usp.br

    2006-12-15

    Atactic poly(methacrylic acid) labeled with acridine and Nile blue (NB) were studied by photophysical techniques in bulk solid state and in solution-cast films over different surfaces (glass, ITO, and polymethylmethacrylate). In the systems with both dyes, energy transfer from acridine to NB occurs with an efficiency depending on the type of substrate (solid or film). The films are more disordered fluorescent rigid media than the bulk chromophoric or bichromophoric polymers, and this effect is ascribed to inhomogeneous distribution of the dyes in the film. This effect enhances dye bimolecular interactions and increases the energy transfer rates between acridine donor and NB acceptor. Bimodal distributions of donor fluorescence lifetimes are observed.

  12. 时间分辨荧光在免疫分析中的应用%The Application of Time-resolved Fluorescence in Immune Analysis

    Institute of Scientific and Technical Information of China (English)

    狄燕清

    2011-01-01

    As a kind of high sensitivity test means, time-resolved fluorescence(TRFIA) in immune analysis is widely used. With rare earth elements with a long fluorescence life and a strong fluorescence intensity as markers, and combed with time resolution, the technology sensitivity is greatly enhanced.Through the discussion of the application reseach of time-resolved fluorescence analysis in DNA analysis, clinic, food inspection,the great significance to the development of medicine and life sciences is revealed. The development of the method in applied field is promoted and related problems get further research, which make it better to serve human beings.%时间分辨荧光免疫分析作为一种高灵敏度的检测手段被应用到各个领域。该技术以荧光寿命长、荧光强度大的稀土元素作为标记物与时间分辨光谱相结合,极大的提高了检测灵敏度。通过探讨时间分辨荧光分析法在DNA分析、临床、食品检验中的应用研究。展示了其对医学及生命科学的发展具有重要意义。促进该方法应用领域的拓展及相关问题得进一步研究,使其更好地为人类所服务。

  13. Density relaxation and particle motion characteristics in a non-ionic deep eutectic solvent (acetamide + urea): Time-resolved fluorescence measurements and all-atom molecular dynamics simulations

    Energy Technology Data Exchange (ETDEWEB)

    Das, Anuradha; Das, Suman; Biswas, Ranjit, E-mail: ranjit@bose.res.in [Chemical, Biological and Macromolecular Sciences, S. N. Bose National Centre for Basic Sciences, Block-JD, Sector-III, Salt Lake, Kolkata, West Bengal 700098 (India)

    2015-01-21

    Temperature dependent relaxation dynamics, particle motion characteristics, and heterogeneity aspects of deep eutectic solvents (DESs) made of acetamide (CH{sub 3}CONH{sub 2}) and urea (NH{sub 2}CONH{sub 2}) have been investigated by employing time-resolved fluorescence measurements and all-atom molecular dynamics simulations. Three different compositions (f) for the mixture [fCH{sub 3}CONH{sub 2} + (1 − f)NH{sub 2}CONH{sub 2}] have been studied in a temperature range of 328-353 K which is ∼120-145 K above the measured glass transition temperatures (∼207 K) of these DESs but much lower than the individual melting temperature of either of the constituents. Steady state fluorescence emission measurements using probe solutes with sharply different lifetimes do not indicate any dependence on excitation wavelength in these metastable molten systems. Time-resolved fluorescence anisotropy measurements reveal near-hydrodynamic coupling between medium viscosity and rotation of a dissolved dipolar solute. Stokes shift dynamics have been found to be too fast to be detected by the time-resolution (∼70 ps) employed, suggesting extremely rapid medium polarization relaxation. All-atom simulations reveal Gaussian distribution for particle displacements and van Hove correlations, and significant overlap between non-Gaussian (α{sub 2}) and new non-Gaussian (γ) heterogeneity parameters. In addition, no stretched exponential relaxations have been detected in the simulated wavenumber dependent acetamide dynamic structure factors. All these results are in sharp contrast to earlier observations for ionic deep eutectics with acetamide [Guchhait et al., J. Chem. Phys. 140, 104514 (2014)] and suggest a fundamental difference in interaction and dynamics between ionic and non-ionic deep eutectic solvent systems.

  14. Exactly soluble model of the time-resolved fluorescence return to thermal equilibrium in many-particle systems after excitation

    Energy Technology Data Exchange (ETDEWEB)

    Czachor, Andrzej, E-mail: a.czachor@ncbj.gov.pl

    2016-02-15

    In this paper we consider the assembly of weakly interacting identical particles, where the occupation of single-particle energy-levels at thermal equilibrium is governed by statistics. The analytic form of the inter-energy-level jump matrix is derived and analytic solution of the related eigen-problem is given. It allows one to demonstrate the nature of decline in time of the energy emission (fluorescence, recombination) of such many-level system after excitation in a relatively simple and unifying way – as a multi-exponential de-excitation. For the system of L energy levels the number of the de-excitation lifetimes is L−1. The lifetimes depend on the energy level spectrum as a whole. Two- and three-level systems are considered in detail. The impact of the energy level degeneracy on the lifetimes is discussed.

  15. Interaction of quinine sulfate with anionic micelles of sodium dodecylsulfate: A time-resolved fluorescence spectroscopy at different pH

    Science.gov (United States)

    Joshi, Sunita; Pant, Debi D.

    2015-09-01

    Photophysical behavior and rotational relaxation dynamics of quinine sulfate (QS) in anionic surfactant, sodium dodecylsulfate (SDS) at different pH have been studied using steady state and time resolved fluorescence spectroscopy. It has been observed that the cationic form of quinine sulfate (at pH 2) forms a fluorescent ion pair complex with the surfactant molecules at lower concentrations of surfactant. However, for higher concentrations of SDS, the probe molecules bind strongly with the micelles and reside at the water-micelle interface. At pH 7, QS is singly protonated in bulk aqueous solution. At lower concentrations of SDS aggregation between probe and surfactant molecules has been observed. However, for higher concentrations of SDS, an additional fluorescence peak corresponding to dicationic form of QS appears and this has been attributed to double protonation of the QS molecule in micellar solution. At pH 7, in the presence of SDS micelles, the photophysical properties of QS showed substantial changes compared to that in the bulk water solution. At pH 12, an increase in fluorescence intensity and lifetime has been observed and this has been attributed to the increase in radiative rate due to the incorporation of QS at the micelle-water interface. The local pH at micellar surface has been found different from the pH of bulk solution.

  16. Surface speciation of Eu3+ adsorbed on kaolinite by time-resolved laser fluorescence spectroscopy (TRLFS) and parallel factor analysis (PARAFAC).

    Science.gov (United States)

    Ishida, Keisuke; Saito, Takumi; Aoyagi, Noboru; Kimura, Takaumi; Nagaishi, Ryuji; Nagasaki, Shinya; Tanaka, Satoru

    2012-05-15

    Time-resolved laser fluorescence spectroscopy (TRLFS) is an effective speciation technique for fluorescent metal ions and can be further extended by the parallel factor analysis (PARAFAC). The adsorption of Eu(3+) on kaolinite as well as gibbsite as a reference mineral was investigated by TRLFS together with batch adsorption measurements. The PAFAFAC modeling provided the fluorescence spectra, decay lifetimes, and relative intensity profiles of three Eu(3+) surface complexes with kaolinite; an outer-sphere (factor A) complex and two inner-sphere (factors B and C) complexes. Their intensity profiles qualitatively explained the measured adsorption of Eu(3+). Based on the TRLFS results in varied H(2)O/D(2)O media, it was shown that the outer-sphere complex exhibited more rapid fluorescence decay than Eu(3+) aquo ion, because of the energy transfer to the surface. Factor B was an inner-sphere complex, which became dominant at relatively high pH, high salt concentration and low Eu(3+) concentration. Its spectrum and lifetime were similar to those of Eu(3+) adsorbed on gibbsite, suggesting its occurrence on the edge face of the gibbsite layer of kaolinite. From the comparison with the spectra and lifetimes of crystalline or aqueous Eu(OH)(3), factor C was considered as a poly-nuclear surface complex of Eu(3+) formed at relatively high Eu(3+) concentration.

  17. Complexation of europium(III) with the zwitterionic form of amino acids studied with ultraviolet-visible and time-resolved laser-induced fluorescence spectroscopy.

    Science.gov (United States)

    Heller, Anne; Rönitz, Olivia; Barkleit, Astrid; Bernhard, Gert; Ackermann, Jörg-Uwe

    2010-08-01

    The complex formation of europium(III) with the zwitterionic form of amino acids (alanine, phenylalanine, and threonine) has been studied in aqueous solution. Measurements were performed at I = 0.1 M (NaCl/NaClO(4)), room temperature, and trace metal concentrations in the range of pH 2 to 8 using ultraviolet-visible (UV-Vis) and time-resolved laser-induced fluorescence spectroscopy (TRLFS). While complexation leads to a significant luminescence enhancement in the emission spectrum of the metal ion, absorption in the UV-Vis spectrum of the amino acid (AA) decreases. As zwitterionic species (AAH), all three ligands form weak complexes with 1:1 stoichiometry and a general formula of EuAAH(3+) with the metal. The complex stability constants were determined to be log K approximately 1 for all complexes, indicating the negligible contribution of the amino acid side chain to the complex formation reaction.

  18. Interaction of Cm(III) and Am(III) with human serum transferrin studied by time-resolved laser fluorescence and EXAFS spectroscopy.

    Science.gov (United States)

    Bauer, Nicole; Fröhlich, Daniel R; Panak, Petra J

    2014-05-14

    The complexation of Cm(III) with human serum transferrin was investigated in a pH range from 3.5 to 11.0 using time-resolved laser fluorescence spectroscopy (TRLFS). At pH ≥ 7.4 Cm(III) is incorporated at the Fe(III) binding site of transferrin whereas at lower pH a partially bound Cm(III) transferrin species is formed. At physiological temperature (310 K) at pH 7.4, about 70% of the partially bound and 30% of the incorporated Cm(III) transferrin species are present in solution. The Cm(III) results obtained by TRLFS are in very good agreement with Am(III) EXAFS results, confirming the incorporation of Am(III) at the Fe(III) binding site at pH 8.5.

  19. Time-resolved optical fluorescence spectroscopy of heterogeneous turbid media with special emphasis on brain tissue structures including diseased regions: A sensitivity analysis

    Science.gov (United States)

    Vaudelle, Fabrice; L'huillier, Jean-Pierre

    2013-09-01

    Fluorescence-enhanced optical imaging based on near-infrared light provides a promising tool to differentiate diseased lesions from normal tissue. However, the measurement sensitivity of the fluorescence signals acquired at the output surface of the tissue is greatly influenced by the tissue structure, the optical properties, the location and the size of the target. In this paper, we present a numerical model based on the Monte Carlo method that allows to simulate time-resolved reflectance signals acquired on the surface of the scalp of a human head model bearing a fluorescent diseased region (tumor, glioma). The influence of tumor depth, tumor size and tumor shape evolution on the computed signals are analyzed by taking into account the multi-layered tissue structure. The simulations show that the mean-time-of-flight and the difference between two mean-times acquired at two source-detector distances are both relevant to this problem type. Furthermore, the simulations suggest that the use of the difference between mean-flight-times may be interesting to probe scattering changes that occur in the cerebrospinal fluid (CSF).

  20. Excited state dynamics and activation parameters of remarkably slow photoinduced CO loss from (η⁶-benzene)Cr(CO)₃ in n-heptane solution: a DFT and picosecond-time-resolved infrared study.

    Science.gov (United States)

    Clark, Ian P; George, Michael W; Greetham, Gregory M; Harvey, Emma C; Long, Conor; Manton, Jennifer C; Pryce, Mary T

    2010-11-01

    The electronic structure of (η⁶-benzene)Cr(CO)₃ has been calculated using density functional theory and a molecular orbital interaction diagram constructed based on the Cr(CO)₃ and benzene fragments. The highest occupied molecular orbitals are mainly metal based. The nature of the lowest energy excited states were determined by time-dependent density functional theory, and the lowest energy excited state was found to have significant metal to carbonyl charge transfer character. The photochemistry of (η⁶-benzene)Cr(CO)₃ was investigated by time-resolved infrared spectroscopy with picosecond time resolution. The low energy excited state was detected following irradiation at 400 nm, and this exhibited ν(CO) bands at lower energy than the equivalent ν(CO) bands of (η⁶-benzene)Cr(CO)₃, consistent with metal to carbonyl charge transfer character, and is formed with excess vibrational energy, relaxing to the v = 0 vibrational state within 3 ps. The resulting "cold" excited state decays to form the CO-loss species (η⁶-benzene)Cr(CO)₂ in approximately 70% yield and to reform (η⁶-benzene)Cr(CO)₃ within 150 ps. The rates of relaxation from the vibrationally hot state to the cold excited state and its subsequent reaction to yield (η⁶-benzene)Cr(CO)₂ were measured over a range of temperatures from 274 to 320 K, and the activation parameters for both processes were obtained from Eyring plots. The vibrational relaxation exhibits a negative activation enthalpy ΔH(‡) (-10 (±4) kJ mol⁻¹) and a negative activation entropy ΔS(‡) (-50 (±16) J mol⁻¹ K⁻¹). A significant barrier (ΔH(‡) = +12 (±4) kJ mol⁻¹) was obtained for the formation of (η⁶-benzene)Cr(CO)₂ with a ΔS(‡) value close to zero. These data are used to propose a model for the CO-loss process to yield (η⁶-benzene)Cr(CO)₂ and to explain why low temperature irradiation of (η⁶-benzene)Cr(CO)₃ with light of wavelengths greater than 400 nm produced

  1. Time-resolved single tryptophan fluorescence in photoactive yellow protein monitors changes in the chromophore structure during the photocycle via energy transfer.

    Science.gov (United States)

    Otto, Harald; Hoersch, Daniel; Meyer, Terry E; Cusanovich, Michael A; Heyn, Maarten P

    2005-12-27

    We show from time-resolved fluorescence intensity and depolarization experiments that the fluorescence of the unique tryptophan W119 of PYP is quenched by energy transfer to the 4-hydroxycinnamoyl chromophore. Whereas the intensity decay has a time constant of 0.18 ns in P, the decay in the absence of the cofactor (apo-PYP) has a single exponential lifetime of 4.8 ns. This difference in lifetime with and without acceptor can be explained quantitatively on the basis of energy transfer and the high-resolution X-ray structure of P, which allows an accurate calculation of the kappa2 factor. Fluorescence depolarization experiments with donor and acceptor indicate that both are immobilized so that kappa2 is constant on the fluorescence time scale. Using background illumination from an LED emitting at 470 nm, we measured the time-resolved fluorescence in a photostationary mixture of P and the intermediates I2 and I2'. The composition of the photostationary mixture depends on pH and changes from mainly I2 at low pH to predominantly I2' at high pH. The I2/I2' equilibrium is pH-dependent with a pKa of approximately 6.3. In I2 the lifetime increases to approximately 0.82 ns. This is not due to a change in distance or to the increase in spectral overlap but is primarily a consequence of a large decrease in kappa2. Kappa2 was calculated from the available X-ray structures and decreases from approximately 2.7 in P to 0.27 in I2. This change in kappa2 is caused by the isomerization of the acceptor, which leads to a reorientation of its transition dipole moment. We have here a rare case of the kappa2 factor dominating the change in energy transfer. The fluorescence decay in the light is pH-dependent. From an SVD analysis of the light/dark difference intensity decay at a number of pH values, we identify three species with associated lifetimes: P (0.18 ns), I2 (0.82 ns), and X (0.04 ns). On the basis of the pH dependence of the amplitudes associated with I2 and X, with a pKa of

  2. Sorption of Eu(III)/Cm(III) on Ca-montmorillonite and Na-illite. Part 1: Batch sorption and time-resolved laser fluorescence spectroscopy experiments

    Science.gov (United States)

    Rabung, Th.; Pierret, M. C.; Bauer, A.; Geckeis, H.; Bradbury, M. H.; Baeyens, B.

    2005-12-01

    Sorption of Cm(III) and Eu(III) at trace concentrations onto Ca-montmorillonite (SWy-1) and Na-illite (Illite du Puy) has been studied under anaerobic conditions by batch sorption experiments and time-resolved laser fluorescence spectroscopy (TRLFS). Comparison of the results from spectroscopic and batch sorption experiments with Cm and Eu indicates the existence of outer-sphere complexes at pH 5 for both clay minerals. Five H 2O/OH - molecules remain in the first metal ion coordination sphere of the sorbed Eu/Cm. Measured fluorescence lifetimes of sorbed Eu/Cm and peak deconvolution of Cm-spectra are consistent with the formation of surface complexes of the form ≡S-O-Eu/Cm(OH) x(2-x)(H 2O) 5-x. At pH ≥ 12 Cm becomes incorporated into a surface precipitate at the Ca-montmorillonite surface presumably composed of Ca(OH) 2 or calcium silicate hydrate. A dramatic shift of the fluorescence emission band by more than 20 nm and a clear increase in the fluorescence lifetime suggests the almost complete displacement of coordinated H 2O and OH -. The pH dependent Eu sorption data obtained in batch experiments are consistent with spectroscopic data on Eu and Cm within experimental uncertainties thus demonstrating the validity of Eu as a homologue for trivalent actinides. Parameterization of a two-site protolysis nonelectrostatic surface complexation and cation exchange model using the batch sorption data and spectroscopic results is discussed in Part 2 of this work.

  3. Speciation of europium (III) surface species on monocrystalline alumina using time-resolved laser-induced fluorescence-scanning near-field optical microscopy

    Energy Technology Data Exchange (ETDEWEB)

    Ghaleb, K.A.; Viala, F.; Miserque, F.; Salmon, L. [CEA Saclay, DEN/DANS/DPC/SCP, Lab Reactivite Surface et Interface, F-91191 Gif Sur Yvette, (France); Reiller, P. [CEA Saclay, DEN/DANS/DPC/SECR, Lab Speciat Radionucleides et Mol, F-91191 Gif Sur Yvette, (France); Moutiers, G. [CEA Saclay, DEN/DANS/DPC, Serv Chim Phys, F-91191 Gif Sur Yvette, (France)

    2008-07-01

    The aim of this work was to perform highly localized spectroscopic surface measurements by combining time-resolved laser spectroscopy and scanning near-field optical microscopy. The final purpose of that was to study surface sorption at the molecular level of trivalent ions in the framework of nuclear waste disposal assessment. Time-resolved laser spectroscopy presents the advantages of being selective, sensitive, and noninvasive and scanning near-field optical microscopy is a promising technique for high resolution surface speciation. Investigation of the interaction between trivalent europium and a monocrystalline alumina (11-bar02) surface was made using different conditions of concentration and pH. We found that the distribution of sorbed europium was always homogeneous with a decay time of europium (III) equal to 350 {mu}s {+-} 15 {mu}s. On the other hand, carbonate species with a decay time of 210 {mu}s {+-} 10 {mu}s or other hydroxide species with a decay time of 180 {mu}s {+-} 10 {mu}s were detected on the surface when a higher concentration or a higher pH solution, respectively, were used. Distribution of these species was heterogeneous and their associated fluorescence signal was relatively high, evoking a precipitated form. X-ray photoelectron spectroscopy (XPS) was also used on the same samples as a complementary technique. A binding energy of 1135.1 eV was obtained for the sorbed europium and another binding energy of 1134.4 eV was obtained for the hydroxide species, thus confirming the presence of two kinds of species on the surface. (authors)

  4. Evaluation of the time resolved fluorescence immunoassay (TRFIA) for the detection of varicella zoster virus (VZV) antibodies following vaccination of healthcare workers

    Science.gov (United States)

    McDonald, S.L.R.; Maple, P.A.C.; Andrews, N.; Brown, K.E.; Ayres, K.L.; Scott, F.T.; Bassam, M. Al; Gershon, A.A.; Steinberg, S.P.; Breuer, J.

    2017-01-01

    Determination of varicella zoster virus (VZV) immunity in healthcare workers without a history of chickenpox is important for identifying those in need of vOka vaccination. Post immunisation, healthcare workers in the UK who work with high risk patients are tested for seroconversion. To assess the performance of the time-resolved fluorescence immunoassay (TRFIA) for the detection of antibody in vaccinated as well as unvaccinated individuals, a cut-off was first calculated. VZV-IgG specific avidity and titres six weeks after the first dose of vaccine were used to identify subjects with pre-existing immunity among a cohort of 110 healthcare workers. Those with high avidity (≥60%) were considered to have previous immunity to VZV and those with low or equivocal avidity (130 mIU/mL which best discriminated between the two groups and this was confirmed by ROC analysis. Using this value, the sensitivity and specificity of TRFIA cut-off were 90% (95% CI 79–96), and 78% (95% CI 61–90) respectively in this population. A subset of samples tested by the gold standard Fluorescence Antibody to Membrane Antigen (FAMA) test showed 84% (54/64) agreement with TRFIA. PMID:21192976

  5. Fulvic acid complexation of Eu(III) and Cm(III) at elevated temperatures studied by time-resolved laser fluorescence spectroscopy.

    Science.gov (United States)

    Fröhlich, Daniel R; Skerencak-Frech, Andrej; Gast, Michael; Panak, Petra J

    2014-11-07

    The interaction of Eu(III) and Cm(III) with three different aquatic fulvic acids (FA) was studied as a function of the temperature (T = 20-80 °C) in 0.1 M NaCl solution by time-resolved laser fluorescence spectroscopy. The speciation of both trivalent metal ions was determined by peak deconvolution of the recorded fluorescence spectra. For each studied metal ion-FA system only one complexed species is formed under the given experimental conditions. The stability constants at 20, 40, 60 and 80 °C (log β'(T)) were determined according to the charge neutralization model. The log β' (20 °C) for the different FAs show similar values (log β(20 °C) = 5.60-6.29). The stability constants increase continuously with increasing temperature by approximately 0.3-1.0 orders of magnitude. The reaction enthalpies and entropies are derived from the integrated Van't Hoff equation. The results show that all investigated complexation reactions are endothermic and entropy-driven.

  6. Synthesis of a highly fluorescent beta-diketone-europium chelate and its utility in time-resolved fluoroimmunoassay of serum total thyroxine.

    Science.gov (United States)

    Wu, Feng-Bo; Han, Shi-Quan; Zhang, Chao; He, You-Feng

    2002-11-15

    A new highly fluorescent beta-diketone-europium chelate was synthesized and employed as a tracer to develop a time-resolved fluoroimmunoassay (TRFIA) for detection of serum total thyroxine (T4). The tetradentate beta-diketone chelator, 1,10-bis(thiophene-2'-yl)-4,4,5,5,6,6,7,7-octafluorodecane-1,3,8,10-tetraone (BTOT), was structurally composed of two units of thenoyltrifluoroacetone (TTA) derivatives but expressed fluorescence that was greatly enhanced, as compared to the original TTA molecules, in the presence of excess amount of Eu3+. The luminescence properties of the europium chelate of BTOT werestudied in aqueous solution. Chlorosulfonylation of BTOT afforded 1, 10-bis(5'-chlorosulfo-thiophene-2'-yl)-4,4,5,5,6,6,7,7-octafluorodecane-1,3,8,10-tetraone (BCTOT), which could be coupled to proteins (i.e., streptavidin or the BSA-T4 conjugate) and used as a tracer for TRFIA. Although the BCTOT-Eu complex could be detected at a very low level (approximately 1.07 x 10(-12) mol/L) in buffered aqueous solution (50 mmoVLTris-HCl; pH, 8.0), the application of the chelate label in direct serum T4 TRFIA experienced a problem of matrix interference, which was probably caused by some unknown chelating components in the samples as a result of the fact that the fluorescence of the BCTOT-Eu chelate was prone to quenching or enhancement by some chelating reagents. To remove this problem, an indirect serum T4 TRFIA was proposed with the use of BCTOT-Eu-labeled streptavidin (SA) as signal generation reagent. The concentrations of T4 in 27 human serums were determined by indirect T4 TRFIA, and the assay results correlated well with those obtained by commercial Coming-CLIA (r = 0.955) and Wallac-DELFIA (r 0.965).

  7. Applications of immunomagnetic capture and time-resolved fluorescence to detect outbreak Escherichia coli O157 and Salmonella in alfalfa sprouts

    Science.gov (United States)

    Tu, Shu-I.; Gordon, Marsha; Fett, William F.; Gehring, Andrew G.; Irwin, Peter L.

    2004-03-01

    Commercially available alfalfa seeds were inoculated with low levels (~ 4 CFU/g) of pathogenic bacteria. The inoculated seeds were then allowed to sprout in sterile tap water at 22°C. After 48 hours, the irrigation water and sprouts were separately transferred to bovine heart infusion (BHI) media. The microbes in the BHI samples were allowed to grow for 4 hours at 37°C and 160 rpm. Specific immunomagnetic beads (IMB) were then applied to capture the E.coli O157 and/or Salmonella in the growth media. Separation and concentration of IMB-captured pathogens were achieved using magnetic separators. The captured E. coli O157:H7 and Salmonella spp were further tagged with europium (Eu) labeled anti-E. coli O157 antibodies and samarium (Sm) labeled anti-Salmonella antibodies, respectively. After washing, the lanthanide labels were extracted out from the complexes by specific chelators to form strongly fluorescent chelates. The specific time-resolved fluorescence (TRF) associated with Eu or Sm was measured to estimate the extent of capture of the E. coli O157 and Salmonella, respectively. The results indicated that the approach could detect E. coli O157 and Salmonella enterica from the seeds inoculated with ~ 4 CFU/g of the pathogens. Non-targeted bacteria, e.g., Aeromonas and Citrobacter exhibited essentially no cross reactivity. Since the pathogen detection from the sprouts was achieved within 6 hours, the developed methodology could be use as a rapid, sensitive and specific screening process for E. coli O157 and Salmonella enterica in this popular salad food.

  8. A cell-based time-resolved fluorescence assay for selection of antibody reagents for G protein-coupled receptor immunohistochemistry.

    Science.gov (United States)

    Su, Jui-Lan; Fornwald, Jim; Rivers, Philip; Goldsworthy, Susan; Looney, Noeleen A; Hanvey, Jeff; Plumpton, Chris; Parham, Janet; Romanos, Michael; Kost, Thomas A; Kull, Frederick C

    2004-08-01

    A cell-based time-resolved fluorescence (celTRF) immunoassay is described for pre-screening antibodies to G protein-coupled receptor (GPCR) peptides that predicts suitability for immunohistochemistry (IHC). Rat GPCRs were expressed in Saos-2 human osteosarcoma cells via recombinant baculoviruses designed for mammalian cell expression, i.e., the transduced cells were used as a "screening lawn". The lawn was fixed and permeabilized similarly to IHC tissue. The celTRF, a dissociation-enhanced lanthanide fluorescence immunoassay (DELFIA), employed Eu-labelled goat anti-rabbit IgG. It exhibited a broad dynamic range upon which enzyme-linked immunosorbant assay (ELISA)-positive affinity-purified anti-peptide antibody reagents were examined for specificity and potency. Over 150 anti-peptide reagents to 27 GPCRs were characterized. All celTRF-positive antibodies were found to be suitable for IHC, whereas ELISA alone did not predict IHC utility. Examples are illustrated with five rabbit anti-neuropeptide FF receptor 1 (NPFF1) antibodies, where a strong correlation between celTRF potency and IHC utility was observed in both applications. In contrast, two high anti-peptide ELISA titer but celTRF-negative antibodies failed to recognize the NPFF1 receptor in IHC. The celTRF assay was performed manually and in an automated fashion, in our case, using a Biomek FX station and Sami scheduling software. The celTRF is the first in vitro automated assay that offers confident pre-selection of antibodies for IHC and the versatility to accommodate the rapid screening of large numbers of GPCRs. The celTRF is readily applicable to other protein target classes.

  9. Ultrafast Time-Resolved Emission and Absorption Spectra of meso-Pyridyl Porphyrins upon Soret Band Excitation Studied by Fluorescence Up-Conversion and Transient Absorption Spectroscopy.

    Science.gov (United States)

    Venkatesh, Yeduru; Venkatesan, M; Ramakrishna, B; Bangal, Prakriti Ranjan

    2016-09-08

    A comprehensive study of ultrafast molecular relaxation processes of isomeric meso-(pyridyl) porphyrins (TpyPs) has been carried out by using femtosecond time-resolved emission and absorption spectroscopic techniques upon pumping at 400 nm, Soret band (B band or S2), in 4:1 dichloromethane (DCM) and tetrahydrofuran (THF) solvent mixture. By combined studies of fluorescence up-conversion, time-correlated single photon counting, and transient absorption spectroscopic techniques, a complete model with different microscopic rate constants associated with elementary processes involved in electronic manifolds has been reported. Besides, a distinct coherent nuclear wave packet motion in Qy state is observed at low-frequency mode, ca. 26 cm(-1) region. Fluorescence up-conversion studies constitute ultrafast time-resolved emission spectra (TRES) over the whole emission range (430-710 nm) starting from S2 state to Qx state via Qy state. Careful analysis of time profiles of up-converted signals at different emission wavelengths helps to reveal detail molecular dynamics. The observed lifetimes are as indicated: A very fast decay component with 80 ± 20 fs observed at ∼435 nm is assigned to the lifetime of S2 (B) state, whereas being a rise component in the region of between 550 and 710 nm emission wavelength pertaining to Qy and Qx states, it is attributed to very fast internal conversion (IC) occurring from B → Qy and B → Qx as well. Two distinct components of Qy emission decay with ∼200-300 fs and ∼1-1.5 ps time constants are due to intramolecular vibrational redistribution (IVR) induced by solute-solvent inelastic collisions and vibrational redistribution induced by solute-solvent elastic collision, respectively. The weighted average of these two decay components is assigned as the characteristic lifetime of Qy, and it ranges between 0.3 and 0.5 ps. An additional ∼20 ± 2 ps rise component is observed in Qx emission, and it is assigned to the formation time of

  10. FLIMX: A Software Package to Determine and Analyze the Fluorescence Lifetime in Time-Resolved Fluorescence Data from the Human Eye

    Science.gov (United States)

    Klemm, Matthias; Schweitzer, Dietrich; Peters, Sven; Sauer, Lydia; Hammer, Martin; Haueisen, Jens

    2015-01-01

    Fluorescence lifetime imaging ophthalmoscopy (FLIO) is a new technique for measuring the in vivo autofluorescence intensity decays generated by endogenous fluorophores in the ocular fundus. Here, we present a software package called FLIM eXplorer (FLIMX) for analyzing FLIO data. Specifically, we introduce a new adaptive binning approach as an optimal tradeoff between the spatial resolution and the number of photons required per pixel. We also expand existing decay models (multi-exponential, stretched exponential, spectral global analysis, incomplete decay) to account for the layered structure of the eye and present a method to correct for the influence of the crystalline lens fluorescence on the retina fluorescence. Subsequently, the Holm-Bonferroni method is applied to FLIO measurements to allow for group comparisons between patients and controls on the basis of fluorescence lifetime parameters. The performance of the new approaches was evaluated in five experiments. Specifically, we evaluated static and adaptive binning in a diabetes mellitus patient, we compared the different decay models in a healthy volunteer and performed a group comparison between diabetes patients and controls. An overview of the visualization capabilities and a comparison of static and adaptive binning is shown for a patient with macular hole. FLIMX’s applicability to fluorescence lifetime imaging microscopy is shown in the ganglion cell layer of a porcine retina sample, obtained by a laser scanning microscope using two-photon excitation. PMID:26192624

  11. Nuclear magnetic resonance, fluorescence correlation spectroscopy and time-resolved fluorescence anisotropy studies of intermolecular interactions in bis(1-methyl-1H-imidazol-3-ium-3-yl)dihydroborate bis(trifluoromethylsulfonyl)amide and its mixtures with various cosolvents

    Science.gov (United States)

    Sahu, Prabhat Kumar; Nanda, Raju; Seth, Sudipta; Ghosh, Arindam; Sarkar, Moloy

    2016-09-01

    Keeping in mind the potential usefulness of mixed ionic liquid (IL)-cosolvents systems in several industrial applications, intermolecular interactions between a borate-based IL, bis(1-methyl-1H-imidazol-3-ium-3-yl)dihydroborate bis(trifluoromethylsulfonyl)amide ([BIMIMDBA][TF2N]), and its binary mixtures with several molecular solvents has been investigated through NMR and fluorescence spectroscopy. Analysis of the 1H chemical shifts (δ/ppm) and translational diffusion coefficients (D) of the IL in different solvent mixtures demonstrate interplay of nonspecific (ion-dipole) and specific (hydrogen bonding) interactions in governing the properties of these mixtures. Fluorescence correlation spectroscopy (FCS) and time-resolved fluorescence anisotropy data provide evidence in favour of different IL-solvent interaction for different IL-cosolvent systems.

  12. Homogeneous Time-Resolved Fluorescence-Based Assay to Monitor Extracellular Signal-Regulated Kinase Signalling in a High-Throughput Format

    Directory of Open Access Journals (Sweden)

    Mohammed Akli eAyoub

    2014-06-01

    Full Text Available The extracellular signal-regulated kinases (ERKs are key components of multiple important cell signalling pathways regulating diverse biological responses. This signalling is characterized by phosphorylation cascades leading to ERK1/2 activation and promoted by various cell surface receptors including G protein-coupled receptors (GPCRs and receptor tyrosine kinases (RTKs. We report the development of a new cell-based phospho-ERK1/2 assay (designated Phospho-ERK, which is a sandwich proximity-based assay using the homogeneous time-resolved fluorescence technology. We have validated the assay on endogenously expressed ERK1/2 activated by the epidermal growth factor (EGFR as a prototypical RTK, as well as various GPCRs belonging to different classes and coupling to different heterotrimeric G proteins. The assay was successfully miniaturized in 384-well plates using various cell lines endogenously, transiently or stably expressing the different receptors. The validation was performed for agonists, antagonists and inhibitors in dose-response as well as kinetic analysis, and the signalling and pharmacological properties of the different receptors were reproduced. Furthermore, the determination of a Z’-factor value of 0.7 indicates the potential of the Phospho-ERK assay for high-throughput screening of compounds that may modulate ERK1/2 signalling. Finally, our study is of great interest in the current context of investigating ERK1/2 signalling with respect to the emerging concepts of biased ligands, G protein-dependent/independent ERK1/2 activation, and functional transactivation between GPCRs and RTKs, illustrating the importance of considering the ERK1/2 pathway in cell signalling.

  13. Out-of-equilibrium biomolecular interactions monitored by picosecond fluorescence in microfluidic droplets.

    Science.gov (United States)

    Maillot, Sacha; Carvalho, Alain; Vola, Jean-Pierre; Boudier, Christian; Mély, Yves; Haacke, Stefan; Léonard, Jérémie

    2014-05-21

    We developed a new experimental approach combining Time-Resolved Fluorescence (TRF) spectroscopy and Droplet Microfluidics (DμF) to investigate the relaxation dynamics of structurally heterogeneous biomolecular systems. Here DμF was used to produce with minimal material consumption an out-of-equilibrium, fluorescently labeled biomolecular complex by rapid mixing within the droplets. TRF detection was implemented with a streak camera to monitor the time evolution of the structural heterogeneity of the complex along its relaxation towards equilibrium while it propagates inside the microfluidic channel. The approach was validated by investigating the fluorescence decay kinetics of a model interacting system of bovine serum albumin and Patent Blue V. Fluorescence decay kinetics are acquired with very good signal-to-noise ratio and allow for global, multicomponent fluorescence decay analysis, evidencing heterogeneous structural relaxation over several 100 ms.

  14. Testing UK blood donors for exposure to human parvovirus 4 using a time-resolved fluorescence immunoassay to screen sera and Western blot to confirm reactive samples.

    Science.gov (United States)

    Maple, Peter A C; Beard, Stuart; Parry, Ruth P; Brown, Kevin E

    2013-10-01

    Human parvovirus 4 (ParV4), a newly described member of the family Parvoviridae, like B19V, has been found in pooled plasma preparations. The extent, and significance, of ParV4 exposure in UK blood donors remain to be determined and reliable detection of ParV4 immunoglobulin (Ig)G, using validated methods, is needed. With ParV4 virus-like particles a ParV4 IgG time-resolved fluorescence immunoassay (TRFIA) was developed. There is no gold standard or reference assay for measuring ParV4 IgG and the utility of the TRFIA was first examined using a panel of sera from people who inject drugs (PWIDS)--a high-prevalence population for ParV4 infection. Western blotting was used to confirm the specificity of TRFIA-reactive sera. Two cohorts of UK blood donor sera comprising 452 sera collected in 1999 and 156 sera collected in 2009 were tested for ParV4 IgG. Additional testing for B19V IgG, hepatitis C virus antibodies (anti-HCV), and ParV4 DNA was also undertaken. The rate of ParV4 IgG seroprevalence in PWIDS was 20.7% and ParV4 IgG was positively associated with the presence of anti-HCV with 68.4% ParV4 IgG-positive sera testing anti-HCV-positive versus 17.1% ParV4 IgG-negative sera. Overall seropositivity for ParV4 IgG, in 608 UK blood donors was 4.76%. The ParV4 IgG seropositivity for sera collected in 1999 was 5.08%, compared to 3.84% for sera collected in 2009. No ParV4 IgG-positive blood donor sera had detectable ParV4 DNA. ParV4 IgG has been found in UK blood donors and this finding needs further investigation. © 2013 American Association of Blood Banks.

  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. 皮秒级时间分辨超快高能脉冲激光光谱%Picosecond time-resolved spectroscopy of ultrafast & high energy pulsed laser

    Institute of Scientific and Technical Information of China (English)

    王小鹏; 薛战理; 曹锋

    2012-01-01

    介绍了一种利用光电摄谱法和条纹管相结合测量ps级时间分辨超快高能脉冲激光光谱的方法.论述了条纹相机工作原理和平面衍射光栅的分光原理,分析指出利用介绍的装置,可以实现波长300 nm~1 600 nm、脉宽>2 ps超快高能脉冲激光的光谱测量.采用1 054 nm超快高能脉冲激光器,实验得到了条纹像,对条纹像进行数据处理后得到测量光谱曲线,通过能量标定后,得到了超快高能脉冲激光器实际光谱曲线,验证了ps级时间分辨超快高能脉冲激光光谱方法.讨论了系统中耦合透镜组对光谱测量和光纤色散角对条纹图像的影响,论述了ps级时间分辨超快高能脉冲激光光谱的作用.随着务纹管制造技术的飞速发展,该方法可用于fs级激光光谱的测量.%The method for measuring the spectrum of ultrafast & high energy pulsed laser in picosecond pulse width was presented with combination of photoelectrical spectrography and streak camera. The operating principle of streak camera and spectrophometric principle of plane diffraction grating were described respectively. Through thorough"analysis, we pointed out that the spectral measurement of ultrafast & high energy pulsed laser with wavelength in 300nm~1600nm and pulse width above 2 ps could be achieved by using our described facility. The streak image was obtained by utilizing ultrafast & high energy pulsed laser in 1054nm wavelength, and the measured spectral curve was derived by processing the data of streak camera, then the actual spectral curve was also given by calibrating the related energy parameters, the method for measuring the spectrum of ultrafast & high energy pulsed laser in picosecond pulse width was proved. The influence of coupling lens on measuring spectrum and grating fiber's dispersion angle on streak image were analyzed finally, furthermore the role of spectrum for ultrafast & high energy pulsed laser with picosecond pulse width was

  17. 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)

  18. Oligomerization of epidermal growth factor receptors (EGFR) on A431 cells studied by time-resolved fluorescence imaging microscopy: a stereochemical model for tyrosine kinase receptor activation

    NARCIS (Netherlands)

    Gadella, Th.W.J.; Jovin, T.M.

    1995-01-01

    The aggregation states of the epidermal growth factor receptor (EGFR) on single A431 human epidermoid carcinoma cells were assessed with two new techniques for determining fluorescence resonance en- ergy transfer: donor photobleaching fluorescence reso- nance energy transfer (pbFRET) microscopy and

  19. Oligomerization of epidermal growth factor receptors (EGFR) on A431 cells studied by time-resolved fluorescence imaging microscopy: a stereochemical model for tyrosine kinase receptor activation

    NARCIS (Netherlands)

    Th.W.J. Gadella; T.M. Jovin

    1995-01-01

    The aggregation states of the epidermal growth factor receptor (EGFR) on single A431 human epidermoid carcinoma cells were assessed with two new techniques for determining fluorescence resonance en- ergy transfer: donor photobleaching fluorescence reso- nance energy transfer (pbFRET) microscopy and

  20. Laser diagnostics in combustion. Elastic scattering and picosecond laser-induced fluorescence

    Energy Technology Data Exchange (ETDEWEB)

    Ossler, Frederik

    1999-05-01

    Elastic scattering and the Lorenz-Mie (LM) theory in particular is used for the characterization of sub-micron- and micron-sized droplets of organic fuels in sprays and aerosols. Calculations on the Lorenz-Mie theory show that backward-sideward scattered visible radiation can be used for unambiguous detection of ensembles of homogeneous droplets of organic substances with diameters around 1 micrometer (size parameter between 2 and 6). A backward feature in the polarization ratio appears with a value considerably higher than one, on the opposite to the case of the rainbow observed for larger droplets. A comparison between measurements and LM calculations showed that a large amount of droplets in aerosols and well-atomized sprays were smaller than one micrometer in diameter. The LM theory was also used to characterize different size groups in a burning spray. A 3 - D technique based on a picosecond laser and a streak camera was demonstrated for measurements of fast and turbulent biphase flows. The entire 3 - D information was obtained within a time-span of less than 15 nanoseconds. A 2 - D technique for lifetime measurements based on a picosecond laser and a streak camera has been demonstrated on static objects. An analysis indicates that the technique may be applied to measurements of lifetimes around or below one picosecond employing femtosecond lasers and femtosecond streak-cameras. The technique may in principle be used to study dynamic systems when two detectors are used. Fluorescence lifetime measurements on hydrogen and oxygen atoms in flames at atmospheric pressure demonstrate the need of lasers with suiting spectral properties such as jitter and linewidth and the need of detectors with high sensitivity in the near IR in the case of oxygen atoms. The fluorescence lifetimes of gas phase acetone and 3-pentanone at 266 nm excitation wavelength have been measured for mixtures with nitrogen and air at temperatures between 323 and 723 K and pressures between 0

  1. Laser diagnostics in combustion: Elastic scattering and picosecond laser-induced fluorescence

    Science.gov (United States)

    Ossler, Frederik E.

    Elastic scattering and the Lorenz-Mie (LM) theory in particular is used for the characterization of submicron- and micron-sized droplets of organic fuels in sprays and aerosols. Calculations on the Lorenz-Mie theory show that backward-sideward scattered visible radiation can be used for unambiguous detection of ensembles of homogeneous droplets of organic substances with diameters around 1 micrometer (size parameter between 2 and 6). A backward feature in the polarization ratio appears with a value considerably higher than one, on the opposite to the case of the rainbow observed for larger droplets. A comparison between measurements and LM calculations showed that a large amount of droplets in aerosols and well-atomized sprays were smaller than one micrometer in diameter. The LM theory was also used to characterize different size groups in a burning spray. A 3-D technique based on a picosecond laser and a streak camera was demonstrated for measurements of fast and turbulent biphase flows. The entire 3-D information was obtained within a time-span of less than 15 nanoseconds. A 2-D technique for lifetime measurements based on a picosecond laser and a streak camera has been demonstrated on static objects. An analysis indicates that the technique may be applied to measurements of lifetimes around or below one picosecond employing femtosecond lasers and femtosecond streak-cameras. The technique may in principle be used to study dynamic systems when two detectors are used. Fluorescence lifetime measurements on hydrogen and oxygen atoms in flames at atmospheric pressure demonstrate the need of lasers with suiting spectral properties such as jitter and linewidth and the need of detectors with high sensitivity in the near IR in the case of oxygen atoms. The fluorescence lifetimes of gas phase acetone and 3- pentanone at 266 nm excitation wavelength have been measured for mixtures with nitrogen and air at temperatures between 323 and 723 K and pressures between 0.01 and 10

  2. 多功能灵敏固相时间分辨荧光免疫分析仪设计%Design of a new solid-phase time-resolved fluorescence immunoassay analyzer

    Institute of Scientific and Technical Information of China (English)

    宋克非; 张佩杰

    2011-01-01

    A new solid-phase time-resolved fluorescence immunoassay analysis system has been designed for solid-phase time-resolved fluorescence spectroscopy measurements. The device uses nitrogen molecular laser as the excitation light source and employs integrating sphere combined with grating monochromator as the fluorescence collecting subsystem to minimize the influences of stray light on the sample fluorescence. Photomultiplier tube is used to convert the sampled optic signal to electronic signal and high resolution measurements of fluorescence spectrum in the range of 500 ~ 700 nm are implemented. The converted electrical signals are sampled and integrated digitally with a single chip micro-computer, which improves the signal to noise ratio of the received signal. The instrument can complete fluorescence lifetime measurement, time-resolved fluorescence spectroscopy measurement and substance concentration measurement. Experimental results show that the measurement sensitivity is up to 10 ~12 mol/L, linearity range is 10 ~'2 ~ 10 "9 mol/L, relative stability error is lass than 3% and the measurement resolution is 0. 5 nm.%针对固相时间分辨荧光光谱的测量,设计出一种全新的固相时间分辨荧光免疫分析系统.使用氮分子激光器作为激发光源,采用积分球和单色仪相结合的荧光收集结构,使杂散光对样品荧光的影响降到最低;用光电倍增管进行光电转换,在500~700 nm范围实现了高分辨荧光光谱测量;利用数字方式实现取样积分功能,提高了系统的信噪比.系统可实现荧光寿命、时间分辨荧光光谱、物质浓度的自动测量,仪器的检测灵敏度可达10 - 12 moL/L,线性范围为10-12~10-9 mol/L,稳定性相对误差小于3%,荧光光谱分辨为0.5nm.

  3. Detection of radiation-induced brain necrosis in live rats using label-free time-resolved fluorescence spectroscopy (TRFS) (Conference Presentation)

    Science.gov (United States)

    Hartl, Brad A.; Ma, Htet S. W.; Sridharan, Shamira; Hansen, Katherine; Klich, Melanie; Perks, Julian; Kent, Michael; Kim, Kyoungmi; Fragoso, Ruben; Marcu, Laura

    2017-02-01

    Differentiating radiation-induced necrosis from recurrent tumor in the brain remains a significant challenge to the neurosurgeon. Clinical imaging modalities are not able to reliably discriminate the two tissue types, making biopsy location selection and surgical management difficult. Label-free fluorescence lifetime techniques have previously been shown to be able to delineate human brain tumor from healthy tissues. Thus, fluorescence lifetime techniques represent a potential means to discriminate the two tissues in real-time during surgery. This study aims to characterize the endogenous fluorescence lifetime signatures from radiation induced brain necrosis in a tumor-free rat model. Fischer rats received a single fraction of 60 Gy of radiation to the right hemisphere using a linear accelerator. Animals underwent a terminal live surgery after gross necrosis had developed, as verified with MRI. During surgery, healthy and necrotic brain tissue was measured with a fiber optic needle connected to a multispectral fluorescence lifetime system. Measurements of the necrotic tissue showed a 48% decrease in intensity and 20% increase in lifetimes relative to healthy tissue. Using a support vector machine classifier and leave-one-out validation technique, the necrotic tissue was correctly classified with 94% sensitivity and 97% specificity. Spectral contribution analysis also confirmed that the primary source of fluorescence contrast lies within the redox and bound-unbound population shifts of nicotinamide adenine dinucleotide. A clinical trial is presently underway to measure these tissue types in humans. These results show for the first time that radiation-induced necrotic tissue in the brain contains significantly different metabolic signatures that are detectable with label-free fluorescence lifetime techniques.

  4. Multimode Surface Functional Group Determination: Combining Steady-State and Time-Resolved Fluorescence with X-ray Photoelectron Spectroscopy and Absorption Measurements for Absolute Quantification.

    Science.gov (United States)

    Fischer, Tobias; Dietrich, Paul M; Unger, Wolfgang E S; Rurack, Knut

    2016-01-19

    The quantitative determination of surface functional groups is approached in a straightforward laboratory-based method with high reliability. The application of a multimode BODIPY-type fluorescence, photometry, and X-ray photoelectron spectroscopy (XPS) label allows estimation of the labeling ratio, i.e., the ratio of functional groups carrying a label after reaction, from the elemental ratios of nitrogen and fluorine. The amount of label on the surface is quantified with UV/vis spectrophotometry based on the molar absorption coefficient as molecular property. The investigated surfaces with varying density are prepared by codeposition of 3-(aminopropyl)triethoxysilane (APTES) and cyanoethyltriethoxysilane (CETES) from vapor. These surfaces show high functional group densities that result in significant fluorescence quenching of surface-bound labels. Since alternative quantification of the label on the surface is available through XPS and photometry, a novel method to quantitatively account for fluorescence quenching based on fluorescence lifetime (τ) measurements is shown. Due to the complex distribution of τ on high-density surfaces, the stretched exponential (or Kohlrausch) function is required to determine representative mean lifetimes. The approach is extended to a commercial Rhodamine B isothiocyanate (RITC) label, clearly revealing the problems that arise from such charged labels used in conjunction with silane surfaces.

  5. In Situ Qualitative Measurement of FDOM in Water Samples by Time-Resolved Fluorescence System%时间分辨荧光法现场原位检测水体中的FDOM

    Institute of Scientific and Technical Information of China (English)

    吴芳; 陈佳宁; 孙海峰; 张振轩; 张勇

    2014-01-01

    利用激光诱导纳秒时间分辨荧光(Laser-induced nanosecond time-resolved fluorescence,LITRF)系统,建立了现场原位检测水体中的荧光溶解态有机物(Fluorescence Dissolved Organic Matter,FDOM)的方法,并将其用于近岸水域(九龙江)水样中FDOM的现场原位检测.通过与传统实验室荧光法检测结果比较,表明使用该系统可实现FDOM中类腐殖质和类蛋白质的同时现场原位检测.

  6. Time-resolved fluorescence spectroscopy investigation of the effect of 4-hydroxynonenal on endogenous NAD(P)H in living cardiac myocytes

    Science.gov (United States)

    Chorvatova, Alzbeta; Aneba, Swida; Mateasik, Anton; Chorvat, Dusan; Comte, Blandine

    2013-06-01

    Lipid peroxidation is a major biochemical consequence of the oxidative deterioration of polyunsaturated lipids in cell membranes and causes damage to membrane integrity and loss of protein function. 4-hydroxy-2-nonenal (HNE), one of the most reactive products of n-6 polyunsaturated fatty acid peroxidation of membrane phospholipids, has been shown to be capable of affecting both nicotinamide adenine dinucleotide (phosphate) reduced [NAD(P)H] as well as NADH production. However, the understanding of its effects in living cardiac cells is still lacking. Our goal was to therefore investigate HNE effects on NAD(P)H noninvasively in living cardiomyocytes. Spectrally resolved lifetime detection of endogenous fluorescence, an innovative noninvasive technique, was employed. Individual fluorescence components were resolved by spectral linear unmixing approach. Gathered results revealed that HNE reduced the amplitude of both resolved NAD(P)H components in a concentration-dependent manner. In addition, HNE increased flavoprotein fluorescence and responsiveness of the NAD(P)H component ratio to glutathione reductase (GR) inhibitor. HNE also increased the percentage of oxidized nucleotides and decreased maximal NADH production. Presented data indicate that HNE provoked an important cell oxidation by acting on NAD(P)H regulating systems in cardiomyocytes. Understanding the precise role of oxidative processes and their products in living cells is crucial for finding new noninvasive tools for biomedical diagnostics of pathophysiological states.

  7. Time-Resolved Autofluorescence Imaging of Human Donor Retina Tissue from Donors with Significant Extramacular Drusen

    Science.gov (United States)

    Schweitzer, Dietrich; Gaillard, Elizabeth R.; Dillon, James; Mullins, Robert F.; Russell, Stephen; Hoffmann, Birgit; Peters, Sven; Hammer, Martin; Biskup, Christoph

    2012-01-01

    Purpose. Time and spectrally resolved measurements of autofluorescence have the potential to monitor metabolism at the cellular level. Fluorophores that emit with the same fluorescence intensity can be discriminated from each other by decay time of fluorescence intensity after pulsed excitation. We performed time-resolved autofluorescence measurements on fundus samples from a donor with significant extramacular drusen. Methods. Tissue sections from two human donors were prepared and imaged with a laser scanning microscope. The sample was excited with a titanium-sapphire laser, which was tuned to 860 nm, and frequency doubled by a BBO crystal to 430 nm. The repetition rate was 76 MHz and the pulse width was 170 femtoseconds (fs). The time-resolved autofluorescence was recorded simultaneously in 16 spectral channels (445–605 nm) and bi-exponentially fitted. Results. RPE can be discriminated clearly from Bruch's membrane, drusen, and choroidal connective tissue by fluorescence lifetime. In RPE, bright fluorescence of lipofuscin could be detected with a maximum at 510 nm and extending beyond 600 nm. The lifetime was 385 ps. Different types of drusen were found. Most of them did not contain lipofuscin and exhibited a weak fluorescence, with a maximum at 470 nm. The lifetime was 1785 picoseconds (ps). Also, brightly emitting lesions, presumably representing basal laminar deposits, with fluorescence lifetimes longer than those recorded in RPE could be detected. Conclusions. The demonstrated differentiation of fluorescent structures by their fluorescence decay time is important for interpretation of in vivo measurements by the new fluorescence lifetime imaging (FLIM) ophthalmoscopy on healthy subjects as well as on patients. PMID:22511622

  8. A study of the time-resolved fluorescence spectrum and red edge effect of ANF in a room-temperature ionic liquid.

    Science.gov (United States)

    Hu, Zhonghan; Margulis, Claudio J

    2006-06-15

    In a recent article, we have analyzed using molecular dynamics simulations the steady-state red edge effect (REE) observed by Samanta and co-workers when the fluorescent probe 2-amino-7-nitrofluorene (ANF) is photoexcited at different wavelengths in 1-butyl-3-methylimidazolium ([BMIM+]) hexafluorophosphate ([PF6-]). In this letter, we predict the time- and wavelength-dependent emission spectra of ANF in the same ionic solvent. From the analysis of our simulated data, we are able to derive an approximate time scale for reorganization of the solvent around the solute probe. The effect that slow varying local liquid environments have on the overall time-dependent signal is also discussed.

  9. Time-Resolved Fluorescence Anisotropy of Bicyclo[1.1.1]pentane/Tolane-Based Molecular Rods Included in Tris(o-phenylenedioxy)cyclotriphosphazene (TPP).

    Science.gov (United States)

    Cipolloni, Marco; Kaleta, Jiří; Mašát, Milan; Dron, Paul I; Shen, Yongqiang; Zhao, Ke; Rogers, Charles T; Shoemaker, Richard K; Michl, Josef

    2015-04-23

    We examine the fluorescence anisotropy of rod-shaped guests held inside the channels of tris(o-phenylenedioxy)cyclotriphosphazene (TPP) host nanocrystals, characterized by powder X-ray diffraction and solid state NMR spectroscopy. We address two issues: (i) are light polarization measurements on an aqueous colloidal solution of TPP nanocrystals meaningful, or is depolarization by scattering excessive? (ii) Can measurements of the rotational mobility of the included guests be performed at low enough loading levels to suppress depolarization by intercrystallite energy transfer? We find that meaningful measurements are possible and demonstrate that the long axis of molecular rods included in TPP channels performs negligible vibrational motion.

  10. Constitutive oligomerization of human D2 dopamine receptors expressed in Spodoptera frugiperda 9 (Sf9) and in HEK293 cells. Analysis using co-immunoprecipitation and time-resolved fluorescence resonance energy transfer.

    Science.gov (United States)

    Gazi, Lucien; López-Giménez, Juan F; Rüdiger, Martin P; Strange, Philip G

    2003-10-01

    Human D2Long (D2L) and D2Short (D2S) dopamine receptor isoforms were modified at their N-terminus by the addition of a human immunodeficiency virus (HIV) or a FLAG epitope tag. The receptors were then expressed in Spodoptera frugiperda 9 (Sf9) cells using the baculovirus system, and their oligomerization was investigated by means of co-immunoprecipitation and time-resolved fluorescence resonance energy transfer (FRET). [3H]Spiperone labelled D2 receptors in membranes prepared from Sf9 cells expressing epitope-tagged D2L or D2S receptors, with a pKd value of approximately 10. Co-immunoprecipitation using antibodies specific for the tags showed constitutive homo-oligomerization of D2L and D2S receptors in Sf9 cells. When the FLAG-tagged D2S and HIV-tagged D2L receptors were co-expressed, co-immunoprecipitation showed that the two isoforms can also form hetero-oligomers in Sf9 cells. Time-resolved FRET with europium and XL665-labelled antibodies was applied to whole Sf9 cells and to membranes from Sf9 cells expressing epitope-tagged D2 receptors. In both cases, constitutive homo-oligomers were revealed for D2L and D2S isoforms. Time-resolved FRET also revealed constitutive homo-oligomers in HEK293 cells expressing FLAG-tagged D2S receptors. The D2 receptor ligands dopamine, R-(-)propylnorapomorphine, and raclopride did not affect oligomerization of D2L and D2S in Sf9 and HEK293 cells. Human D2 dopamine receptors can therefore form constitutive oligomers in Sf9 cells and in HEK293 cells that can be detected by different approaches, and D2 oligomerization in these cells is not regulated by ligands.

  11. Ultrafast time resolved vibrational spectroscopy in liquid systems

    Energy Technology Data Exchange (ETDEWEB)

    Seifert, G.; Hofmann, M.; Weidlich, K.; Graener, H. [Physics Institute, University of Bayreuth, D-95440 Bayreuth (Germany)

    1996-04-01

    The ultrafast dynamics of small molecules in the liquid phase can successfully be studied tracing the relaxation pathways of vibrational excess energy. Two complementing experimental techniques, picosecond IR double resonance spectroscopy and time resolved incoherent Anti-Stokes Raman spectroscopy, are very powerful tools for such studies. The capabilities of investigations combining these methods are discussed on the example of new experimental data on liquid dichloromethane (CH{sub 2}Cl{sub 2}). {copyright} {ital 1996 American Institute of Physics.}

  12. Time-resolved rotational spectroscopy of para-difluorobenzene·Ar

    Science.gov (United States)

    Weichert, A.; Riehn, C.; Matylitsky, V. V.; Jarzeba, W.; Brutschy, B.

    2002-07-01

    We report on time-resolved rotational spectroscopy experiments of the cluster para-difluorobenzene·Ar ( pDFB·Ar) by picosecond laser pulses in a supersonic expansion. Rotational coherences of pDFB·Ar are generated by resonant electronic excitation and probed by time-resolved fluorescence depletion spectroscopy and time-resolved photoionization ((1+1') PPI) spectroscopy. The former allows the determination of both ground and excited state rotational constants, whereas the latter technique enables the separate study of the excited state with the benefit of mass-selective detection. Since pDFB·Ar represents a near symmetric oblate rotor, persistent J-type transients with tJ≈ n/2( A+ B) could be measured. From their analysis, (A″+B″)=2234.9±2 MHz and (A'+B')=2237.9±2 MHz were obtained. A structural investigation, based on data of the pDFB monomer, is presented resulting in a pDFB·Ar center-of-mass distance of both moieties of R z=3.543±0.017 Å with a change of ΔR z=-0.057±0.009 Å upon electronic excitation. These results are compared to data of former frequency-resolved experiments and ab initio computations.

  13. Time-resolved non-contact fluorescence diffuse optical tomography measurements with ultra-fast time-correlated single photon counting avalanche photodiodes

    Science.gov (United States)

    Bérubé-Lauzière, Yves; Robichaud, Vincent; Lapointe, Éric

    2007-07-01

    The design and fabrication of time-correlated single photon counting (TCSPC) avalanche photodiodes (APDs) and associated quenching circuits have made significant progresses in recent years. APDs with temporal resolutions comparable to microchannel plate photomultiplier tubes (MCP-PMTs) are now available. MCP-PMTs were until these progresses the best TCSPC detectors with timing resolutions down to 30ps. APDs can now achieve these resolutions at a fraction of the cost. Work is under way to make the manufacturing of TCSPC APDs compatible with standard electronics fabrication practices. This should allow to further reduce their cost and render them easier to integrate in complex multi-channel TCSPC electronics, as needed in diffuse optical tomography (DOT) systems. Even if their sensitive area is much smaller than that of the ubiquitous PMT used in TCSPC, we show that with appropriate selection of optical components, TCSPC APDs can be used in time-domain DOT. To support this, we present experimental data and calculations clearly demonstrating that comparable measurements can be obtained with APDs and PMTs. We are, to our knowledge, the first group using APDs in TD DOT, in particular in non-contact TD fluorescence DOT.

  14. Time-resolved fluorescence of 2-aminopurine in DNA duplexes in the presence of the EcoP15I Type III restriction-modification enzyme.

    Science.gov (United States)

    Ma, Long; Wu, Xiaohua; Wilson, Geoffrey G; Jones, Anita C; Dryden, David T F

    2014-06-20

    EcoP15I is a Type III DNA restriction and modification enzyme of Escherichia coli. We show that it contains two modification (Mod) subunits for sequence-specific methylation of DNA and one copy of a restriction endonuclease (Res) subunit for cleavage of DNA containing unmethylated target sequences. Previously the Mod2 dimer in the presence of cofactors was shown to use nucleotide flipping to gain access to the adenine base targeted for methylation (Reddy and Rao, J. Mol. Biol. 298 (2000) 597-610.). Surprisingly the Mod2 enzyme also appeared to flip a second adenine in the target sequence, one which was not subject to methylation. We show using fluorescence lifetime measurements of the adenine analogue, 2-aminopurine, that only the methylatable adenine undergoes flipping by the complete Res1Mod2 enzyme and that this occurs even in the absence of cofactors. We suggest that this is due to activation of the Mod2 core by the Res subunit.

  15. Comparison of microenvironments of aqueous sodium dodecyl sulfate micelles in the presence of inorganic and organic salts: a time-resolved fluorescence anisotropy approach.

    Science.gov (United States)

    Dutt, G B

    2005-11-08

    Microenvironments of aqueous sodium dodecyl sulfate (SDS) micelles was examined in the presence of additives such as sodium chloride and p-toluidine hydrochloride (PTHC) by monitoring the fluorescence anisotropy decays of two hydrophobic probes, 2,5-dimethyl-1,4-dioxo-3,6-diphenylpyrrolo[3,4-c]pyrrole (DMDPP) and coumarin 6 (C6). It has been well-established that SDS micelles undergo a sphere-to-rod transition and that their mean hydrodynamic radius increases from 19 to 100 A upon the addition of 0.0-0.7 M NaCl at 298 K. A similar size and shape transition is induced by PTHC at concentrations that are 20 times lower compared to that of NaCl. This study was undertaken to find out how the microviscosity of the micelles is influenced under these circumstances. It was noticed that the microviscosity of the SDS/NaCl system increased by approximately 45%, whereas there was a less than 10% variation in the microviscosity of the SDS/PTHC system. The large increase in the microviscosity of the former system with salt concentration has been rationalized on the basis of the high concentration of sodium ions in the headgroup region of the micelles and their ability to strongly coordinate with the water present in this region, which decreases the mobility of the probe molecules.

  16. 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...

  17. 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.

  18. TIME-RESOLVED VIBRATIONAL SPECTROSCOPY

    Energy Technology Data Exchange (ETDEWEB)

    Andrei Tokmakoff, MIT (Conference Chair); Paul Champion, Northeastern University; Edwin J. Heilweil, NIST; Keith A. Nelson, MIT; Larry Ziegler, Boston University

    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 five of 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.

  19. Picosecond wide-field time-correlated single photon counting fluorescence microscopy with a delay line anode detector

    Science.gov (United States)

    Hirvonen, Liisa M.; Becker, Wolfgang; Milnes, James; Conneely, Thomas; Smietana, Stefan; Le Marois, Alix; Jagutzki, Ottmar; Suhling, Klaus

    2016-08-01

    We perform wide-field time-correlated single photon counting-based fluorescence lifetime imaging (FLIM) with a crossed delay line anode image intensifier, where the pulse propagation time yields the photon position. This microchannel plate-based detector was read out with conventional fast timing electronics and mounted on a fluorescence microscope with total internal reflection (TIR) illumination. The picosecond time resolution of this detection system combines low illumination intensity of microwatts with wide-field data collection. This is ideal for fluorescence lifetime imaging of cell membranes using TIR. We show that fluorescence lifetime images of living HeLa cells stained with membrane dye di-4-ANEPPDHQ exhibit a reduced lifetime near the coverslip in TIR compared to epifluorescence FLIM.

  20. Time-resolved molecular imaging

    Science.gov (United States)

    Xu, Junliang; Blaga, Cosmin I.; Agostini, Pierre; DiMauro, Louis F.

    2016-06-01

    Time-resolved molecular imaging is a frontier of ultrafast optical science and physical chemistry. In this article, we review present and future key spectroscopic and microscopic techniques for ultrafast imaging of molecular dynamics and show their differences and connections. The advent of femtosecond lasers and free electron x-ray lasers bring us closer to this goal, which eventually will extend our knowledge about molecular dynamics to the attosecond time domain.

  1. Engineering out motion: a surface disulfide bond alters the mobility of tryptophan 22 in cytochrome b5 as probed by time-resolved fluorescence and 1H NMR experiments.

    Science.gov (United States)

    Storch, E M; Grinstead, J S; Campbell, A P; Daggett, V; Atkins, W M

    1999-04-20

    In the accompanying paper [Storch et al. (1999) Biochemistry 38, 5054-5064] equilibrium denaturation studies and molecular dynamics (MD) simulations were used to investigate localized dynamics on the surface of cytochrome b5 (cyt b5) that result in the formation of a cleft. In those studies, an S18C:R47C disulfide mutant was engineered to inhibit cleft mobility. Temperature- and urea-induced denaturation studies revealed significant differences in Trp 22 fluorescence between the wild-type and mutant proteins. On the basis of the results, it was proposed that wild type populates a conformational ensemble that is unavailable to the disulfide mutant and is mediated by cleft mobility. As a result, the solvent accessibility of Trp 22 is decreased in S18C:R47C, suggesting that the local environment of this residue is less mobile due to the constraining effects of the disulfide on cleft dynamics. To further probe the structural effects on the local environment of Trp 22 caused by inhibition of cleft formation, we report here the results of steady-state and time-resolved fluorescence quenching, differential phase/modulation fluorescence anisotropy, and 1H NMR studies. In Trp fluorescence experiments, the Stern-Volmer quenching constant increases in wild type versus the oxidized disulfide mutant with increasing temperature. At 50 degrees C, KSV is nearly 1.5-fold greater in wild type compared to the oxidized disulfide mutant. In the reduced disulfide mutant, KSV was the same as wild type. The bimolecular collisional quenching constant, kq, for acrylamide quenching of Trp 22 increases 2.7-fold for wild type and only 1.8-fold for S18C:R47C, upon increasing the temperature from 25 to 50 degrees C. The time-resolved anisotropy decay at 25 degrees C was fit to a double-exponential decay for both the wild type and S18C:R47C. Both proteins exhibited a minor contribution from a low-amplitude fast decay, consistent with local motion of Trp 22. This component was more prevalent in

  2. Complexation of Cm(III) and Eu(III) with a hydrophilic 2,6-bis(1,2,4-triazin-3-yl)-pyridine studied by time-resolved laser fluorescence spectroscopy.

    Science.gov (United States)

    Ruff, Christian M; Müllich, Udo; Geist, Andreas; Panak, Petra J

    2012-12-28

    The complexation of Cm(III) and Eu(III) with 2,6-bis(5,6-di(sulfophenyl)-1,2,4-triazin-3-yl)pyridine (aq-BTP) is studied in water at pH 3.0 applying time-resolved laser fluorescence spectroscopy. With increasing ligand concentration [M(H(2)O)(9-3n)(aq-BTP)(n)] (M = Cm(III)/Eu(III), n = 1, 2, 3) complex species are spectroscopically identified. The conditional stability constants of the M(III) 1 : 3 complex species with aq-BTP are log β(03) = 12.2 for Cm(III) and log β(03) = 10.2 for Eu(III). The complexation reaction is enthalpy- and entropy-driven for both metal ions, while the enthalpy change ΔH(03) is 9.7 kJ mol(-1) more negative for Cm(III); changes in ΔS(03) are marginal. The difference in ΔG(03) of -12.7 kJ mol(-1) between the formation of the [M(aq-BTP)(3)] complexes agrees with aq-BTP's selectivity in liquid-liquid extraction studies.

  3. Time-resolved terahertz spectroscopy of semiconductor nanostructures

    DEFF Research Database (Denmark)

    Porte, Henrik

    of the photoconductivity is observed, due the release of carriers from the quantum dots into the conducting barrier states. Secondly, the carrier dynamics in InGaN/GaN quantum wells subject to a built-in piezoelectric eld is described. An initial fast decay of the photoconductivity as the piezoelectric eld is screened......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...

  4. Fluorescence rejection in resonance Raman spectroscopy using a picosecond-gated intensified charge-coupled device camera.

    Science.gov (United States)

    Efremov, Evtim V; Buijs, Joost B; Gooijer, Cees; Ariese, Freek

    2007-06-01

    A Raman instrument was assembled and tested that rejects typically 98-99% of background fluorescence. Use is made of short (picosecond) laser pulses and time-gated detection in order to record the Raman signals during the pulse while blocking most of the fluorescence. Our approach uses an ultrafast-gated intensified charge-coupled device (ICCD) camera as a simple and straightforward alternative to ps Kerr gating. The fluorescence rejection efficiency depends mainly on the fluorescence lifetime and on the closing speed of the gate (which is about 80 ps in our setup). A formula to calculate this rejection factor is presented. The gated intensifier can be operated at 80 MHz, so high repetition rates and low pulse energies can be used, thus minimizing photodegradation. For excitation we use a frequency-tripled or -doubled Ti : sapphire laser with a pulse width of 3 ps; it should not be shorter in view of the required spectral resolution. Other critical aspects tested include intensifier efficiency as a function of gate width, uniformity of the gate pulse across the spectrum, and spectral resolution in comparison with ungated detection. The total instrumental resolution is 7 cm(-1) in the blue and 15 cm(-1) in the ultraviolet (UV) region. The setup allows one to use resonance Raman spectroscopy (RRS) for extra sensitivity and selectivity, even in the case of strong background fluorescence. Excitation wavelengths in the visible or UV range no longer have to be avoided. The effectiveness of this setup is demonstrated on a test system: pyrene in the presence of toluene fluorescence (lambda(exc) = 257 nm). Furthermore, good time-gated RRS spectra are shown for a strongly fluorescent flavoprotein (lambda(exc) = 405 nm). Advantages and disadvantages of this approach for RRS are discussed.

  5. Research on time resolved fluorescence immunoassay in quantitative detection of the anti-HBs of children's serum%时间分辨技术定量检测儿童乙肝病毒抗-HBs水平的研究

    Institute of Scientific and Technical Information of China (English)

    程邦宁; 李林; 金载璇; 郝家砚; 孙亮; 许莉莉; 张功

    2011-01-01

    Objective To detect the anti-HBs of children's serum quantitatively, so as to analyze their immunity to hepatitis B virus (HBV). Methods Time resolved fluorescence immunoassay was used to measure the anti-HBs of 3480 serum samples from the children of non-infective HBV. Results There were 817 cases in 0~ mIU/ml about con-tent of the anti-HBs (23.5%), 1142 cases in 10-100 mlU/ml (32.8%), 1 521 cases > 100 mlU/ml (43.7%). There was no statistical difference between deferent sex of the anti-HBs (Z = 0.34,P = 0.735). There was statistical dif-ference between different age groups (Z = 3 634.00, P100 mIU/ml 1 521人(43.7%),不同性别间抗-HBs含量差异无统计学意义(Z=0.34,P=0.735);不同年龄组之间抗-HBs含量差异有统计学意义(Z=3 634.00,P<0.001),且年龄组与抗-HBs含量呈现负相关(rs=-0.217,P<0.001).结论 安徽省部分儿童对HBV的免疫力不容乐观,且随着年龄的增长,抗-HBs水平呈下降趋势,因此定期定量检测抗-HBs含量和加强乙肝疫苗预防接种非常必要.

  6. Picosecond measurements using photoacoustic detection

    Science.gov (United States)

    Heritier, J.-M.; Siegman, A. E.

    1983-01-01

    A report is presented of experimental results on picosecond time-resolved photoacoustic measurements of excited-state lifetimes, cross sections, and polarization properties for organic dye molecules in solution, using a new technique in which the total photoacoustic impulse produced by two ultrashort optical pulses with variable time delay between them is detected. The picosecond photoacoustic detection technique reported here appears to be a promising new way to observe weak excited-state cross sections and to perform picosecond lifetime measurements in a large variety of weakly absorbing and/or nonfluorescing atomic and molecular systems.

  7. Time-resolved terahertz spectroscopy in a parallel-plate waveguide

    DEFF Research Database (Denmark)

    Cooke, David; Jepsen, Peter Uhd

    2009-01-01

    Time-resolved THz spectroscopy is a powerful tool to investigate photoconductivity dynamics in a wide variety of materials with sub-picosecond resolution, all without applying contacts to the material. This technique uses coherently detected and broadband pulses of far-infrared light, known as THz...

  8. Discrimination of Crude Oil Samples Using Laser-Induced Time-Resolved Fluorescence Spectroscopy%基于激光诱导时间分辨荧光的原油识别方法研究

    Institute of Scientific and Technical Information of China (English)

    韩晓爽; 刘德庆; 栾晓宁; 郭金家; 刘永信; 郑荣儿

    2016-01-01

    在柴油、汽油、重质燃料油等成品油和原油等溢油油源的区分方面 ,荧光光谱结合模式识别手段得到了广泛的应用.传统的三维荧光光谱分析方法虽然能够获得溢油样品丰富的成分信息 ,但难以适应现场应用的要求 ,目前还停留在实验室检测的阶段.发展适用于现场应用的原油识别方法 ,对于海洋溢油污染的快速响应与处理意义重大.面向激光雷达的需要 ,发展了一种基于激光诱导时间分辨荧光手段、结合支持向量机(SVM )模型的原油识别方法 ,从时间和波长两个不同维度出发 ,通过对时间窗口和波长范围的选取进行优化 ,获得了理想的油种识别准确率.实验结果表明通过选取ICCD探测延时为54~74 ns可以将分类正确率从全谱线数据的83. 3% 提高到88. 1% .通过选取波长范围为387. 00~608. 87 nm的谱线数据 ,可将疑似油种的分类正确率从全谱线数据的84% 提高到100% .激光荧光雷达在实际工作中 ,受波浪、运载平台晃动等因素的影响 ,探测延时会出现一定的波动.本文介绍的分类识别方法通过时间和波长两个维度的筛选 ,更加适用于现场探测数据的识别 ,并进一步凸显了原油时间分辨荧光光谱特征 ,为疑似油种分类识别过程中数据量的压缩提供了重要依据.%The Laser-induced fluorescence spectra combined with pattern recognition method has been widely applied in discrimi-nation of different spilled oil ,such as diesel ,gasoline ,and crude oil .However ,traditional three-dimension fluorescence analysis method ,which is not adapted to requirement of field detection ,is limited to laboratory investigatio ns .The development of oil identification method for field detection is significant to quick response and operation of oil spill .In this paper ,a new method based on laser-induced time-resolved fluorescence combined with support vector machine (SVM ) model was introduced to dis

  9. Combined time-resolved laser fluorescence spectroscopy and extended X-ray absorption fine structure spectroscopy study on the complexation of trivalent actinides with chloride at T = 25-200 °C.

    Science.gov (United States)

    Skerencak-Frech, Andrej; Fröhlich, Daniel R; Rothe, Jörg; Dardenne, Kathy; Panak, Petra J

    2014-01-21

    The complexation of trivalent actinides (An(III)) with chloride is studied in the temperature range from 25 to 200 °C by spectroscopic methods. Time-resolved laser fluorescence spectroscopy (TRLFS) is applied to determine the thermodynamic data of Cm(III)-Cl(-) complexes, while extended X-ray absorption fine structure spectroscopy (EXAFS) is used to determine the structural data of the respective Am(III) complexes. The experiments are performed in a custom-built high-temperature cell which is modified for the respective spectroscopic technique. The TRLFS results show that at 25 °C the speciation is dominated mainly by the Cm(3+) aquo ion. Only a minor fraction of the CmCl(2+) complex is present in solution. As the temperature increases, the fraction of this species decreases further. Simultaneously, the fraction of the CmCl2(+) complex increases strongly with the temperature. Also, the CmCl3 complex is formed to a minor extent at T > 160 °C. The conditional stability constant log β'2 is determined as a function of the temperature and extrapolated to zero ionic strength with the specific ion interaction theory approach. The log β°2(T) values increase by more than 3 orders of magnitude in the studied temperature range. The temperature dependency of log β°2 is fitted by the extended van't Hoff equation to determine ΔrH°m, ΔrS°m, and ΔrC°p,m. The EXAFS results support these findings. The results confirm the absence of americium(III) chloride complexes at T = 25 and 90 °C ([Am(III)] = 10(-3) m, [Cl(-)] = 3.0 m), and the spectra are described by 9-10 oxygen atoms at a distance of 2.44-2.48 Å. At T = 200 °C two chloride ligands are present in the inner coordination sphere of Am(III) at a distance of 2.78 Å.

  10. Time-resolved imaging of latent fingerprints with nanosecond resolution

    Science.gov (United States)

    Seah, L. K.; Dinish, U. S.; Ong, S. K.; Chao, Z. X.; Murukeshan, V. M.

    2004-07-01

    Imaging of latent fingerprints using time-resolved (TR) method offers a broader platform to eliminate the unwanted background emission. In this paper, a novel TR imaging technique is demonstrated and implemented, which facilitates the detection of latent fingerprints with nanosecond resolution. Simulated experiments were carried out with two overlapping fingerprints treated with two fluorescent powders having different lifetimes in nanosecond range. The dependence of the fluorescence emission intensity in nanosecond resolution of TR imaging is also revealed.

  11. Time-resolved luminescence from quartz

    NARCIS (Netherlands)

    Chithambo, M.L.; Ankjærgaard, C.; Pagonis, V.

    2016-01-01

    Time-resolved optical stimulation of luminescence has become established as a key method for measurement of optically stimulated luminescence from quartz, feldspar and α-Al2O3:C, all materials of interest in dosimetry. The aim of time-resolved optical stimulation is to separ

  12. Determination of Dimethachlon in Tobacco by Time-resolved Fluorescence Immunoassay%时间分辨荧光免疫分析方法检测烟草中菌核净残留

    Institute of Scientific and Technical Information of China (English)

    刘媛; 刘蓉蓉; 刘贤金; 方敦煌; 宋春满; Huovinen Tuomas; Vehni(a)inen Markus; L(o)vgren Timo

    2012-01-01

    A sensitive time-resolved fluorescence immunoassay (TRFIA) with a cleanup-free pretreat-ment for dimethachlon in tobacco was developed The competitive indirect TRFIA for dimethachlon was established by using goat anti-rabbit IgG conjugated with a Eu-N1 delate as a tracer. The detection limit ( I10) and I50 for this assay was 1. 98 μg/L and 32. 00 μg/L, respectively. And the linear range for detection is between 3. 97 -128. 76 μg/L. Meanwhile, the effect of tobacco matrix to TRFIA was also studied. It was demonstrated that the linear range of inhibition curve with 1 % tobacco matrix was parallel to the standard curve; so the extract of tobacco would be diluted 200 times before assay, the index of matrix interference (Im) was calculated as 17. 1. Three levels of dimethachon (1,7 and 24 mg/L) were spiked into tobacco, the overall recoveries and the relative standard deviations (RSDs) were in the range of 73%-128% and 4. 3 -13. 2, and the practical detection limit for the method was 1 mg/L. This assay is a suitable tool for screening dimethachlon residue in tobacco samples%建立了简便、灵敏地检测烟草中菌核净残留的时间分辨荧光免疫分析方法(TRFIA),及配套的无净化的快速前处理技术.采用镧系元素螯合物Eu-N1标记亲和纯化后的羊抗兔IgG示踪抗体.采用间接竞争TRFIA法建立了菌核净标准抑制曲线,方法的检出限为2.0 μg/L;抑制终浓度I30为32.00 μg/L;检测线性范围为4~128 μg/L.考察了丙酮提取后33%,10%和1%的烟草基质对菌核净-TRFIA分析方法的影响,表明在1%烟叶基质条件下,建立的菌核净的抑制曲线的线性范围与标准抑制曲线趋于平行,确定烟草样品的前处理稀释倍数为100倍,计算得到基质影响因子(Im)为17.1.对烟叶样品中添加1,7和24 mg/L的菌核净标样,连续3d的添加回收实验表明,方法的回收率为73%~128%,相对标准标准偏差(RSD)在4.3%~13.2%之间;烟草中菌核净

  13. Probing Local Environments by Time-Resolved Stimulated Emission Spectroscopy

    Directory of Open Access Journals (Sweden)

    Ana Rei

    2012-01-01

    Full Text Available Time-resolved stimulated emission spectroscopy was employed to probe the local environment of DASPMI (4-(4-(dimethylaminostyryl-N-methyl-pyridinium iodide in binary solvents of different viscosity and in a sol-gel matrix. DASPMI is one of the molecules of choice to probe local environments, and the dependence of its fluorescence emission decay on viscosity has been previously used for this purpose in biological samples, solid matrices as well as in solution. The results presented in this paper show that time-resolved stimulated emission of DASPMI is a suitable means to probe the viscosity of local environments. Having the advantage of a higher time resolution, stimulated emission can provide information that is complementary to that obtained from fluorescence decay measurements, making it feasible to probe systems with lower viscosity.

  14. Picosecond Spin Seebeck Effect

    Science.gov (United States)

    Kimling, Johannes; Choi, Gyung-Min; Brangham, Jack T.; Matalla-Wagner, Tristan; Huebner, Torsten; Kuschel, Timo; Yang, Fengyuan; Cahill, David G.

    2017-02-01

    We report time-resolved magneto-optic Kerr effect measurements of the longitudinal spin Seebeck effect in normal metal /Y3Fe5 O12 bilayers driven by an interfacial temperature difference between electrons and magnons. The measured time evolution of spin accumulation induced by laser excitation indicates transfer of angular momentum across normal metal /Y3Fe5 O12 interfaces on a picosecond time scale, too short for contributions from a bulk temperature gradient in an yttrium iron garnet. The product of spin-mixing conductance and the interfacial spin Seebeck coefficient determined is of the order of 108 A m-2 K-1 .

  15. Picosecond spin Seebeck effect

    OpenAIRE

    Kimling, Johannes; Choi, Gyung-Min; Brangham, Jack T.; Matalla-Wagner, Tristan; Huebner, Torsten; Kuschel, Timo; Yang, Fengyuan; Cahill, David G.

    2016-01-01

    We report time-resolved magneto-optic Kerr effect measurements of the longitudinal spin Seebeck effect driven by an interfacial temperature difference between itinerant electrons and magnons. The measured time-evolution of spin accumulation induced by laser-excitation indicates transfer of angular momentum across Au/Y$_3$Fe$_5$O$_{12}$ and Cu/Y$_3$Fe$_5$O$_{12}$ interfaces on a picosecond time-scale. The product of spin-mixing conductance and interfacial spin Seebeck coefficient determined is...

  16. Study of the interaction of trivalent actinide and lanthanide ions with human serum transferrin by means of time-resolved laser-fluorescence spectroscopy; Untersuchung der Wechselwirkung trivalenter Actinid- und Lanthanidionen mit humanem Serumtransferrin mittels zeitaufgeloester Laserfluoreszenzspektroskopie

    Energy Technology Data Exchange (ETDEWEB)

    Bauer, Nicole

    2015-04-27

    In the present work the complexation of Cm(III), Eu(III) and Am(III) with human serum transferrin is studied. The aim of this work was the identification and the spectroscopic and thermodynamic characterization of An(III) and Ln(III) transferrin complex species. Different speciation methods, such as time-resolved laser fluorescence spectroscopy (TRLFS), luminescence spectroscopy and EXAFS (Extended X-Ray Absorption Fine Structure) spectroscopy were applied. Using TRLFS two unambiguously different Cm(III) transferrin species were identified for the first time. In the pH range from 3.5 to 9.7 the Cm(III) transferrin species I is formed revealing complexation of the metal ion at a nonspecific site of the protein surface. In case of the Cm(III) transferrin species II Cm(III) is bound at the Fe(III) binding site of the protein resulting in a 4-fold coordination via amino acid groups of the protein (His, Asp, 2 x Tyr) and coordination of two water molecules and three additional ligands, e.g. OH{sup -} or CO{sub 3}{sup 2-}. Due to the kinetic and thermodynamic differences of the binding sites of the N- and C-lobe, the experimental conditions ensure exclusive coordination of Cm(III) at the C-terminal binding site. In addition to the complexation studies of Cm(III) with transferrin, the interaction with the recombinant N-lobe of human serum transferrin (hTf/2N) as a model component for the transferrin N-lobe was investigated. At pH≥7.4 a Cm(III) hTf/2N species with Cm(III) bound at the Fe(III) binding site is formed which is comparable to the Cm(III) transferrin species II. An increase of the temperature from room temperature (T=296 K) to physiological temperature (T=310 K) favors the complexation of Cm(III) with both transferrin and hTf/2N. The complexation of Cm(III) with transferrin was investigated at three different carbonate concentrations (c(carbonate){sub tot}=0 mM, 0,23 mM und 25 mM (physiological carbonate concentration)). An increase of the total carbonate

  17. Time resolved thermal lens in edible oils

    Science.gov (United States)

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

    2003-01-01

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

  18. Steady-state and time-resolved Thioflavin-T fluorescence can report on morphological differences in amyloid fibrils formed by Aβ(1-40) and Aβ(1-42)

    Energy Technology Data Exchange (ETDEWEB)

    Lindberg, David J. [Department of Biology and Biological Engineering, Division of Chemical Biology, Chalmers University of Technology, Kemivägen 10, SE-41296 Gothenburg (Sweden); Wranne, Moa S.; Gilbert Gatty, Mélina [Department of Chemistry and Chemical Engineering, Division of Physical Chemistry, Chalmers University of Technology, Kemivägen 10, SE-41296 Gothenburg (Sweden); Westerlund, Fredrik [Department of Biology and Biological Engineering, Division of Chemical Biology, Chalmers University of Technology, Kemivägen 10, SE-41296 Gothenburg (Sweden); Esbjörner, Elin K., E-mail: eline@chalmers.se [Department of Biology and Biological Engineering, Division of Chemical Biology, Chalmers University of Technology, Kemivägen 10, SE-41296 Gothenburg (Sweden)

    2015-03-06

    Thioflavin-T (ThT) is one of the most commonly used dyes for amyloid detection, but the origin of its fluorescence enhancement is not fully understood. Herein we have characterised the ThT fluorescence response upon binding to the Aβ(1-40) and Aβ(1-42) variants of the Alzheimer's-related peptide amyloid-β, in order to explore how the photophysical properties of this dye relates to structural and morphological properties of two amyloid fibril types formed by peptides with a high degree of sequence homology. We show that the steady-state ThT fluorescence is 1.7 times more intense with Aβ(1-40) compared to Aβ(1-42) fibrils in concentration matched samples prepared under quiescent conditions. By measuring the excited state lifetime of bound ThT, we also demonstrate a distinct difference between the two fibril isoforms, with Aβ(1-42) fibrils producing a longer ThT fluorescence lifetime compared to Aβ(1-40). The substantial steady-state intensity difference is therefore not explained by differences in fluorescence quantum yield. Further, we find that the ThT fluorescence intensity, but not the fluorescence lifetime, is dependent on the fibril preparation method (quiescent versus agitated conditions). We therefore propose that the fluorescence lifetime is inherent to each isoform and sensitively reports on fibril microstructure in the protofilament whereas the total fluorescence intensity relates to the amount of exposed β-sheet in the mature Aβ fibrils and hence to differences in their morphology. Our results highlight the complexity of ThT fluorescence, and demonstrate its extended use in amyloid fibril characterisation. - Highlights: • ThT emission is more intense with Aβ(1-40) fibrils than with Aβ(1-42) fibrils. • Aβ(1-42) fibrils induce longer ThT fluorescence lifetimes and higher quantum yield. • ThT emission intensity in Aβ fibril samples reports on fibril morphology. • The ThT fluorescence lifetime is a characteristic feature of each A

  19. Comparison of nanosecond and picosecond excitation for interference-free two-photon laser-induced fluorescence detection of atomic hydrogen in flames.

    Science.gov (United States)

    Kulatilaka, Waruna D; Patterson, Brian D; Frank, Jonathan H; Settersten, Thomas B

    2008-09-10

    Two-photon laser-induced fluorescence (TP-LIF) line imaging of atomic hydrogen was investigated in a series of premixed CH4/O2/N2, H2/O2, and H2/O2/N2 flames using excitation with either picosecond or nanosecond pulsed lasers operating at 205 nm. Radial TP-LIF profiles were measured for a range of pulse fluences to determine the maximum interference-free signal levels and the corresponding picosecond and nanosecond laser fluences in each of 12 flames. For an interference-free measurement, the shape of the TP-LIF profile is independent of laser fluence. For larger fluences, distortions in the profile are attributed to photodissociation of H2O, CH3, and/or other combustion intermediates, and stimulated emission. In comparison with the nanosecond laser, excitation with the picosecond laser can effectively reduce the photolytic interference and produces approximately an order of magnitude larger interference-free signal in CH4/O2/N2 flames with equivalence ratios in the range of 0.5laser fluence in all flames, stimulated emission, occurring between the laser-excited level, H(n=3), and H(n=2), is the limiting factor for picosecond excitation in the flames with the highest H atom concentration. Nanosecond excitation is advantageous in the richest (Phi=1.64) CH4/O2/N2 flame and in H2/O2/N2 flames. The optimal excitation pulse width for interference-free H atom detection depends on the relative concentrations of hydrogen atoms and photolytic precursors, the flame temperature, and the laser path length within the flame.

  20. Ultrafast Time Resolved X-ray Diffraction Studies of Laser Heated Metals and Semiconductors

    Science.gov (United States)

    Chen, Peilin; Tomov, I. V.; Rentzepis, P. M.

    1998-03-01

    Time resolved hard x-ray diffraction has been employed to study the dynamics of lattice structure deformation. When laser pulse energy is deposited in a material it generates a non uniform transient temperature distribution, which alters the lattice structure of the crystal. The deformed crystal lattice will change the angle of diffraction for a monochromatic x-ray beam. We report picosecond and nanosecond time resolved x-ray diffraction measurements of the lattice temperature distribution, transient structure and stress, in Pt (111) and GaAs (111) crystals, caused by pulsed UV laser irradiation. An ArF excimer laser operated at 300 Hz was used, both, to drive an x-ray diode with copper anode and heat the crystal. Bragg diffracted x-ray radiation was recorded by a direct imaging x-ray CCD. Changes in the diffraction patterns induced by a few millijouls pulse energy were observed at different time delays between the laser heating pulse and the x-ray probing pulse. A kinematical model for time resolved x-ray diffraction was used to analyze the experimental data. Good agreement between the measured and calculated scattered x-ray intensities profiles was achieved, indicating that detailed time resolved x-ray diffraction measurements can be made with nanosecond and picosecond resolution for small temperature changes. Our system can detect changes in the lattice spacing of about 10-3 A.

  1. 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

  2. 基于稀土铕离子配合物的时间分辨荧光pH 探针的合成及应用%The Synthesis and Application of Time-Resolved Fluorescence pH Probe Based on Rare Earth Europium Ion Complex

    Institute of Scientific and Technical Information of China (English)

    黄大伟; 邴永鑫; 洪伟; 崔恺; 虢清伟

    2016-01-01

    A rare earth ternary europium ion complex with fluorescent lifetime of 0.544 0 ms was synthesized by using 4,7-diphenyl-1,10-phenanthroline and 2-thenoyltrifluoroacetone as synergic agents andβ-diketone ligands. The complex was used as fluorescent probe for pH determination of environmental water samples by time-resolved fluorescence analysis.The fluorescent probe showed the maximum and stable time-resolved fluorescence intensity when the pH ranged from 7.00 to 8.95,while the time-resolved fluorescence intensity changed obviously in acidic (pH 8.95 )conditions.The time-resolved fluorescence quenching of the fluorescent probe showed linear response toward pH in the range of 2.50-7.00 or 9.91 -14.00.The prepared fluorescent probe was insensitive to dissolved oxygen and ionic strength.The prepared fluorescent probe was used to determine pH of real water samples,giving results in consistent with those obtained by glass electrode and RSDs (n=8)in the range of 4.3%-8.1%.%以4,7-二苯基-1,10-菲啉(母体)和2-噻吩甲酰三氟丙酮为协同剂和β-二酮配体,合成了一种稀土三元铕离子配合物,其荧光寿命为0.5440 ms,并以其为荧光探针对水环境的 pH 进行时间分辨荧光测定。荧光探针的时间分辨荧光强度在 pH 7.00~8.95时达到最大值并保持较好的稳定性;在 pH 小于7.00和 pH 大于8.95时,荧光探针的时间分辨荧光强度随着 pH 变化而变化;在 pH 2.50~7.00和 pH 9.91~14.00时,荧光探针的时间分辨荧光猝灭率与 pH 呈线性关系。溶解氧浓度和离子强度变化对 pH 测定结果无影响。采用荧光探针测定实际水样的 pH,结果与玻璃电极的测定结果相符,测定值的相对标准偏差(n=8)在4.3%~8.1%之间。

  3. Comparison of the rate constants for energy transfer in the light-harvesting protein, C-phycocyanin, calculated from Foerster`s theory and experimentally measured by time-resolved fluorescence spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Debreczeny, M.P.

    1994-05-01

    We have measured and assigned rate constants for energy transfer between chromophores in the light-harvesting protein C-phycocyanin (PC), in the monomeric and trimeric aggregation states, isolated from Synechococcus sp. PCC 7002. In order to compare the measured rate constants with those predicted by Fdrster`s theory of inductive resonance in the weak coupling limit, we have experimentally resolved several properties of the three chromophore types ({beta}{sub 155} {alpha}{sub 84}, {beta}{sub 84}) found in PC monomers, including absorption and fluorescence spectra, extinction coefficients, fluorescence quantum yields, and fluorescence lifetimes. The cpcB/C155S mutant, whose PC is missing the {beta}{sub 155} chromophore, was, useful in effecting the resolution of the chromophore properties and in assigning the experimentally observed rate constants for energy transfer to specific pathways.

  4. 异丙醇-水配合液的荧光偏振和时间分辨特性%Fluorescence Polarization and Time Resolved Characteristics of Isopropanol-water Mixture

    Institute of Scientific and Technical Information of China (English)

    韩彩芹; 段培同; 吴斌; 刘莹; 骆晓森; 倪晓武

    2011-01-01

    The polarization fluorescence spectra of isopropanol-water mixture excited by ultraviolet light was studied experimentally. The decay process of fluorescence intensity was detected at different center emission peaks. The curve was fitted by an exponential function and the processing data was obtained by deconvolution. Both the polarization degree and fluorescence lifetime were calculated, and mathematical characterization was performed for the fluorescence counts decay curves. The fluorescence emission and polarization characteristics were discussed. It is found that the isopropanol-water mixture excited by ultraviolet light obtains partially polarized fluorescence with certain molecular orientation. The polarization degree and anisotropy degree are 0.542 and 0.441, respectively. Induced by exciting light with wavelengths of 220 nm and 232 nm, the fluorescence lifetime of isopropanol-water mixture at peaks of 277, 284, 293,309 nm is about 17 ns. While the average fluorescence lifetime at peaks of 328 nm, 345 nm and 362 nm is around 21, 22, 16 ns, respectively. It is related with the molecular cluster structure relative stability of isopropanol-water mixture by the action of hydrogen bond. The research will contribute to the study of the molecular characteristic of isopropanol-water cluster.%研究了紫外光照射下异丙醇-水配合液的偏振荧光光谱,以及不同荧光峰处光子强度随时间的衰变过程,计算了偏振度并讨论了其偏振特性,测试了不同峰位对应的荧光寿命并分析了其荧光发射特性.结果表明,异丙醇-水配合液在紫外光激励下发射的荧光为具有确定分子取向的部分偏振光,偏振度和各向异性度分别为0.542和0.441.在波长为220 nm和232 nm的激发光照射下,荧光峰位于277,284,293,309 nm,对应寿命均约为17 ns.而328,345,362 nm荧光峰对应的平均寿命分别约为21,22,16 ns,这与氢键作用下异丙醇和水形成团簇结构的相对稳定性有关.

  5. Time-resolved photoluminescence spectroscopy of organic-plasmonic hybrids

    DEFF Research Database (Denmark)

    Leißner, Till; Brewer, Jonathan R.; Fiutowski, Jacek

    We study the optical properties of organic thin films and crystalline organic nanofibers as well as their interaction with plasmonic materials by means of laser-scanning fluorescence lifetime imaging microscopy (FLIM) and time-resolved photoluminescence spectroscopy (TR-PLS). The aim of our......-carrier dynamics in such systems. In this contribution we will show how the interaction of organic nanofibers placed on top of regular arrays of nanostructures leads to a significantly enhanced second-harmonic response and, at the same time, an increased decay rate of the photoluminescence lifetime....

  6. Natural killer cell cytotoxicity assay with time-resolved fluorimetry

    Institute of Scientific and Technical Information of China (English)

    李建中; 章竹君; 金伯泉; 田方

    1996-01-01

    A new time-resolved fluorimetric method for the measurement of natural killer (NK) cell cytotoxicity has been developed by labelling the target cell K562 with a new synthesized fluorescence marker KLUK. The method has advantages of higher sensitivity, time-saving, good reproducibility and has no radioactivity problems. A satisfactory result is obtained by comparing it with 51Cr release method. It demonstrates that the new marker provides an alternative to currently used radioactive markers for the assessment of in vitro cellular cytotoxicity.

  7. Time-resolved photoemission using attosecond streaking

    CERN Document Server

    Nagele, Stefan; Wais, Michael; Wachter, Georg; Burgdörfer, Joachim

    2014-01-01

    We theoretically study time-resolved photoemission in atoms as probed by attosecond streaking. We review recent advances in the study of the photoelectric effect in the time domain and show that the experimentally accessible time shifts can be decomposed into distinct contributions that stem from the field-free photoionization process itself and from probe-field induced corrections. We perform accurate quantum-mechanical as well as classical simulations of attosecond streaking for effective one-electron systems and determine all relevant contributions to the time delay with attosecond precision. In particular, we investigate the properties and limitations of attosecond streaking for the transition from short-ranged potentials (photodetachment) to long-ranged Coulomb potentials (photoionization). As an example for a more complex system, we study time-resolved photoionization for endohedral fullerenes $A$@$\\text{C}_{60}$ and discuss how streaking time shifts are modified due to the interaction of the $\\text{C}_...

  8. Time-resolved photoemission using attosecond streaking

    Science.gov (United States)

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

    2014-04-01

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

  9. 原油样品激光诱导荧光的时间分辨光谱特性研究%Characterization of Time-Resolved Laser-Induced Fluorescence from Crude Oil Samples

    Institute of Scientific and Technical Information of China (English)

    刘德庆; 栾晓宁; 韩晓爽; 郭金家; 安居白; 郑荣儿

    2015-01-01

    为探索激光诱导时间分辨荧光光谱技术应用于海洋悬浮溢油原位探测的可行性,对来自胜利油田六个不同井区不同密度的原油样品的时间分辨荧光光谱进行了探测分析。结果发现,各原油样品荧光发射的持续时间基本相同,从ICCD中数字延时发生器(DDG )的输入延时52 ns开始,到输入延时82 ns左右结束,各原油样品的荧光峰强度随时间变化曲线的半高宽约10 ns;不同原油样品的最强荧光峰位及其衰减寿命不尽相同,并且与样品密度有一定相关性,密度相近的原油具有相近的最强荧光峰位和相似的荧光寿命。对比六种原油样品的时间分辨荧光光谱发现,在荧光增强时,原油荧光光谱峰位不变,当荧光从最大强度开始衰减时,六种原油样品的荧光光谱峰位均出现了不同程度(17~30 nm )的红移现象,这一定程度上反映出原油中各荧光组分的荧光衰减速率存在差异,或者存在荧光组分之间的能量传递。所观测到的原油密度相关的时间分辨光谱信息和荧光峰红移现象可望成为水下悬浮溢油识别的有效特征之一。%To evaluate the feasibility of laser induced time‐resolved fluorescence technique for in‐situ detection of underwater sus‐pended oil spill ,extensive investigations have been carried out with different densities of crude oil samples from six different wells of Shengli Oilfield in this work .It was found that the fluorescence emission durations of these crude oil samples were al‐most the same ,the Gate Pulse Delay of DDG (Digital Delay Generator ) in the ICCD started at 52ns and ended at 82ns with a width (FWHM ) of 10 ns .It appears that the peak location and lifetime of fluorescence for different crude oil samples varied with their densities ,and those with similar densities shared a similar lifespan with the closer peak locations of fluorescence .It is also observed that

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

    Science.gov (United States)

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

    2015-03-17

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

  11. Time resolved spectroscopic studies on some nanophosphors

    Indian Academy of Sciences (India)

    Harish Chander; Santa Chawla

    2008-06-01

    Time resolved spectroscopy is an important tool for studying photophysical processes in phosphors. Present work investigates the steady state and time resolved photoluminescence (PL) spectroscopic characteristics of ZnS, ZnO and (Zn, Mg)O nanophosphors both in powder as well as thin film form. Photoluminescence (PL) of ZnS nanophosphors typically exhibit a purple/blue emission peak termed as self activated (SA) luminescence and emission at different wavelengths arising due to dopant impurities e.g. green emission for ZnS : Cu, orange emission for ZnS : Mn and red emission for ZnS : Eu. The lifetimes obtained from decay curves range from ns to ms level and suggest the radiative recombination path involving donor–acceptor pair recombination or internal electronic transitions of the impurity atom. A series of ZnMgO nanophosphor thin films with varied Zn : Mg ratios were prepared by chemical bath deposition. Photoluminescence (PL) excitation and emission spectra exhibit variations with changing Mg ratio. Luminescence lifetime as short as 10-10 s was observed for ZnO and ZnMgO (100 : 10) nanophosphors. With increasing Mg ratio, PL decay shifts into microsecond range. ZnO and ZnMgO alloys up to 50% Mg were prepared as powder by solid state mixing and sintering at high temperature in reducing atmosphere. Time resolved decay of PL indicated lifetime in the microsecond time scale. The novelty of the work lies in clear experimental evidence of dopants (Cu, Mn, Eu and Mg) in the decay process and luminescence life times in II–VI semiconductor nanocrystals of ZnS and ZnO. For ZnS, blue self activated luminescence decays faster than Cu and Mn related emission. For undoped ZnO nanocrystals, PL decay is in the nanosecond range whereas with Mg doping the decay becomes much slower in the microsecond range.

  12. Time-resolved photoelectron spectroscopy of a dinuclear Pt(II) complex: Tunneling autodetachment from both singlet and triplet excited states of a molecular dianion

    Science.gov (United States)

    Winghart, Marc-Oliver; Yang, Ji-Ping; Vonderach, Matthias; Unterreiner, Andreas-Neil; Huang, Dao-Ling; Wang, Lai-Sheng; Kruppa, Sebastian; Riehn, Christoph; Kappes, Manfred M.

    2016-02-01

    Time-resolved pump-probe photoelectron spectroscopy has been used to study the relaxation dynamics of gaseous [Pt2(μ-P2O5H2)4 + 2H]2- after population of its first singlet excited state by 388 nm femtosecond laser irradiation. In contrast to the fluorescence and phosphorescence observed in condensed phase, a significant fraction of the photoexcited isolated dianions decays by electron loss to form the corresponding monoanions. Our transient photoelectron data reveal an ultrafast decay of the initially excited singlet 1A2u state and concomitant rise in population of the triplet 3A2u state, via sub-picosecond intersystem crossing (ISC). We find that both of the electronically excited states are metastably bound behind a repulsive Coulomb barrier and can decay via delayed autodetachment to yield electrons with characteristic kinetic energies. While excited state tunneling detachment (ESETD) from the singlet 1A2u state takes only a few picoseconds, ESETD from the triplet 3A2u state is much slower and proceeds on a time scale of hundreds of nanoseconds. The ISC rate in the gas phase is significantly higher than in solution, which can be rationalized in terms of changes to the energy dissipation mechanism in the absence of solvent molecules. [Pt2(μ-P2O5H2)4 + 2H]2- is the first example of a photoexcited multianion for which ESETD has been observed following ISC.

  13. Control and femtosecond time-resolved imaging of torsion in a chiral molecule

    CERN Document Server

    Hansen, Jonas L; Madsen, Christian Bruun; Lindhardt, Anders Thyboe; Johansson, Mikael P; Skrydstrup, Troels; Madsen, Lars Bojer; Stapelfeldt, Henrik

    2012-01-01

    We study how the combination of long and short laser pulses, can be used to induce torsion in an axially chiral biphenyl derivative (3,5-difluoro-3',5'-dibromo-4'-cyanobiphenyl). A long, with respect to the molecular rotational periods, elliptically polarized laser pulse produces 3D alignment of the molecules, and a linearly polarized short pulse initiates torsion about the stereogenic axis. The torsional motion is monitored in real-time by measuring the dihedral angle using femtosecond time-resolved Coulomb explosion imaging. Within the first 4 picoseconds, torsion occurs with a period of 1.25 picoseconds and an amplitude of 3 degrees in excellent agreement with theoretical calculations. At larger times the quantum states of the molecules describing the torsional motion dephase and an almost isotropic distribution of the dihedral angle is measured. We demonstrate an original application of covariance analysis of two-dimensional ion images to reveal strong correlations between specific ejected ionic fragments...

  14. Space-Time Resolved Capillary Wave Turbulence

    CERN Document Server

    Berhanu, Michael

    2012-01-01

    We report experiments on the full space and time resolved statistics of capillary wave turbulence at the air-water interface. The three-dimensional shape of the free interface is measured as a function of time by using the optical method of Diffusing Light Photography associated with a fast camera. Linear and nonlinear dispersion relations are extracted from the spatio-temporal power spectrum of wave amplitude. When wave turbulence regime is reached, we observe power-law spectra both in frequency and in wave number, whose exponents are found in agreement with the predictions of capillary wave turbulence theory. Finally, the temporal dynamics of the spatial energy spectrum highlights the occurrence of stochastic bursts transferring wave energy through the spatial scales.

  15. 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 photoconduct......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...

  16. 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

    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......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...

  17. Time resolved studies of bond activation by organometallic complexes

    Energy Technology Data Exchange (ETDEWEB)

    Wilkens, M J [Univ. of California, Berkeley, CA (United States). Dept. of Chemistry

    1998-05-01

    In 1971, Jetz and Graham discovered that the silicon-hydrogen bond in silanes could be broken under mild photochemical conditions in the presence of certain transition metal carbonyls. Such reactions fall within the class of oxidative addition. A decade later, similar reactivity was discovered in alkanes. In these cases a C-H bond in non-functionalized alkanes was broken through the oxidative addition of Cp*Ir(H){sub 2}L (Cp* = (CH{sub 3}){sub 5}C{sub 5}, L = PPh{sub 3}, Ph = C{sub 6}H{sub 5}) to form Cp*ML(R)(H) or of Cp*Ir(CO){sub 2} to form Cp*Ir(CO)(R)(H). These discoveries opened an entirely new field of research, one which naturally included mechanistic studies aimed at elucidating the various paths involved in these and related reactions. Much was learned from these experiments but they shared the disadvantage of studying under highly non-standard conditions a system which is of interest largely because of its characteristics under standard conditions. Ultrafast time-resolved IR spectroscopy provides an ideal solution to this problem; because it allows the resolution of chemical events taking place on the femto-through picosecond time scale, it is possible to study this important class of reactions under the ambient conditions which are most of interest to the practicing synthetic chemist. Certain of the molecules in question are particularly well-suited to study using the ultrafast IR spectrophotometer described in the experimental section because they contain one or more carbonyl ligands.

  18. Time resolved studies of bond activation by organometallic complexes

    Energy Technology Data Exchange (ETDEWEB)

    Wilkens, Matthew J. [Univ. of California, Berkeley, CA (United States). Dept. of Chemistry

    1998-05-01

    In 1971, Jetz and Graham discovered that the silicon-hydrogen bond in silanes could be broken under mild photochemical conditions in the presence of certain transition metal carbonyls. Such reactions fall within the class of oxidative addition. A decade later, similar reactivity was discovered in alkanes. In these cases a C-H bond in non-functionalized alkanes was broken through the oxidative addition of Cp*Ir(H)2L (Cp* = (CH3)5C5, L = PPh3, Ph = C6H5) to form Cp*ML(R)(H) or of Cp*Ir(CO)2 to form Cp*Ir(CO)(R)(H). These discoveries opened an entirely new field of research, one which naturally included mechanistic studies aimed at elucidating the various paths involved in these and related reactions. Much was learned from these experiments but they shared the disadvantage of studying under highly non-standard conditions a system which is of interest largely because of its characteristics under standard conditions. Ultrafast time-resolved IR spectroscopy provides an ideal solution to this problem; because it allows the resolution of chemical events taking place on the femto-through picosecond time scale, it is possible to study this important class of reactions under the ambient conditions which are most of interest to the practicing synthetic chemist. Certain of the molecules in question are particularly well-suited to study using the ultrafast IR spectrophotometer described in the experimental section because they contain one or more carbonyl ligands.

  19. Picosecond calorimetry

    DEFF Research Database (Denmark)

    Georgiou, Panayiotis; Vincent, Jonathan; Andersson, Magnus

    2006-01-01

    Liquid phase time-resolved x-ray diffraction with 100 ps resolution has recently emerged as a powerful technique for probing the structural dynamics of transient photochemical species in solution. It is intrinsic to the method, however, that a structural signal is observed not only from the photo...

  20. Time-Resolved Single-State Measurements of the Electronic Structure of Isochoric Heated Copper

    Energy Technology Data Exchange (ETDEWEB)

    Nelson, A J; Dunn, J; Widmann, K; Ao, T; Ping, Y; Hunter, J; Ng, A

    2004-10-22

    Time-resolved x-ray photoelectron spectroscopy is used to probe the non-steady-state evolution of the valence band electronic structure of laser heated ultra-thin (50 nm) Cu. Single-shot x-ray laser induced time-of-flight photoelectron spectroscopy with picosecond time resolution is used in conjunction with optical measurements of the disassembly dynamics that have shown the existence of a metastable liquid phase in fs-laser heated Cu foils persisting 4-5 ps. This 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 500 x 700 {micro}m{sup 2} spot to create heated conditions of 0.07-1.8 x 10{sup 12} W cm{sup -2} intensity. Valence band photoemission spectra showing the changing occupancy of the Cu 3d level with heating are presented. These are the first picosecond x-ray laser time-resolved photoemission spectra of laser-heated ultra-thin Cu foil showing changes in electronic structure. The ultrafast nature of this technique lends itself to true single-state measurements of shocked and heated materials.

  1. Advancements in time-resolved x-ray laser induced time-of-flight photoelectron spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Nelson, A J; Dunn, J; Widmann, K; Ao, T; Ping, Y; Hunter, J; Ng, A

    2005-07-28

    Time-resolved soft x-ray photoelectron spectroscopy is used to probe the non-steady-state evolution of the valence band electronic structure of laser heated ultra-thin (50 nm) metal foils and bulk semiconductors. Single-shot soft x-ray laser induced time-of-flight photoelectron spectroscopy with picosecond time resolution was used in combination with optical measurements of the disassembly dynamics that have shown the existence of a metastable liquid phase in fs-laser heated metal foils persisting 4-5 ps. This metastable phase is studied using a 527 nm wavelength 400 fs laser pulse containing 0.3-2.5 mJ laser energy focused in a large 500 x 700 {micro}m{sup 2} spot to create heated conditions of 0.2-1.8 x 10{sup 12} W cm{sup -2} intensity. The unique LLNL COMET compact tabletop soft x-ray laser source provided the necessary high photon flux, highly monoenergetic, picosecond pulse duration, and coherence for observing the evolution of changes in the valence band electronic structure of laser heated metals and semiconductors with picosecond time resolution. This work demonstrates the continuing development of a powerful new technique for probing reaction dynamics and changes of local order on surfaces on their fundamental timescales including phenomena such as non-thermal melting, chemical bond formation, intermediate reaction steps, and the existence of transient reaction products.

  2. 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.

  3. Time-resolved spectroscopy using synchrotron radiation

    Energy Technology Data Exchange (ETDEWEB)

    Poliakoff, E.D.

    1979-08-01

    Work performed at the Stanford Synchrotron Radiation Laboratory (SSRL) is reported. The timing characteristics of the SPEAR beam (pulse width less than or equal to 0.4 nsec, pulse repetition period = 780 nsec) were exploited to determine dynamic behavior of atomic, molecular, excimeric, and photodissociative gas-phase species excited by vacuum-ultraviolet (VUV) radiation. Fast fluorescence timing measurements were done to determine excited-state lifetimes of Kr and Xe. Pressure-dependent timing studies on Xe gas at higher concentrations demonstrated some of the problems associated with previous kinetic modeling of the Xe/sub 2/ system. It was found that even qualitative agreement of observed Xe/sub 2/ lifetimes as a function of pressure required the assumption that the radiative lifetime was a strong function of internuclear separation. The radiative decays of chemically unstable fragments, CN* (B/sup 2/..sigma../sup +/) and XeF* (B/sup 2/..sigma../sup +/ and C/sup 2/ Pi/sub 3/2//), were studied by pulsed photodissociation of stable parent compounds, ICN and XeF/sub 2/. When the polarization of the CN* (B/sup 2/..sigma../sup +/) fragment fluorescence was measured, it was found to be non-zero and strongly dependent on excitation wavelength. This polarization is related to the symmetry of the photodissociative surface via a classical model, and the variations in the polarization with wavelength is attributed to symmetry and lifetime effects of a predissociating parent molecule. Despite the drawbacks of limited availability and low radiation flux, synchrotron radiation is definitely a useful spectroscopic tool for VUV studies of gas-phase systems.

  4. Two-photon excitation with pico-second fluorescence lifetime imaging to detect nuclear association of flavanols.

    Science.gov (United States)

    Mueller-Harvey, Irene; Feucht, Walter; Polster, Juergen; Trnková, Lucie; Burgos, Pierre; Parker, Anthony W; Botchway, Stanley W

    2012-03-16

    Two-photon excitation enabled for the first time the observation and measurement of excited state fluorescence lifetimes from three flavanols in solution, which were ~1.0 ns for catechin and epicatechin, but <45 ps for epigallocatechin gallate (EGCG). The shorter lifetime for EGCG is in line with a lower fluorescence quantum yield of 0.003 compared to catechin (0.015) and epicatechin (0.018). In vivo experiments with onion cells demonstrated that tryptophan and quercetin, which tend to be major contributors of background fluorescence in plant cells, have sufficiently low cross sections for two-photon excitation at 630 nm and therefore do not interfere with detection of externally added or endogenous flavanols in Allium cepa or Taxus baccata cells. Applying two-photon excitation to flavanols enabled 3-D fluorescence lifetime imaging microscopy and showed that added EGCG penetrated the whole nucleus of onion cells. Interestingly, EGCG and catechin showed different lifetime behaviour when bound to the nucleus: EGCG lifetime increased from <45 to 200 ps, whilst catechin lifetime decreased from 1.0 ns to 500 ps. Semi-quantitative measurements revealed that the relative ratios of EGCG concentrations in nucleoli associated vesicles: nucleus: cytoplasm were ca. 100:10:1. Solution experiments with catechin, epicatechin and histone proteins provided preliminary evidence, via the appearance of a second lifetime (τ(2)=1.9-3.1 ns), that both flavanols may be interacting with histone proteins. We conclude that there is significant nuclear absorption of flavanols. This advanced imaging using two-photon excitation and biophysical techniques described here will prove valuable for probing the intracellular trafficking and functions of flavanols, such as EGCG, which is the major flavanol of green tea.

  5. Two-photon excitation with pico-second fluorescence lifetime imaging to detect nuclear association of flavanols

    Energy Technology Data Exchange (ETDEWEB)

    Mueller-Harvey, Irene, E-mail: i.mueller-harvey@reading.ac.uk [Chemistry and Biochemistry Laboratory, Food Production and Quality Research Division, School of Agriculture, Policy and Development, University of Reading, P O Box 236, Reading RG6 6AT (United Kingdom); Feucht, Walter, E-mail: walter.feucht@gmail.com [Department of Plant Sciences, Technical University of Munich (TUM), Wissenschaftszentrum Weihenstephan (WZW), D-85354 Freising (Germany); Polster, Juergen, E-mail: j.polster@wzw.tum.de [Department of Physical Biochemistry, Technical University of Munich (TUM), Wissenschaftszentrum Weihenstephan (WZW), D-85354 Freising (Germany); Trnkova, Lucie, E-mail: lucie.trnkova@uhk.cz [University of Hradec Kralove, Faculty of Science, Department of Chemistry, Rokitanskeho 62, 50003 Hradec Kralove (Czech Republic); Burgos, Pierre, E-mail: pierre.burgos@stfc.ac.uk [Central Laser Facility, Research Complex at Harwell, Science and Technology Facilities Council, Rutherford Appleton Laboratory, Harwell-Oxford, Didcot, Oxfordshire, OX11 0QX (United Kingdom); Parker, Anthony W., E-mail: tony.parker@stfc.ac.uk [Central Laser Facility, Research Complex at Harwell, Science and Technology Facilities Council, Rutherford Appleton Laboratory, Harwell-Oxford, Didcot, Oxfordshire, OX11 0QX (United Kingdom); Botchway, Stanley W., E-mail: stan.botchway@stfc.ac.uk [Central Laser Facility, Research Complex at Harwell, Science and Technology Facilities Council, Rutherford Appleton Laboratory, Harwell-Oxford, Didcot, Oxfordshire, OX11 0QX (United Kingdom)

    2012-03-16

    Highlights: Black-Right-Pointing-Pointer This fluorescence lifetime imaging microscopy (FLIM) technique for flavanols overcomes autofluorescence interference in cells. Black-Right-Pointing-Pointer Plant flavanols differed in their lifetimes. Black-Right-Pointing-Pointer Dissolved and bound flavanols revealed contrasting lifetime changes. Black-Right-Pointing-Pointer This technique will allow studying of flavanol trafficking in live cells. - Abstract: Two-photon excitation enabled for the first time the observation and measurement of excited state fluorescence lifetimes from three flavanols in solution, which were {approx}1.0 ns for catechin and epicatechin, but <45 ps for epigallocatechin gallate (EGCG). The shorter lifetime for EGCG is in line with a lower fluorescence quantum yield of 0.003 compared to catechin (0.015) and epicatechin (0.018). In vivo experiments with onion cells demonstrated that tryptophan and quercetin, which tend to be major contributors of background fluorescence in plant cells, have sufficiently low cross sections for two-photon excitation at 630 nm and therefore do not interfere with detection of externally added or endogenous flavanols in Allium cepa or Taxus baccata cells. Applying two-photon excitation to flavanols enabled 3-D fluorescence lifetime imaging microscopy and showed that added EGCG penetrated the whole nucleus of onion cells. Interestingly, EGCG and catechin showed different lifetime behaviour when bound to the nucleus: EGCG lifetime increased from <45 to 200 ps, whilst catechin lifetime decreased from 1.0 ns to 500 ps. Semi-quantitative measurements revealed that the relative ratios of EGCG concentrations in nucleoli associated vesicles: nucleus: cytoplasm were ca. 100:10:1. Solution experiments with catechin, epicatechin and histone proteins provided preliminary evidence, via the appearance of a second lifetime ({tau}{sub 2} = 1.9-3.1 ns), that both flavanols may be interacting with histone proteins. We conclude that there

  6. Steady state and time-resolved autofluorescence studies of human colonic tissues

    Institute of Scientific and Technical Information of China (English)

    Buhong Li; Zhenxi Zhang; Shusen Xie

    2006-01-01

    Steady state and time-resolved autofluorescence spectroscopies are employed to study the autofluorescence characteristics of human colonic tissues in vitro. The excitation wavelength varies from 260 to 540 nm, and the corresponding fluorescence emission spectra are acquired from 280 to 800 nm. Significant difference in fluorescence intensity of excitation-emission matrices (EEMs) is observed between normal and tumor colonic tissues. Compared with normal colonic tissue, low nicotinamide adenine dinucleotide (phosphate) (NAD(P)H) and flavin adenine dinucleotide (FAD), and high amino acids and protoporphyrin Ⅸ (PpⅨ) fluorescences characterize high-grade malignant tissue. Moreover, the autofluorescence lifetimes of normal and carcinomatous colonic tissues at 635 nm under 397-nm excitation are about 4.32±0.12 and 18.45±0.05 ns, respectively. The high accumulation of endogenous PpⅨ in colonic cancers is demonstrated in both steady state and time-resolved autofluorescence spectroscopies.

  7. Time-resolved spectral analysis of Radachlorin luminescence in water

    Science.gov (United States)

    Belik, V. P.; Gadzhiev, I. M.; Semenova, I. V.; Vasyutinskii, O. S.

    2017-05-01

    We report results of spectral- and time-resolved study of Radachlorin photosensitizer luminescence in water in the spectral range of 950-1350nm and for determination of the photosensitizer triplet state and the singlet oxygen lifetimes responsible for singlet oxygen generation and degradation. At any wavelength within the explored spectral range the luminescence decay contained two major contributions: a fast decay at the ns time scale and a slow evolution at the μs time scale. The fast decay was attributed to electric dipole fluorescence transitions in photosensitizer molecules and the slow evolution to intercombination phosphorescence transitions in singlet oxygen and photosensitizer molecules. Relatively high-amplitude ns peak observed at all wavelengths suggests that singlet oxygen monitoring with spectral isolation methods alone, without additional temporal resolution can be controversial. In the applied experimental conditions the total phosphorescence signal at any wavelength contained a contribution from the photosensitizer triplet state decay, while at 1274nm the singlet oxygen phosphorescence dominated. The results obtained can be used for optimization of the methods of singlet oxygen monitoring and imaging.

  8. Novel aspects of fluorescence lifetime for molecules positioned close to metal surfaces

    Science.gov (United States)

    Aussenegg, F. R.; Leitner, A.; Lippitsch, M. E.; Reinisch, H.; Riegler, M.

    1987-10-01

    On metal surfaces with submicroscopic corrugations, surface-enhanced optical processes can be observed. Results obtained by picosecond time-resolved fluorescence spectroscopy for dye molecules in the proximity (0-50 nm) of silver islands films are reported. It is demonstrated how the rather complex dependence of the integral fluorescence intensity on the distance dye-islands, can be resolved in the contributions of different mechanisms by analysing the fluorescence decay curves at various distances. It turns out, that the enhancement of absorption influences only the peak fluorescence intensity without changing the decay time, while the enhancement of emission and dissipative losses reduces the decay time. Thus time-resolved spectroscopy opens the possibility to test theoretical concepts on surface enhancement and provides basic data for tailoring molecule-metal structures with well-defined surface-enhancement properties.

  9. Fluorescence and picosecond induced absorption from the lowest singlet excited states of quercetin in solutions and polymer films

    Science.gov (United States)

    Bondarev, S. L.; Tikhomirov, S. A.; Buganov, O. V.; Knyukshto, V. N.; Raichenok, T. F.

    2017-03-01

    The spectroscopic and photophysical properties of the biologically important plant antioxidant quercetin in organic solvents, polymer films of polyvinyl alcohol, and a buffer solution at pH 7.0 are studied by stationary luminescence and femtosecond laser spectroscopy at room temperature and 77 K. The large magnitude of the dipole moment of the quercetin molecule in the excited Franck-Condon state μ e FC = 52.8 C m indicates the dipolar nature of quercetin in this excited state. The transient induced absorption spectra S 1→ S n in all solvents are characterized by a short-wave band at λ abs max = 460 nm with exponential decay times in the range of 10.0-20.0 ps. In the entire spectral range at times of >100 ps, no residual induced absorption was observed that could be attributed to the triplet-triplet transitions T 1 → T k in quercetin. In polar solvents, two-band fluorescence was also recorded at room temperature, which is due to the luminescence of the initial enol form of quercetin ( 415 nm) and its keto form with a transferred proton (550 nm). The short-wave band is absent in nonpolar 2-methyltetrahydrofuran (2-MTHF). The spectra of fluorescence and fluorescence excitation exhibit a low dependence on the wavelength of excitation and detection, which may be related to the solvation and conformational changes in the quercetin molecule. Decreasing the temperature of a glassy-like freezing quercetin solution in ethanol and 2-MTHF to 77 K leads to a strong increase in the intensity (by a factor of 100) of both bands. The energy circuits for the proton transfer process are proposed depending on the polarity of the medium. The main channel for the exchange of electronic excitation energy in the quercetin molecule at room temperature is the internal conversion S 1 ⇝ S 0, induced by the state with a proton transfer.

  10. Time-resolved photoelectron spectroscopy of a dinuclear Pt(II) complex: Tunneling autodetachment from both singlet and triplet excited states of a molecular dianion

    Energy Technology Data Exchange (ETDEWEB)

    Winghart, Marc-Oliver, E-mail: marc-oliver.winghart@kit.edu; Unterreiner, Andreas-Neil [Institute of Physical Chemistry, Karlsruhe Institute of Technology, P.O. Box 6980, 76049 Karlsruhe (Germany); Yang, Ji-Ping [Institute of Physical Chemistry, Karlsruhe Institute of Technology, P.O. Box 6980, 76049 Karlsruhe (Germany); School of Sciences, Hefei University of Technology, Hefei 230009 (China); Vonderach, Matthias [Centre for Proteome Research, Institute of Integrative Biology, University of Liverpool, Liverpool L69 7ZB (United Kingdom); Huang, Dao-Ling; Wang, Lai-Sheng [Department of Chemistry, Brown University, Providence, Rhode Island 02912 (United States); Kruppa, Sebastian; Riehn, Christoph [Fachbereich Chemie und Landesforschungszentrum OPTIMAS, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 52–54, 67663 Kaiserslautern (Germany); Kappes, Manfred M., E-mail: manfred.kappes@kit.edu [Institute of Physical Chemistry, Karlsruhe Institute of Technology, P.O. Box 6980, 76049 Karlsruhe (Germany); Institute of Nanotechnology, Karlsruhe Institute of Technology, P.O. Box 3640, 76021 Karlsruhe (Germany)

    2016-02-07

    Time-resolved pump-probe photoelectron spectroscopy has been used to study the relaxation dynamics of gaseous [Pt{sub 2}(μ-P{sub 2}O{sub 5}H{sub 2}){sub 4} + 2H]{sup 2−} after population of its first singlet excited state by 388 nm femtosecond laser irradiation. In contrast to the fluorescence and phosphorescence observed in condensed phase, a significant fraction of the photoexcited isolated dianions decays by electron loss to form the corresponding monoanions. Our transient photoelectron data reveal an ultrafast decay of the initially excited singlet {sup 1}A{sub 2u} state and concomitant rise in population of the triplet {sup 3}A{sub 2u} state, via sub-picosecond intersystem crossing (ISC). We find that both of the electronically excited states are metastably bound behind a repulsive Coulomb barrier and can decay via delayed autodetachment to yield electrons with characteristic kinetic energies. While excited state tunneling detachment (ESETD) from the singlet {sup 1}A{sub 2u} state takes only a few picoseconds, ESETD from the triplet {sup 3}A{sub 2u} state is much slower and proceeds on a time scale of hundreds of nanoseconds. The ISC rate in the gas phase is significantly higher than in solution, which can be rationalized in terms of changes to the energy dissipation mechanism in the absence of solvent molecules. [Pt{sub 2}(μ-P{sub 2}O{sub 5}H{sub 2}){sub 4} + 2H]{sup 2−} is the first example of a photoexcited multianion for which ESETD has been observed following ISC.

  11. Cervical cancer detection by time-resolved spectra of blood components

    Science.gov (United States)

    Kalaivani, Rudran; Masilamani, Vadivel; AlSalhi, Mohamad Saleh; Devanesan, Sandhanasamy; Ramamurthy, P.; Palled, Siddanna R.; Ganesh, K. M.

    2014-05-01

    Fluorescence spectral techniques are very sensitive, and hence they are gaining importance in cancer detection. The biomarkers indicative of cancer could be identified and quantified by spectral or time domain fluorescence spectroscopy. The results of an investigation of time-resolved spectra of cellular components of blood obtained from cervical cancer patients and normal controls are given. The cancer indicative biomarker in this paper is porphyrin; it has a fluorescence decay time of 60% more in samples of cancer patients than those of normal controls. Based on such measurements, a randomized set comprising samples from cancer patients and controls (N=27 in total) could be classified with sensitivity (92%) and specificity (86%).

  12. MONSTIR II: A 32-channel, multispectral, time-resolved optical tomography system for neonatal brain imaging

    Energy Technology Data Exchange (ETDEWEB)

    Cooper, Robert J., E-mail: robert.cooper@ucl.ac.uk; Magee, Elliott; Everdell, Nick; Magazov, Salavat; Varela, Marta; Airantzis, Dimitrios; Gibson, Adam P.; Hebden, Jeremy C. [Biomedical Optics Research Laboratory, Department of Medical Physics and Bioengineering, University College London, London WC1E 6BT (United Kingdom)

    2014-05-15

    We detail the design, construction and performance of the second generation UCL time-resolved optical tomography system, known as MONSTIR II. Intended primarily for the study of the newborn brain, the system employs 32 source fibres that sequentially transmit picosecond pulses of light at any four wavelengths between 650 and 900 nm. The 32 detector channels each contain an independent photo-multiplier tube and temporally correlated photon-counting electronics that allow the photon transit time between each source and each detector position to be measured with high temporal resolution. The system's response time, temporal stability, cross-talk, and spectral characteristics are reported. The efficacy of MONSTIR II is demonstrated by performing multi-spectral imaging of a simple phantom.

  13. MONSTIR II: A 32-channel, multispectral, time-resolved optical tomography system for neonatal brain imaging

    Science.gov (United States)

    Cooper, Robert J.; Magee, Elliott; Everdell, Nick; Magazov, Salavat; Varela, Marta; Airantzis, Dimitrios; Gibson, Adam P.; Hebden, Jeremy C.

    2014-05-01

    We detail the design, construction and performance of the second generation UCL time-resolved optical tomography system, known as MONSTIR II. Intended primarily for the study of the newborn brain, the system employs 32 source fibres that sequentially transmit picosecond pulses of light at any four wavelengths between 650 and 900 nm. The 32 detector channels each contain an independent photo-multiplier tube and temporally correlated photon-counting electronics that allow the photon transit time between each source and each detector position to be measured with high temporal resolution. The system's response time, temporal stability, cross-talk, and spectral characteristics are reported. The efficacy of MONSTIR II is demonstrated by performing multi-spectral imaging of a simple phantom.

  14. Ultrafast structural dynamics studied by kilohertz time-resolved x-ray diffraction

    Institute of Scientific and Technical Information of China (English)

    郭鑫; 江舟亚; 陈龙; 陈黎明; 辛建国; 陈洁

    2015-01-01

    Ultrashort multi-keV x-ray pulses are generated by electron plasma produced by the irradiation of femtosecond pulses on metals. These sub-picosecond x-ray pulses have extended the field of x-ray spectroscopy into the femtosecond time domain. However, pulse-to-pulse instability and long data acquisition time restrict the application of ultrashort x-ray systems operating at low repetition rates. Here we report on the performance of a femtosecond laser plasma-induced hard x-ray source that operates at 1-kHz repetition rate, and provides a flux of 2.0 × 1010 photons/s of Cu Kα radiation. Using this system for time-resolved x-ray diffraction experiments, we record in real time, the transient processes and structural changes induced by the interaction of 400-nm femtosecond pulse with the surface of a 200-nm thick Au (111) single crystal.

  15. Theme Article - Time-Resolved X-Ray Scattering from Coherent Excitations in Solids

    Energy Technology Data Exchange (ETDEWEB)

    Trigo, Mariano; Reis, David (SLAC)

    2010-10-22

    Recent advances in pulsed x-ray sources have opened up new opportunities to study the dynamics of matter directly in the time domain with picosecond to femtosecond resolution. In this article, we present recent results from a variety of ultrafast sources on time-resolved x-ray scattering from elementary excitations in periodic solids. A few representative examples are given on folded acoustic phonons, coherent optical phonons, squeezed phonons, and polaritons excited by femtosecond lasers. Next-generation light sources, such as the x-ray-free electron laser, will lead to improvements in coherence, flux, and pulse duration. These experiments demonstrate potential opportunities for studying matter far from equilibrium on the fastest time scales and shortest distances that will be available in the coming years.

  16. Time-Resolved Cavity Nano-Optomechanics in the 20-100 GHz range

    CERN Document Server

    Anguiano, S; Jusserand, B; Favero, I; Lamperti, F R; Lanco, L; Sagnes, I; Lemaître, A; Lanzillotti-Kimura, N D; Senellart, P; Fainstein, A

    2016-01-01

    Applications of cavity optomechanics span from gravitational wave detection to the study of quantum motion states in mesoscopic mechanical systems. The engineering of resonators supporting strongly interacting mechanical and optical modes is central to these developments. However, current technological and experimental approaches limit the accessible mechanical frequencies to a few GHz, imposing hard constraints on quantum mechanical studies. Here we demonstrate the optical control of 20-100~GHz mechanical modes confined in the three dimensions within semiconductor nano-optomechanical pillar cavities. We use a time-resolved transient optical reflectivity technique and access both the energy spectrum and dynamics of the mechanical modes at the picosecond timescale. A strong increase of the optomechanical coupling upon reducing the pillar size is observed together with unprecedent room temperature Q-frequency products above $10^{14}$. The measurements also reveal sideband generation in the optomechanical respon...

  17. Single-State Electronic Structure Measurements Using Time-Resolved X-Ray Laser Induced Photoelectron Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Nelson, A J; Dunn, J; van Buuren, T; Hunter, J

    2004-11-11

    We demonstrate single-shot x-ray laser induced time-of-flight photoelectron spectroscopy on semiconductor and metal surfaces with picosecond time resolution. The LLNL COMET compact tabletop x-ray laser source provides the necessary high photon flux (>10{sup 12}/pulse), monochromaticity, picosecond pulse duration, and coherence for probing ultrafast changes in the city, chemical and electronic structure of these materials. Static valence band and shallow core-level photoemission spectra are presented for ambient temperature Ge(100) and polycrystalline Cu foils. Surface contamination was removed by UV ozone cleaning prior to analysis. In addition, the ultrafast nature of this technique lends itself to true single-state measurements of shocked and heated materials. Time-resolved electron time-of-flight photoemission results for ultra-thin Cu will be presented.

  18. Noninvasive detection of concealed explosives: depth profiling through opaque plastics by time-resolved Raman spectroscopy.

    Science.gov (United States)

    Petterson, Ingeborg E Iping; López-López, María; García-Ruiz, Carmen; Gooijer, Cees; Buijs, Joost B; Ariese, Freek

    2011-11-15

    The detection of explosives concealed behind opaque, diffusely scattering materials is a challenge that requires noninvasive analytical techniques for identification without having to manipulate the package. In this context, this study focuses on the application of time-resolved Raman spectroscopy (TRRS) with a picosecond pulsed laser and an intensified charge-coupled device (ICCD) detector for the noninvasive identification of explosive materials through several millimeters of opaque polymers or plastic packaging materials. By means of a short (250 ps) gate which can be delayed several hundred picoseconds after the laser pulse, the ICCD detector allows for the temporal discrimination between photons from the surface of a sample and those from deeper layers. TRRS was applied for the detection of the two main isomers of dinitrotoluene, 2,4-dinitrotoluene, and 2,6-dinitrotoluene as well as for various other components of explosive mixtures, including akardite II, diphenylamine, and ethyl centralite. Spectra were obtained through different diffuse scattering white polymer materials: polytetrafluoroethylene (PTFE), polyoxymethylene (POM), and polyethylene (PE). Common packaging materials of various thicknesses were also selected, including polystyrene (PS) and polyvinyl chloride (PVC). With the demonstration of the ability to detect concealed, explosives-related compounds through an opaque first layer, this study may have important applications in the security and forensic fields.

  19. Steady state and time resolved spectroscopy of photoswitchable systems

    NARCIS (Netherlands)

    Hou, Lili

    2013-01-01

    Steady state en time resolved spectroscopie zijn twee fundamentele methodes voor het bestuderen van fotochemische processen. In dit proefschrift zijn drie zelf-opgezette spectroscopische systemen beschreven, waarmee samen met andere spectroscopische methoden verscheidende met licht schakelbare syste

  20. Direct observation of ultrafast atomic motion using time-resolved X-ray diffraction

    Energy Technology Data Exchange (ETDEWEB)

    Shymanovich, U.

    2007-11-13

    This thesis is dedicated to the study of the atomic motion in laser irradiated solids on a picosecond to subpicosecond time-scale using the time-resolved X-ray diffraction technique. In the second chapter, the laser system, the laser-plasma based X-ray source and the experimental setup for optical pump / X-ray probe measurements were presented. Chapter 3 is devoted to the characterization and comparison of different types of X-ray optics. Chapter 4 presented the time-resolved X-ray diffraction experiments performed for this thesis. The first two sections of this chapter discuss the measurements of initially unexpected strain-induced transient changes of the integrated reflectivity of the X-ray probe beam. The elimination of the strain-induced transient changes of the integrated reflectivity represented an important prerequisite to perform the study of lattice heating in Germanium after femtosecond optical excitation by measuring the transient Debye-Waller effect. The third section describes the investigations of acoustic waves upon ultrafast optical excitation and discusses the two different pressure contributions driving them: the thermal and the electronic ones. (orig.)

  1. Time-Resolved Photoluminescence Studies of InGaN/AlGaN Multiple Quantum Wells

    Science.gov (United States)

    Zeng, K. C.; Smith, M.; Lin, J. Y.; Jiang, H. X.; Robert, J. C.; Piner, E. L.; McIntosh, F. G.; Bahbahani, M.; Bedair, S. M.; Zavada, J.

    1997-03-01

    Picosecond time-resolved photoluminescence (PL) spectroscopy has been employed to study the dynamic processes of optical transitions in InGaN/AlGaN multiple quantum wells (MQW) grown by metal-organic chemical vapor deposition (MOCVD). The dynamical behavior of the PL emission reveals that the main emission line in these MQW is the combination of the localized exciton and a band-to-impurity emission lines. The spectral lineshape and the recombination dynamics of the localized exciton and of the band-to-impurity transitions have been systematically investigated at different temperatures and excitation intensities and for MQW with different structures and growth conditions. From these studies, important parameters, including the localization energy and the recombination lifetimes of the localized excitons in InGaN/AlGaN quantum wells, the well width fluctuation, alloy compositions in the well and the barrier materials, and the band offset between InGaN and AlGaN can be deduced. Comparing with time-resolved PL results of InGaN/GaN and GaN/AlGaN MQW, important effects of interface on the optical properties of the III-nitride MQW have been evaluated. Implications of our results to device applications will be discussed.

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

    Science.gov (United States)

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

    2016-07-01

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

  3. Time-resolved microscopy studies of laser damage dynamics at 0.5-1ps, 1030nm

    Science.gov (United States)

    Gallais, L.; Ollé, A.; Sozet, M.; Berthelot, J.; Monneret, S.; Néauport, J.; Lamaignère, L.

    2016-12-01

    Based on an experimental system that can be used for simultaneous laser damage testing and time-resolved acquisition of intensity and phase images, we describe different experiments related to the study of laser damage process in the sub-picosecond regime. We report firstly on quantitative measurement of the Kerr effect in a fused silica substrate at fluences closed to the Laser Induced Damage Threshold. Then we study the damage initiation process in optical coatings, linked to intrinsic properties of the materials, and the dynamics of free electron generation and relaxation. At last, damage growth sequences are analyzed with time-resolved microscopy in order to understand laser damage growth in the case of High Reflective mirrors.

  4. Electron-hole recombination on ZnO(0001) single-crystal surface studied by time-resolved soft X-ray photoelectron spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Yukawa, R.; Yamamoto, S.; Ogawa, M.; Yamamoto, Sh.; Fujikawa, K.; Hobara, R.; Matsuda, I., E-mail: imatsuda@issp.u-tokyo.ac.jp [Institute for Solid State Physics, The University of Tokyo, Kashiwa, Chiba 277-8581 (Japan); Ozawa, K. [Department of Chemistry and Materials Science, Tokyo Institute of Technology, Meguro-ku, Tokyo 152-8551 (Japan); Emori, M.; Sakama, H. [Department of Physics, Sophia University, Chiyoda-ku, Tokyo 102-8554 (Japan); Kitagawa, S.; Daimon, H. [Nara Institute of Science and Technology (NAIST), Ikoma, Nara 630-0192 (Japan)

    2014-10-13

    Time-resolved soft X-ray photoelectron spectroscopy (PES) experiments were performed with time scales from picoseconds to nanoseconds to trace relaxation of surface photovoltage on the ZnO(0001) single crystal surface in real time. The band diagram of the surface has been obtained numerically using PES data, showing a depletion layer which extends to 1 μm. Temporal evolution of the photovoltage effect is well explained by a recombination process of a thermionic model, giving the photoexcited carrier lifetime of about 1 ps at the surface under the flat band condition. This lifetime agrees with a temporal range reported by the previous time-resolved optical experiments.

  5. Visualizing a protein quake with time-resolved X-ray scattering at a free-electron laser

    DEFF Research Database (Denmark)

    Arnlund, David; Johansson, Linda C.; Wickstrand, Cecilia;

    2014-01-01

    We describe a method to measure ultrafast protein structural changes using time-resolved wide-angle X-ray scattering at an X-ray free-electron laser. We demonstrated this approach using multiphoton excitation of the Blastochloris viridis photosynthetic reaction center, observing an ultrafast global...... conformational change that arises within picoseconds and precedes the propagation of heat through the protein. This provides direct structural evidence for a 'protein quake': the hypothesis that proteins rapidly dissipate energy through quake-like structural motions....

  6. 农产品中黄曲霉毒素的时间分辨荧光免疫层析快速检测技术研究%Study on Time-Resolved Fluorescence Immunochromatography for Afaltoxin Determination in Agricultural Product

    Institute of Scientific and Technical Information of China (English)

    张兆威; 李培武; 张奇; 丁小霞

    2014-01-01

    时间分辨荧光免疫层析检测技术灵敏度高、线性范围宽,重复性和稳定性好,是一种适合中国国情的实用快速检测技术,具有广阔的应用前景。%[Objective]Aflatoxin contaminates agricultural product severely, threatens health and life of people and livestocks. It is one of the major focus issues and attracts both governmental and social concerns. Thus, it is required to establish a rapid and sensitive determination method for aflatoxin. High specific and sensitive monoclonal antibody against aflatoxin has been developed. In this study, using the as-prepared monoclonal antibody against aflatoxin, the aim is to establish time-resolved fluorescence immunochromatography for afaltoxin determination in agricultural product, in order to provide technical support for agricultural product quality supervision and risk assessment. [Method] Herein, monoclonal antibody against aflatoxin was coupled with emulsion europium for labeling. With the home-made time-resolved fluorescence immunochromatographic strip, aflatoxin could be determined quantitatively, by using the signal value ratio of test line to control line and natural logarithm of concentration in standard aflatoxin solution. Regarding to various agricultural product samples (as peanut, rice and vegetable oil), an integration technology was developed that combined grinding and homogenization in one step. The methodological evaluation was conducted, in which aflatoxin in real agricultural products such as peanut, rice and vegetable oil. Moreover, these results via time-resolved fluorescence immunochromatography were compared with those via HPLC method. [Result] Results showed a detecting limit of 0.3μg·kg-1, a liner range of 0.8-25, 0.8-15, 0.8-30 μg·kg-1, for peanut, rice, plant oil, respectively. The standard curves were recorded as y=0.238x+0.654 (R2=0.992), y=0.321x+0.811 (R2=0.990), and y=0.146x+0.173 (R2=0.993), for peanut, rice, and plant oil, respectively

  7. 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.

  8. Opportunities and challenges for time-resolved studies of protein structural dynamics at X-ray free-electron lasers.

    Science.gov (United States)

    Neutze, Richard

    2014-07-17

    X-ray free-electron lasers (XFELs) are revolutionary X-ray sources. Their time structure, providing X-ray pulses of a few tens of femtoseconds in duration; and their extreme peak brilliance, delivering approximately 10(12) X-ray photons per pulse and facilitating sub-micrometre focusing, distinguish XFEL sources from synchrotron radiation. In this opinion piece, I argue that these properties of XFEL radiation will facilitate new discoveries in life science. I reason that time-resolved serial femtosecond crystallography and time-resolved wide angle X-ray scattering are promising areas of scientific investigation that will be advanced by XFEL capabilities, allowing new scientific questions to be addressed that are not accessible using established methods at storage ring facilities. These questions include visualizing ultrafast protein structural dynamics on the femtosecond to picosecond time-scale, as well as time-resolved diffraction studies of non-cyclic reactions. I argue that these emerging opportunities will stimulate a renaissance of interest in time-resolved structural biochemistry.

  9. Opportunities and challenges for time-resolved studies of protein structural dynamics at X-ray free-electron lasers

    Science.gov (United States)

    Neutze, Richard

    2014-01-01

    X-ray free-electron lasers (XFELs) are revolutionary X-ray sources. Their time structure, providing X-ray pulses of a few tens of femtoseconds in duration; and their extreme peak brilliance, delivering approximately 1012 X-ray photons per pulse and facilitating sub-micrometre focusing, distinguish XFEL sources from synchrotron radiation. In this opinion piece, I argue that these properties of XFEL radiation will facilitate new discoveries in life science. I reason that time-resolved serial femtosecond crystallography and time-resolved wide angle X-ray scattering are promising areas of scientific investigation that will be advanced by XFEL capabilities, allowing new scientific questions to be addressed that are not accessible using established methods at storage ring facilities. These questions include visualizing ultrafast protein structural dynamics on the femtosecond to picosecond time-scale, as well as time-resolved diffraction studies of non-cyclic reactions. I argue that these emerging opportunities will stimulate a renaissance of interest in time-resolved structural biochemistry. PMID:24914150

  10. Quantum-dot-based homogeneous time-resolved fluoroimmunoassay of alpha-fetoprotein

    Energy Technology Data Exchange (ETDEWEB)

    Chen Meijun; Wu Yingsong; Lin Guanfeng; Hou Jingyuan; Li Ming [Institute of Antibody Engineering, School of Biotechnology, Southern Medical University, Guangzhou, 510515 (China); Liu Tiancai, E-mail: liutc@smu.edu.cn [Institute of Antibody Engineering, School of Biotechnology, Southern Medical University, Guangzhou, 510515 (China)

    2012-09-05

    Highlights: Black-Right-Pointing-Pointer QDs-based homogeneous time-resolved fluoroimmunoassay was developed to detect AFP. Black-Right-Pointing-Pointer The conjugates were prepared with QDs-doped microspheres and anti-AFP McAb. Black-Right-Pointing-Pointer The conjugates were prepared with LTCs and another anti-AFP McAb. Black-Right-Pointing-Pointer Excess amounts of conjugates were used for detecting AFP without rinsing. Black-Right-Pointing-Pointer The wedding of QPs and LTCs was suitable for HTRFIA to detect AFP. - Abstract: Quantum dots (QDs) with novel photoproperties are not widely used in clinic diagnosis, and homogeneous time-resolved fluorescence assays possess many advantages over current methods for alpha-fetoprotein (AFP) detection. A novel QD-based homogeneous time-resolved fluorescence assay was developed and used for detection of AFP, a primary marker for many cancers and diseases. QD-doped carboxyl-modified polystyrene microparticles (QPs) were prepared by doping oil-soluble QDs possessing a 605 nm emission peak. The antibody conjugates (QPs-E014) were prepared from QPs and an anti-AFP monoclonal antibody, and luminescent terbium chelates (LTCs) were prepared and conjugated to a second anti-AFP monoclonal antibody (LTCs-E010). In a double-antibodies sandwich structure, QPs-E014 and LTCs-E010 were used for detection of AFP, serving as energy acceptor and donor, respectively, with an AFP bridge. The results demonstrated that the luminescence lifetime of these QPs was sufficiently long for use in a time-resolved fluoroassay, with the efficiency of time-resolved Foerster resonance transfer (TR-FRET) at 67.3% and the spatial distance of the donor to acceptor calculated to be 66.1 Angstrom-Sign . Signals from TR-FRET were found to be proportional to AFP concentrations. The resulting standard curve was log Y = 3.65786 + 0.43863{center_dot}log X (R = 0.996) with Y the QPs fluorescence intensity and X the AFP concentration; the calculated sensitivity was 0

  11. Time-Resolved Spectroscopy in Complex Liquids An Experimental Perspective

    CERN Document Server

    Torre, Renato

    2007-01-01

    Time-Resolved Spectroscopy in Complex Liquids introduces current state-of-the-art techniques in the study of complex dynamical problems in liquid phases. With a unique focus on the experimental aspects applied to complex liquids, this volume provides an excellent overview into the quickly emerging field of soft-matter science. Researchers and engineers will find a comprehensive review of current non-linear spectroscopic and optical Kerr effect techniques, in addition to an in-depth look into relaxation dynamics in complex liquids. This volume offers current experimental findings in transient grating spectroscopy and their application to viscoelastic phenomena in glass-formers, dynamics of confined liquid-crystals, and a time-resolved analysis of the host-quest interactions of dye molecules in liquid-crystal matter. Time-Resolved Spectroscopy in Complex Liquids provides a cohesive introduction suitable for individuals involved in this emerging field, complete with the latest experimental procedures of complex ...

  12. 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. .

  13. Time-resolved photon emission from layered turbid media

    Energy Technology Data Exchange (ETDEWEB)

    Hielscher, A.H. [Department of Electrical and Computer Engineering, Rice University, 6100 South Main, Houston, Texas 77251-1892 (United States); Liu, H.; Chance, B. [Department of Biochemistry and Biophysics, University of Pennsylvania, D501 Richards Building, Philadelphia, Pennsylvania 19104-6089 (United States); Tittel, F.K. [Department of Electrical and Computer Engineering, Rice University, 6100 South Main, Houston, Texas 77251-1892 (United States); Jacques, S.L. [Laser Biology Research Laboratory, Box 17, The University of Texas M.D. Anderson Cancer Center, 1515 Holcombe Boulevard, Houston, Texas 77030 (United States)

    1996-02-01

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

  14. Watching proteins function with time-resolved x-ray crystallography

    Science.gov (United States)

    Šrajer, Vukica; Schmidt, Marius

    2017-09-01

    Macromolecular crystallography was immensely successful in the last two decades. To a large degree this success resulted from use of powerful third generation synchrotron x-ray sources. An expansive database of more than 100 000 protein structures, of which many were determined at resolution better than 2 Å, is available today. With this achievement, the spotlight in structural biology is shifting from determination of static structures to elucidating dynamic aspects of protein function. A powerful tool for addressing these aspects is time-resolved crystallography, where a genuine biological function is triggered in the crystal with a goal of capturing molecules in action and determining protein kinetics and structures of intermediates (Schmidt et al 2005a Methods Mol. Biol. 305 115-54, Schmidt 2008 Ultrashort Laser Pulses in Biology and Medicine (Berlin: Springer) pp 201-41, Neutze and Moffat 2012 Curr. Opin. Struct. Biol. 22 651-9, Šrajer 2014 The Future of Dynamic Structural Science (Berlin: Springer) pp 237-51). In this approach, short and intense x-ray pulses are used to probe intermediates in real time and at room temperature, in an ongoing reaction that is initiated synchronously and rapidly in the crystal. Time-resolved macromolecular crystallography with 100 ps time resolution at synchrotron x-ray sources is in its mature phase today, particularly for studies of reversible, light-initiated reactions. The advent of the new free electron lasers for hard x-rays (XFELs; 5-20 keV), which provide exceptionally intense, femtosecond x-ray pulses, marks a new frontier for time-resolved crystallography. The exploration of ultra-fast events becomes possible in high-resolution structural detail, on sub-picosecond time scales (Tenboer et al 2014 Science 346 1242-6, Barends et al 2015 Science 350 445-50, Pande et al 2016 Science 352 725-9). We review here state-of-the-art time-resolved crystallographic experiments both at synchrotrons and XFELs. We also outline

  15. Watching proteins function with time-resolved x-ray crystallography

    Energy Technology Data Exchange (ETDEWEB)

    Šrajer, Vukica; Schmidt, Marius

    2017-08-22

    Macromolecular crystallography was immensely successful in the last two decades. To a large degree this success resulted from use of powerful third generation synchrotron x-ray sources. An expansive database of more than 100 000 protein structures, of which many were determined at resolution better than 2 Å, is available today. With this achievement, the spotlight in structural biology is shifting from determination of static structures to elucidating dynamic aspects of protein function. A powerful tool for addressing these aspects is time-resolved crystallography, where a genuine biological function is triggered in the crystal with a goal of capturing molecules in action and determining protein kinetics and structures of intermediates (Schmidt et al 2005a Methods Mol. Biol. 305 115–54, Schmidt 2008 Ultrashort Laser Pulses in Biology and Medicine (Berlin: Springer) pp 201–41, Neutze and Moffat 2012 Curr. Opin. Struct. Biol. 22 651–9, Šrajer 2014 The Future of Dynamic Structural Science (Berlin: Springer) pp 237–51). In this approach, short and intense x-ray pulses are used to probe intermediates in real time and at room temperature, in an ongoing reaction that is initiated synchronously and rapidly in the crystal. Time-resolved macromolecular crystallography with 100 ps time resolution at synchrotron x-ray sources is in its mature phase today, particularly for studies of reversible, light-initiated reactions. The advent of the new free electron lasers for hard x-rays (XFELs; 5–20 keV), which provide exceptionally intense, femtosecond x-ray pulses, marks a new frontier for time-resolved crystallography. The exploration of ultra-fast events becomes possible in high-resolution structural detail, on sub-picosecond time scales (Tenboer et al 2014 Science 346 1242–6, Barends et al 2015 Science 350 445–50, Pande et al 2016 Science 352 725–9). We review here state-of-the-art time-resolved crystallographic experiments both at synchrotrons and XFELs. We

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

    Science.gov (United States)

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

    2016-10-01

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

  17. Time-resolved vibrational spectroscopy of a molecular shuttle

    NARCIS (Netherlands)

    Panman, M.R.; Bodis, P.; Shaw, D.J.; Bakker, B.H.; Newton, A.C.; Kay, E.R.; Leigh, D.A.; Buma, W.J.; Brouwer, A.M.; Woutersen, S.

    2012-01-01

    Time-resolved vibrational spectroscopy is used to investigate the inter-component motion of an ultraviolet-triggered two-station molecular shuttle. The operation cycle of this molecular shuttle involves several intermediate species, which are observable in the amide I and amide II regions of the mid

  18. Time-resolved terahertz spectroscopy of black silicon

    DEFF Research Database (Denmark)

    Porte, Henrik; Turchinovich, Dmitry; Jepsen, Peter Uhd;

    2010-01-01

    The ultrafast photoconductivity dynamics of black silicon is measured by time-resolved terahertz spectroscopy. Black silicon is produced by laser annealing of an a-Si:H film. We show that the decay time of the photoconductivity depends on the annealing method and fluence used in the production...

  19. Time-resolved luminescence spectra of porous Si

    OpenAIRE

    Miyoshi, Tadaki; Lee, Kyu-Seok; Aoyagi, Yoshinobu

    1992-01-01

    Time-resolved luminescence spectra of porous Si were measured under an N_2 laser excitation. The luminescence shows a nonexponential decay with an initial time constant of less than 5 ns and more than 200 ns for the secondary decay. The luminescence is considered to be associated with localized states, which are probably conduction and valence sublevels in Si microstructures.

  20. 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...

  1. Advances in Time-Resolved Tomographic Particle Image Velocimetry

    NARCIS (Netherlands)

    Lynch, K.P.

    2015-01-01

    This thesis details advanced developments in 3-D particle image velocimetry (PIV) based on the tomographic PIV technique, with an emphasis on time-resolved experiments. Tomographic PIV is a technique introduced in 2006 to measure the flow velocity in a three-dimensional volume. When measurements are

  2. Optimizing a time-resolved X-ray absorption experiment

    CERN Document Server

    Bressler, C; Chergui, M; Abela, R; Pattison, P

    2001-01-01

    Calculations are presented of the optimum conditions for performing a laser-pump X-ray probe time-resolved X-ray absorption experiment. The results concerning sensitivity and feasibility for implementing the method are illustrated for the case of the nascent I radical environment following I sup - photolysis in H sub 2 O.

  3. Time-Resolved 2PPE and Time-Resolved PEEM as a Probe of LSP's in Silver Nanoparticles

    Directory of Open Access Journals (Sweden)

    D. Bayer

    2008-01-01

    Full Text Available The time-resolved two-photon photoemission technique (TR-2PPE has been applied to study static and dynamic properties of localized surface plasmons (LSP in silver nanoparticles. Laterally, integrated measurements show the difference between LSP excitation and nonresonant single electron-hole pair creation. Studies below the optical diffraction limit were performed with the detection method of time-resolved photoemission electron microscopy (TR-PEEM. This microscopy technique with a resolution down to 40 nm enables a systematic study of retardation effects across single nanoparticles. In addition, as will be shown in this paper, it is a highly sensitive sensor for coupling effects between nanoparticles.

  4. FY05 LDRD Final ReportTime-Resolved Dynamic Studies using Short Pulse X-Ray Radiation

    Energy Technology Data Exchange (ETDEWEB)

    Nelson, A; Dunn, J; van Buuren, T; Budil, K; Sadigh, B; Gilmer, G; Falcone, R; Lee, R; Ng, A

    2006-02-10

    Established techniques must be extended down to the ps and sub-ps time domain to directly probe product states of materials under extreme conditions. We used short pulse ({le} 1 ps) x-ray radiation to track changes in the physical properties in tandem with measurements of the atomic and electronic structure of materials undergoing fast laser excitation and shock-related phenomena. The sources included those already available at LLNL, including the picosecond X-ray laser as well as the ALS Femtosecond Phenomena beamline and the SSRL based sub-picosecond photon source (SPPS). These allow the temporal resolution to be improved by 2 orders of magnitude over the current state-of-the-art, which is {approx} 100 ps. Thus, we observed the manifestations of dynamical processes with unprecedented time resolution. Time-resolved x-ray photoemission spectroscopy and x-ray scattering were used to study phase changes in materials with sub-picosecond time resolution. These experiments coupled to multiscale modeling allow us to explore the physics of materials in high laser fields and extreme non-equilibrium states of matter. The ability to characterize the physical and electronic structure of materials under extreme conditions together with state-of-the-art models and computational facilities will catapult LLNL's core competencies into the scientific world arena as well as support its missions of national security and stockpile stewardship.

  5. Advances in frequency-domain fluorometry, gigahertz instrumentation, time-dependent photomigration, and fluorescence lifetime imaging

    Science.gov (United States)

    Lakowicz, Joseph R.; Gryczynski, Ignacy; Szmacinski, Henryk; Nowaczyk, Kazimierz; Johnson, Michael L.

    1992-02-01

    During the past seven years, there have been remarkable advances in the frequency-domain method for measurement of time-resolved emission or light scattering. In this presentation we describe the recent extension of the frequency range to 10 GHz using a specially designed microchannel plate PMT. Experimental data will be shown for measurement of picosecond rotational diffusion and for sub-picosecond resolution of time delays. The resolution of ps to ns timescale processes is not obtained at the expense of sensitivity or is it shown by measurements on the intrinsic tryptophan emission from hemoglobin. We also describe a time- resolved reflectance imaging experiment on a scattering medium containing an absorbing object. Time-resolved imaging of the back-scattered light is realized by means of a RF-phase- sensitive camera, synchronized to the laser pulses. By processing the stored images, a final image can be created, the contrast of which is based only on time differences of the back- scattered photons. This image reveals the presence and position of the absorber within the scattering medium. And finally, we describe a new methodology, fluorescence lifetime imaging (FLIM), in which the contrast depends on the fluorescence lifetime at each point in a two-dimensional image, and not the local concentration and/or intensity of the fluorophore. We used FLIM to create lifetime images of NADH when free in solution and when bound to malate dehydrogenase. FLIM has numerous potential applications in cell biology and imaging.

  6. BRIEF COMMUNICATIONS: Picosecond spectroscopy of pyrrol pigments

    Science.gov (United States)

    Lippitsch, M. E.; Leitner, A.; Riegler, M.; Aussenegg, F. R.

    1982-05-01

    Picosecond fluorescence and absorption spectroscopy methods were used to study pyrromethenone, pyrromethene, and biliverdin. These methods made it possible to determine some details of the kinetics of various relaxation mechanisms. The results obtained provided a better understanding of the biological action of pyrrol pigments.

  7. The analysis of time-resolved optical waveguide absorption spectroscopy based on positive matrix factorization.

    Science.gov (United States)

    Liu, Ping; Li, Zhu; Li, Bo; Shi, Guolong; Li, Minqiang; Yu, Daoyang; Liu, Jinhuai

    2013-08-01

    Time-resolved optical waveguide absorption spectroscopy (OWAS) makes use of an evanescent field to detect the polarized absorption spectra of sub-monomolecular adlayers. This technique is suitable for the investigation of kinetics at the solid/liquid interface of dyes, pigments, fluorescent molecules, quantum dots, metallic nanoparticles, and proteins with chromophores. In this work, we demonstrate the application of positive matrix factorization (PMF) to analyze time-resolved OWAS for the first time. Meanwhile, PCA is researched to compare with PMF. The absorption/desorption kinetics of Rhodamine 6G (R6G) onto a hydrophilic glass surface and the dynamic process of Meisenheimer complex between Cysteine and TNT are selected as samples to verify experimental system and analytical methods. The results are shown that time-resolved OWAS can well record the absorption/desorption of R6G onto a hydrophilic glass surface and the dynamic formation process of Meisenheimer complexes. The feature of OWAS extracted by PMF is dynamic and consistent with the results analyzed by the traditional function of time/wavelength-absorbance. Moreover, PMF prevents the negative factors from occurring, avoids contradicting physical reality, and makes factors more easily interpretable. Therefore, we believe that PMF will provide a valuable analysis route to allow processing of increasingly large and complex data sets.

  8. Time-resolved spatially offset Raman spectroscopy for depth analysis of diffusely scattering layers.

    Science.gov (United States)

    Iping Petterson, Ingeborg E; Dvořák, Patrick; Buijs, Joost B; Gooijer, Cees; Ariese, Freek

    2010-12-01

    The objective of this study is to use time-resolved (TR) Raman spectroscopy, spatially offset Raman spectroscopy (SORS), and a combination of these approaches to obtain high quality Raman spectra from materials hidden underneath an opaque layer. Both TR Raman and SORS are advanced techniques that allow for an increased relative selectivity of photons from deeper layers within a sample. Time-resolved detection reduces fluorescence background, and the selectivity for the second layer is improved. By combining this with spatially offset excitation we additionally increased selectivity for deeper layers. Test samples were opaque white polymer blocks of several mm thicknesses. Excitation was carried out with a frequency-doubled Ti:sapphire laser at 460 nm, 3 ps pulse width and 76 MHz repetition rate. Detection was either with a continuous-wave CCD camera or in time-resolved mode using an intensified CCD camera with a 250 ps gate width. The Raman photons were collected in backscatter mode, with or without lateral offset. By measuring the delay of the Raman signal from the second layer (polyethylene terephthalate/PET/Arnite), the net photon migration speeds through Teflon, polythene, Delrin and Nylon were determined. Raman spectra could be obtained from a second layer of PET through Teflon layers up to 7 mm of thickness. The ability to obtain chemical information through layers of diffusely scattering materials has powerful potential for biomedical applications.

  9. 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...... Alert System in the ISGRI field of view. Although the burst was fairly weak (fluence F20-200 keV similar or equal to 3.5x10(-6) erg cm(-2)) it was possible to perform time resolved spectroscopy with a resolution of a few seconds. The GRB shows a spectrum in the 20-400 keV range which is consistent...

  10. Time resolved Schlieren imaging of DBD actuator flow fields

    Science.gov (United States)

    Nourgostar, Cyrus; Oksuz, Lutfi; Hershkowitz, Noah

    2009-10-01

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

  11. Time-resolved CT angiography in aortic dissection

    Energy Technology Data Exchange (ETDEWEB)

    Meinel, Felix G., E-mail: felix.meinel@med.uni-muenchen.de [Department of Clinical Radiology, Ludwig Maximilians-University, Marchioninistr. 15, 81377 Munich (Germany); Nikolaou, Konstantin, E-mail: konstantin.nikolaou@med.uni-muenchen.de [Department of Clinical Radiology, Ludwig Maximilians-University, Marchioninistr. 15, 81377 Munich (Germany); Weidenhagen, Rolf, E-mail: rolf.weidenhagen@med.uni-muenchen.de [Department of Surgery, Ludwig Maximilians-University, Marchioninistr. 15, 81377 Munich (Germany); Hellbach, Katharina, E-mail: katharina.hellbach@med.uni-muenchen.de [Department of Clinical Radiology, Ludwig Maximilians-University, Marchioninistr. 15, 81377 Munich (Germany); Helck, Andreas, E-mail: andreas.helck@med.uni-muenchen.de [Department of Clinical Radiology, Ludwig Maximilians-University, Marchioninistr. 15, 81377 Munich (Germany); Bamberg, Fabian, E-mail: fabian.bamberg@med.uni-muenchen.de [Department of Clinical Radiology, Ludwig Maximilians-University, Marchioninistr. 15, 81377 Munich (Germany); Reiser, Maximilian F., E-mail: maximilian.reiser@med.uni-muenchen.de [Department of Clinical Radiology, Ludwig Maximilians-University, Marchioninistr. 15, 81377 Munich (Germany); Sommer, Wieland H., E-mail: wieland.sommer@med.uni-muenchen.de [Department of Clinical Radiology, Ludwig Maximilians-University, Marchioninistr. 15, 81377 Munich (Germany)

    2012-11-15

    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.

  12. Time-resolved laser-induced breakdown spectroscopy of aluminum

    Institute of Scientific and Technical Information of China (English)

    LIU Xian-yun; ZHANG Wei-jun; WANG Zhen-ya; HAO Li-qing; HUANG Ming-qiang; ZHAO Wen-wu; LONG Bo; Zhao Wei

    2008-01-01

    We develop a system to measure the elemental composition of unprepared samples using laser-induced breakdown spectroscopy (LIBS) in our laboratory, which can be used for the determination of elements in solids, liquids and aerosols. A description of the instrumentation, including laser, sample chamber and detection, is followed by a brief discussion. The time-resolved LIBS of aluminum at atmospheric pressure is presented. At the end, the possibilities and later uses of this technique are briefly discussed.

  13. On the interpretation of time-resolved anisotropic diffraction patterns

    DEFF Research Database (Denmark)

    Lorenz, Ulf; Møller, Klaus Braagaard; Henriksen, Niels Engholm

    2010-01-01

    In this paper, we review existing systematic treatments for the interpretation of anisotropic diffraction patterns from partially aligned symmetric top molecules. Such patterns arise in the context of time-resolved diffraction experiments. We calculate diffraction patterns for ground-state NaI ex......I excited with an ultraviolet laser. The results are interpreted with the help of a qualitative analytic model, and general recommendations on the analysis and interpretation of anisotropic diffraction patterns are given....

  14. 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...... coherent detection, respectively. We find that the measured frequency dependent conductivity can be well described by a Drude-Smith model, supplemented by a Lorentz model oscillating near 5 THz....

  15. Time-resolved THz spectroscopy in a parallel plate waveguide

    DEFF Research Database (Denmark)

    Cooke, David; Jepsen, Peter Uhd

    2009-01-01

    We demonstrate time-resolved terahertz spectroscopy inside a novel parallel plate waveguide where one of the metallic plates is replaced by a transparent conducting oxide. Considerable improvements to the waveguide loss coefficient are shown, with a power absorption coefficient of 4cm-1 at 0.5 THz....... The time resolution of the technique is shown to be limited by the spatial excitation profile, which for sharply focused beams can approach ~1 ps time scales....

  16. Introductory lecture: Time-resolved chemistry at atomic resolution.

    Science.gov (United States)

    Coppens, Philip; Novozhilova, Irina V

    2003-01-01

    Though time-resolved studies are still at an early stage, the field is rapidly being developed and applied to an increasingly broad spectrum of problems with timescales varying from seconds or more down to femtoseconds. In this overview a number of different techniques are discussed, with emphasis on chemical applications in which information is obtained at the atomic level. The need to correlate with theory, both for calibration of theoretical methods and to obtain related information not accessible experimentally, is stressed.

  17. 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....

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2006-10-24

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

  19. Time-resolved MR angiography with limited projections.

    Science.gov (United States)

    Huang, Yuexi; Wright, Graham A

    2007-08-01

    A method for reconstruction of time-resolved MRI called highly-constrained backprojection (HYPR) has been developed. To evaluate the HYPR reconstruction in relation to data sparsity and temporal dynamics, computer simulations were performed, investigating signal modulations under different situations that reflect dynamic contrast-enhanced MR angiography (MRA). In vivo studies were also performed with gadolinium diethylenetriamine pentaacetic acid (Gd-DTPA) for abdominal MRA in a canine model to demonstrate the application of HYPR for three-dimensional (3D) time-resolved MRA. When contrast dynamics vary over space, large vessels (e.g., veins) tend to introduce signal interference to small vessels (e.g., arteries) in HYPR, particularly when the vessels are in close proximity. The enhancement of background tissue signals may also alter the arterial and venous temporal profiles in HYPR. However, the artifacts are manifest as intensity modulation rather than structural interference, and therefore have little impact on structural diagnosis. Increasing the number of projections per time point increases temporal blur while reducing corruption of temporal behavior from adjacent tissues. Uniformly interleaved acquisition order, such as the bit-reversed order, is important to reduce artifacts. With high signal-to-noise ratio (SNR) and limited artifacts, HYPR reconstruction has potential to greatly improve time-resolved MRA in clinical practice.

  20. Ultrafast dynamics of surface plasmons in InAs by time-resolved infrared nanospectroscopy.

    Science.gov (United States)

    Wagner, Martin; McLeod, Alexander S; Maddox, Scott J; Fei, Zhe; Liu, Mengkun; Averitt, Richard D; Fogler, Michael M; Bank, Seth R; Keilmann, Fritz; Basov, D N

    2014-08-13

    We report on time-resolved mid-infrared (mid-IR) near-field spectroscopy of the narrow bandgap semiconductor InAs. The dominant effect we observed pertains to the dynamics of photoexcited carriers and associated surface plasmons. A novel combination of pump-probe techniques and near-field nanospectroscopy accesses high momentum plasmons and demonstrates efficient, subpicosecond photomodulation of the surface plasmon dispersion with subsequent tens of picoseconds decay under ambient conditions. The photoinduced change of the probe intensity due to plasmons in InAs is found to exceed that of other mid-IR or near-IR media by 1-2 orders of magnitude. Remarkably, the required control pulse fluence is as low as 60 μJ/cm(2), much smaller than fluences of ∼ 1-10 mJ/cm(2) previously utilized in ultrafast control of near-IR plasmonics. These low excitation densities are easily attained with a standard 1.56 μm fiber laser. Thus, InAs--a common semiconductor with favorable plasmonic properties such as a low effective mass--has the potential to become an important building block of optically controlled plasmonic devices operating at infrared frequencies.

  1. Time-Resolved Photoluminescence Studies of AlInGaN Alloys

    Institute of Scientific and Technical Information of China (English)

    董逊; 黄劲松; 黎大兵; 刘祥林; 徐仲英; 王占国

    2003-01-01

    We study the two samples of AIInGaN, i.e., 1-μm GaN grown at 1030℃ on the buffer and followed by a 0.6-μm-thick epilayer of AIInGaN under the Iow pressure of 76 Torr and the AIInGaN layer deposited directly on the buffer layer without the high-temperature GaN layer, by temperature-dependent photoluminescence (PL)spectroscopy and picosecond time-resolved photoluminescence (TRPL) spectroscopy. The TRPL signals of both the samples were fitted well as a stretched exponential decay at all temperatures, indicating significant disorder in the material. We attribute the disorder to nanoscale quantum dots or discs of high indium concentration.Temperature dependence of dispersive exponentβ shows that the stretched exponential decay of the two samples comes from different mechanisms. The different depths of the localization potential account for the difference,which is illustrated by the results of temperature dependence of radiative recombination lifetime and PL peak energy.

  2. Time-resolved X-ray Absorption Spectroscopy for Electron Transport Study in Warm Dense Gold

    Science.gov (United States)

    Lee, Jong-Won; Bae, Leejin; Engelhorn, Kyle; Heimann, Philip; Ping, Yuan; Barbrel, Ben; Fernandez, Amalia; Beckwith, Martha Anne; Cho, Byoung-Ick; GIST Team; IBS Team; LBNL Collaboration; SLAC Collaboration; LLNL Collaboration

    2015-11-01

    The warm dense Matter represents states of which the temperature is comparable to Fermi energy and ions are strongly coupled. One of the experimental techniques to create such state in the laboratory condition is the isochoric heating of thin metal foil with femtosecond laser pulses. This concept largely relies on the ballistic transport of electrons near the Fermi-level, which were mainly studied for the metals in ambient conditions. However, they were barely investigated in warm dense conditions. We present a time-resolved x-ray absorption spectroscopy measured for the Au/Cu dual layered sample. The front Au layer was isochorically heated with a femtosecond laser pulse, and the x-ray absorption changes around L-edge of Cu, which was attached on the backside of Au, was measured with a picosecond resolution. Time delays between the heating of the `front surface' of Au layer and the alternation of x-ray spectrum of Cu attached on the `rear surface' of Au indicate the energetic electron transport mechanism through Au in the warm dense conditions. IBS (IBS-R012-D1) and the NRF (No. 2013R1A1A1007084) of Korea.

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

    Science.gov (United States)

    Chergui, Majed

    2016-05-01

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

  4. 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.

  5. Time-resolved neutron scattering provides new insight into protein substrate processing by a AAA+ unfoldase

    Science.gov (United States)

    Ibrahim, Ziad; Martel, Anne; Moulin, Martine; Kim, Henry S.; Härtlein, Michael; Franzetti, Bruno; Gabel, Frank

    2017-01-01

    We present a combination of small-angle neutron scattering, deuterium labelling and contrast variation, temperature activation and fluorescence spectroscopy as a novel approach to obtain time-resolved, structural data individually from macromolecular complexes and their substrates during active biochemical reactions. The approach allowed us to monitor the mechanical unfolding of a green fluorescent protein model substrate by the archaeal AAA+ PAN unfoldase on the sub-minute time scale. Concomitant with the unfolding of its substrate, the PAN complex underwent an energy-dependent transition from a relaxed to a contracted conformation, followed by a slower expansion to its initial state at the end of the reaction. The results support a model in which AAA ATPases unfold their substrates in a reversible power stroke mechanism involving several subunits and demonstrate the general utility of this time-resolved approach for studying the structural molecular kinetics of multiple protein remodelling complexes and their substrates on the sub-minute time scale. PMID:28102317

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

    Science.gov (United States)

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

    2016-08-01

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

  7. Time Resolved Phonon Spectroscopy, Version 1.0

    Energy Technology Data Exchange (ETDEWEB)

    2016-12-22

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

  8. Time resolved structural dynamics of butadiyne-linked porphyrin dimers.

    Science.gov (United States)

    Camargo, Franco V A; Hall, Christopher R; Anderson, Harry L; Meech, Stephen R; Heisler, Ismael A

    2016-03-01

    In this work, the timescales and mechanisms associated with the structural dynamics of butadiyne-linked porphyrin dimers are investigated through time resolved narrowband pump/broadband probe transient absorption spectroscopy. Our results confirm previous findings that the broadening is partly due to a distribution of structures with different (dihedral) angular conformations. Comparison of measurements with excitations on the red and blue sides of the Q-band unravel the ground and excited state conformational re-equilibration timescales. Further comparison to a planarized dimer, through the addition of a ligand, provides conclusive evidence for the twisting motion performed by the porphyrin dimer in solution.

  9. Time resolved structural dynamics of butadiyne-linked porphyrin dimers

    Directory of Open Access Journals (Sweden)

    Franco V. A. Camargo

    2016-03-01

    Full Text Available In this work, the timescales and mechanisms associated with the structural dynamics of butadiyne-linked porphyrin dimers are investigated through time resolved narrowband pump/broadband probe transient absorption spectroscopy. Our results confirm previous findings that the broadening is partly due to a distribution of structures with different (dihedral angular conformations. Comparison of measurements with excitations on the red and blue sides of the Q-band unravel the ground and excited state conformational re-equilibration timescales. Further comparison to a planarized dimer, through the addition of a ligand, provides conclusive evidence for the twisting motion performed by the porphyrin dimer in solution.

  10. TIME-RESOLVED PHOTOLUMINESCENCE OF SINTERED ZnO CERAMICS

    Institute of Scientific and Technical Information of China (English)

    WEN XIAO-MING(文小明); N.OHNO; ZHANG ZHONG-MING(张中明)

    2001-01-01

    The time-resolved photoluminescence (TRPL) of sintered ZnO ceramics was measured at low temperatures. A broad luminescence band was observed in the visible region. The TRPL experiment shows that photolurninescence decay behaviour can be depicted as t-π(r). The decay rate n(r) and lifetime are wavelength dependent, and the former varies exponentially with wavelength. The power-lowering behaviour of the luminescence intensity indicates that the luminescence band originates from the recombination of donor-acceptor pairs.

  11. Time resolved cryogenic cooling analysis of the Cornell Injector Cryomodule

    Science.gov (United States)

    Eichhorn, R.; Markham, S.; Smith, E.; Quigley, P.

    2015-12-01

    Managing parallel cryogenic flows has become a key challenge in designing efficient and smart cryo-modules for particle accelerators. In analysing the heating dynamics of the Cornell high current injector module a computational tool has been set-up allowing time resolved analysis and optimization. We describe the computational methods and data sets we have used, report the results and compare them to measured data from the module being in good agreement. Mitigation strategies developed on basis of this model have helped us in pushing the operational limitations.

  12. Filming the invisible - time-resolved visualization of compressible flows

    Science.gov (United States)

    Kleine, H.

    2010-04-01

    Essentially all processes in gasdynamics are invisible to the naked eye as they occur in a transparent medium. The task to observe them is further complicated by the fact that most of these processes are also transient, often with characteristic times that are considerably below the threshold of human perception. Both difficulties can be overcome by combining visualization methods that reveal changes in the transparent medium, and high-speed photography techniques that “stop” the motion of the flow. The traditional approach is to reconstruct a transient process from a series of single images, each taken in a different experiment at a different instant. This approach, which is still widely used today, can only be expected to give reliable results when the process is reproducible. Truly time-resolved visualization, which yields a sequence of flow images in a single experiment, has been attempted for more than a century, but many of the developed camera systems were characterized by a high level of complexity and limited quality of the results. Recent advances in digital high-speed photography have changed this situation and have provided the tools to investigate, with relative ease and in sufficient detail, the true development of a transient flow with characteristic time scales down to one microsecond. This paper discusses the potential and the limitations one encounters when using density-sensitive visualization techniques in time-resolved mode. Several examples illustrate how this approach can reveal and explain a number of previously undetected phenomena in a variety of highly transient compressible flows. It is demonstrated that time-resolved visualization offers numerous advantages which normally outweigh its shortcomings, mainly the often-encountered loss in resolution. Apart from the capability to track the location and/or shape of flow features in space and time, adequate time-resolved visualization allows one to observe the development of deliberately

  13. CCD time-resolved photometry of faint cataclysmic variables. III

    Science.gov (United States)

    Howell, Steve B.; Szkody, Paula; Kreidl, Tobias J.; Mason, Keith O.; Puchnarewicz, E. M.

    1990-01-01

    CCD time-resolved photometry in V, B, and near-IR for 17 faint cataclysmic variables (CVs) is presented and analyzed. The data are obtained at Kitt Peak National Observatory, the Perkins reflector, Lowell Observatory, and the Observatorio del Roque de los Muchachos from April-June 1989. The degree of variability and periodicities for the CVs are examined. It is observed that the variability of most of the stars is consistent with CV class behavior. Orbital periods for five CVs are determined, and three potential eclipsing systems are detected.

  14. Timely resolved measurements on CdSe nanoparticles; Zeitaufgeloeste Messungen an CdSe Nanopartikeln

    Energy Technology Data Exchange (ETDEWEB)

    Holt, B.E. von

    2006-06-06

    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{sub 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{sub 3/2}-1S-e and 1P{sub 3/2}-1P{sub e} but not the intermediately lyingt transition 2S{sub 3/2}-1S{sub 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{sub e} and 1P{sub 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

  15. On the biphoton excitation of the fluorescence of the bacteriochlorophyll molecules of purple photosynthetic bacteria by powerful near IR femto-picosecond pulses

    Energy Technology Data Exchange (ETDEWEB)

    Borisov, A. Yu., E-mail: borissov@belozersky.msu.ru [Moscow State University, Belozersky Institute of Physicochemical Biology (Russian Federation)

    2011-11-15

    The authors of a number of experimental works detected nonresonance biphoton excitation of bacteriochlorophyll molecules, which represent the main pigment in the light-absorbing natural 'antenna' complexes of photosynthesizing purple bacteria, by femtosecond IR pulses (1250-1500 nm). They believe that IR quanta excite hypothetic forbidden levels of the pigments of these bacteria in the double frequency range 625-750 nm. We propose and ground an alternative triplet mechanism to describe this phenomenon. According to our hypothesis, the mechanism of biphoton excitation of molecules by IR quanta can manifest itself specifically, through high triplet levels of molecules in the high fields induced by femtosecond-picosecond laser pulses.

  16. Time Resolved FTIR Analysis of Tailpipe Exhaust for Several Automobiles

    Science.gov (United States)

    White, Allen R.; Allen, James; Devasher, Rebecca B.

    2011-06-01

    The automotive catalytic converter reduces or eliminates the emission of various chemical species (e.g. CO, hydrocarbons, etc.) that are the products of combustion from automobile exhaust. However, these units are only effective once they have reached operating temperature. The design and placement of catalytic converters has changed in order to reduce both the quantity of emissions and the time that is required for the converter to be effective. In order to compare the effectiveness of catalytic converters, time-resolved measurements were performed on several vehicles, including a 2010 Toyota Prius, a 2010 Honda Fit, a 1994 Honda Civic, and a 1967 Oldsmobile 442 (which is not equipped with a catalytic converter but is used as a baseline). The newer vehicles demonstrate bot a reduced overall level of CO and hydrocarbon emissions but are also effective more quickly than older units. The time-resolved emissions will be discussed along with the impact of catalytic converter design and location on the measured emissions.

  17. Time-resolved multispectral imaging of combustion reaction

    Science.gov (United States)

    Huot, Alexandrine; Gagnon, Marc-André; Jahjah, Karl-Alexandre; Tremblay, Pierre; Savary, Simon; Farley, Vincent; Lagueux, Philippe; Guyot, Éric; Chamberland, Martin; Marcotte, Fréderick

    2015-05-01

    Thermal infrared imaging is a field of science that evolves rapidly. Scientists have used for years the simplest tool: thermal broadband cameras. This allows to perform target characterization in both the longwave (LWIR) and midwave (MWIR) infrared spectral range. Infrared thermal imaging is used for a wide range of applications, especially in the combustion domain. For example, it can be used to follow combustion reactions, in order to characterize the injection and the ignition in a combustion chamber or even to observe gases produced by a flare or smokestack. Most combustion gases such as carbon dioxide (CO2) selectively absorb/emit infrared radiation at discrete energies, i.e. over a very narrow spectral range. Therefore, temperatures derived from broadband imaging are not reliable without prior knowledge about spectral emissivity. This information is not directly available from broadband images. However, spectral information is available using spectral filters. In this work, combustion analysis was carried out using Telops MS-IR MW camera which allows multispectral imaging at a high frame rate. A motorized filter wheel allowing synchronized acquisitions on eight (8) different channels was used to provide time-resolved multispectral imaging of combustion products of a candle in which black powder has been burnt to create a burst. It was then possible to estimate the temperature by modeling spectral profile derived from information obtained with the different spectral filters. Comparison with temperatures obtained using conventional broadband imaging illustrates the benefits of time-resolved multispectral imaging for the characterization of combustion processes.

  18. Time-resolved multispectral imaging of combustion reactions

    Science.gov (United States)

    Huot, Alexandrine; Gagnon, Marc-André; Jahjah, Karl-Alexandre; Tremblay, Pierre; Savary, Simon; Farley, Vincent; Lagueux, Philippe; Guyot, Éric; Chamberland, Martin; Marcotte, Frédérick

    2015-10-01

    Thermal infrared imaging is a field of science that evolves rapidly. Scientists have used for years the simplest tool: thermal broadband cameras. These allow to perform target characterization in both the longwave (LWIR) and midwave (MWIR) infrared spectral range. Infrared thermal imaging is used for a wide range of applications, especially in the combustion domain. For example, it can be used to follow combustion reactions, in order to characterize the injection and the ignition in a combustion chamber or even to observe gases produced by a flare or smokestack. Most combustion gases, such as carbon dioxide (CO2), selectively absorb/emit infrared radiation at discrete energies, i.e. over a very narrow spectral range. Therefore, temperatures derived from broadband imaging are not reliable without prior knowledge of spectral emissivity. This information is not directly available from broadband images. However, spectral information is available using spectral filters. In this work, combustion analysis was carried out using a Telops MS-IR MW camera, which allows multispectral imaging at a high frame rate. A motorized filter wheel allowing synchronized acquisitions on eight (8) different channels was used to provide time-resolved multispectral imaging of combustion products of a candle in which black powder has been burnt to create a burst. It was then possible to estimate the temperature by modeling spectral profiles derived from information obtained with the different spectral filters. Comparison with temperatures obtained using conventional broadband imaging illustrates the benefits of time-resolved multispectral imaging for the characterization of combustion processes.

  19. Time-resolved flowfield measurements in a turbine stage

    Science.gov (United States)

    Holt, J. L.

    1985-06-01

    Time-resolved flowfield measurements for a 0.5-meter diameter, high work transonic turbine have been completed in the MIT Turbine Blowdown Facility (TBF). Measurements were taken: to determine the blade-to-blade total temperature profile for comparison with predictions from the Euler turbine equation; to determine the effect of using time-averaged pressures to calculate turbine performance; and to provide a complete set of time-resolved turbine stage data. A preliminary objective (given a 6 kHz blade passing frequency) was to determine the frequency response characteristics of the instrumentation used to make the flowfield measurements. A shock tube was built for this purpose. Measurements were taken with high-frequency response instrumentation including a dual-hot-wire aspirating probe, a four-way angle probe, and two cobra head total pressure probes incorporating silicon diaphragm pressure transducers. The aspirating probe is found to have a natural frequency of 15.5 kHz in the test gas with a damping ratio of 0.36; the angle probe a characteristic frequency of 45 kHz with a settling time of 18 usec. Both results are satisfactory for application in the TBF. The measured total temperature profile shows a peak-to-peak variation of 65 C (20%) and a characteristic frequency twice that of the blade passing frequency.

  20. Time resolved spectroscopy of GRB030501 using INTEGRAL

    CERN Document Server

    Beckmann, V; Courvoisier, Thierry J L; Goetz, D; Hudec, R; Hroch, F; Lund, N; Mereghetti, S; Shaw, S E; Wigger, C

    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 positiioning of GRBs and broad band spectral analysis, while SPI provides high resolution spectroscopy. GRB 030501 was discovered by the INTEGRAL Burst Alert System in the ISGRI field of view. Although the burst was fairly weak (fluence F = 3.5 * 10^-6 erg cm^-2 in the 20-200 keV energy band) it was possible to perform time resolved spectroscopy with a resolution of a few seconds. The GRB shows a spectrum in the 20 - 400 keV range which is consistent with a spectral photon index of -1.7. No emission line or spectral break was detectable in the spectrum. Although the flux seems to be correlated with the hardness of the GRB spectrum, there is no clear soft to hard evolution seen over the duration of the burst. The INTEGRAL data have been compared with results from the Ulysses and RHESSI experiments.

  1. Picosecond electron injection dynamics in dye-sensitized oxides in the presence of electrolyte

    NARCIS (Netherlands)

    Pijpers, J.J.H.; Ulbricht, R.; Derossi, S.; Reek, J.N.H.; Bonn, M.

    2011-01-01

    We employ time-resolved terahertz (THz) spectroscopy (TRTS) to directly monitor the picosecond dynamics of electron transfer in dye-sensitized oxides in the presence of an electrolyte phase. Understanding the time scale on which electrons are injected from the dye into the oxide phase in the presenc

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

    Energy Technology Data Exchange (ETDEWEB)

    Niedzwiedzki, Dariusz; Fuciman, Marcel; Kobayashi, Masayuki; Frank, Harry A; Blankenship, R. E.

    2011-10-08

    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.

  3. Time-Resolved Nucleic Acid Hybridization Beacons Utilizing Unimolecular and Toehold-Mediated Strand Displacement Designs.

    Science.gov (United States)

    Massey, Melissa; Ancona, Mario G; Medintz, Igor L; Algar, W Russ

    2015-12-01

    Nucleic acid hybridization probes are sought after for numerous assay and imaging applications. These probes are often limited by the properties of fluorescent dyes, prompting the development of new probes where dyes are paired with novel or nontraditional luminescent materials. Luminescent terbium complexes are an example of such a material, and these complexes offer several unique spectroscopic advantages. Here, we demonstrate two nonstem-loop designs for light-up nucleic acid hybridization beacons that utilize time-resolved Förster resonance energy transfer (TR-FRET) between a luminescent Lumi4-Tb cryptate (Tb) donor and a fluorescent reporter dye, where time-resolved emission from the dye provides an analytical signal. Both designs are based on probe oligonucleotides that are labeled at their opposite termini with Tb and a fluorescent reporter dye. In one design, a probe is partially blocked with a quencher dye-labeled oligonucleotide, and target hybridization is signaled through toehold-mediated strand displacement and loss of a competitive FRET pathway. In the other design, the intrinsic folding properties of an unblocked probe are utilized in combination with a temporal mechanism for signaling target hybridization. This temporal mechanism is based on a recently elucidated "sweet spot" for TR-FRET measurements and exploits distance control over FRET efficiencies to shift the Tb lifetime within or outside the time-gated detection window for measurements. Both the blocked and unblocked beacons offer nanomolar (femtomole) detection limits, response times on the order of minutes, multiplexing through the use of different reporter dyes, and detection in complex matrices such as serum and blood. The blocked beacons offer better mismatch selectivity, whereas the unblocked beacons are simpler in design. The temporal mechanism of signaling utilized with the unblocked beacons also plays a significant role with the blocked beacons and represents a new and effective

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

    CERN Document Server

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

    2015-01-01

    In non-destructive evaluation with X-rays light elements embedded in dense, heavy (or high-Z) matrices show little contrast and their structural details can hardly be revealed. Neutron radiography, on the other hand, provides a solution for those cases, in particular for hydrogenous materials, owing to the large neutron scattering cross section of hydrogen and uncorrelated dependency of neutron cross section on the atomic number. The majority of neutron imaging experiments at the present time is conducted with static objects mainly due to the limited flux intensity of neutron beamline facilities and sometimes due to the limitations of the detectors. However, some applications require the studies of dynamic phenomena and can now be conducted at several high intensity beamlines such as the recently rebuilt ANTARES beam line at the FRM-II reactor. In this paper we demonstrate the capabilities of time resolved imaging for repetitive processes, where different phases of the process can be imaged simultaneously and...

  5. Time-resolved vibrational spectroscopy of a molecular shuttle.

    Science.gov (United States)

    Panman, Matthijs R; Bodis, Pavol; Shaw, Danny J; Bakker, Bert H; Newton, Arthur C; Kay, Euan R; Leigh, David A; Buma, Wybren Jan; Brouwer, Albert M; Woutersen, Sander

    2012-02-14

    Time-resolved vibrational spectroscopy is used to investigate the inter-component motion of an ultraviolet-triggered two-station molecular shuttle. The operation cycle of this molecular shuttle involves several intermediate species, which are observable in the amide I and amide II regions of the mid-IR spectrum. Using ab initio calculations on specific parts of the rotaxane, and by comparing the transient spectra of the normal rotaxane with that of the N-deuterated version, we can assign the observed vibrational modes of each species occurring during the shuttling cycle in an unambiguous way. The complete time- and frequency-dependent data set is analyzed using singular value decomposition (SVD). Using a kinetic model to describe the time-dependent concentrations of the transient species, we derive the absorption spectra associated with each stage in the operation cycle of the molecular shuttle, including the recombination of the charged species.

  6. Spectral characteristics of time resolved magnonic spin Seebeck effect

    Energy Technology Data Exchange (ETDEWEB)

    Etesami, S. R.; Chotorlishvili, L.; Berakdar, J. [Institut für Physik, Martin-Luther-Universität Halle-Wittenberg, 06099 Halle (Germany)

    2015-09-28

    Spin Seebeck effect (SSE) holds promise for new spintronic devices with low-energy consumption. The underlying physics, essential for a further progress, is yet to be fully clarified. This study of the time resolved longitudinal SSE in the magnetic insulator yttrium iron garnet concludes that a substantial contribution to the spin current stems from small wave-vector subthermal exchange magnons. Our finding is in line with the recent experiment by S. R. Boona and J. P. Heremans [Phys. Rev. B 90, 064421 (2014)]. Technically, the spin-current dynamics is treated based on the Landau-Lifshitz-Gilbert equation also including magnons back-action on thermal bath, while the formation of the time dependent thermal gradient is described self-consistently via the heat equation coupled to the magnetization dynamics.

  7. Spectral characteristics of time resolved magnonic spin Seebeck effect

    Science.gov (United States)

    Etesami, S. R.; Chotorlishvili, L.; Berakdar, J.

    2015-09-01

    Spin Seebeck effect (SSE) holds promise for new spintronic devices with low-energy consumption. The underlying physics, essential for a further progress, is yet to be fully clarified. This study of the time resolved longitudinal SSE in the magnetic insulator yttrium iron garnet concludes that a substantial contribution to the spin current stems from small wave-vector subthermal exchange magnons. Our finding is in line with the recent experiment by S. R. Boona and J. P. Heremans [Phys. Rev. B 90, 064421 (2014)]. Technically, the spin-current dynamics is treated based on the Landau-Lifshitz-Gilbert equation also including magnons back-action on thermal bath, while the formation of the time dependent thermal gradient is described self-consistently via the heat equation coupled to the magnetization dynamics.

  8. 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.

  9. Time-resolved spectroscopy of low-dimensional semiconductor structures

    Science.gov (United States)

    Murphy, Joseph R.

    This dissertation is a survey of ultrafast time-resolved optical measurements conducted on a variety of low-dimensional semiconductor systems to further the understanding of the dynamic behavior in the following systems: ZnMnTe/ZnSe quantum dots, ZnTe/ZnMnSe quantum dots, InGaAs quantum wells, CdMnSe colloidal quantum dots, multi-shell CdSe/CdMnS/CdS colloidal nanoplatelets, and graphene and graphene-related solutions and films. Using time-resolved photoluminescence to study epitaxially-grown ZnTe and ZnMnTe quantum dots in corresponding ZnMnSe and ZnSe matrices, the location dependence of manganese ions in respect to magnetic polaron formation is shown. The structure with manganese ions located in the matrix exhibited magnetic polaron behavior consistent with previous literature, whereas the structure with the magnetic ions located within the quantum dots exhibited unconventional magnetic polaron properties. These properties, including temperature and magnetic field insensitivity, were explained through the use of a model that predicted an increased internal magnetic field due to a decreased effective volume of the magnetic polaron and a higher effective temperature due to laser heating. Magneto-time-resolved photoluminescence measurements on a system of colloidal CdMnSe quantum dots show that the magnetic polaron properties differ significantly from the epitaxially grown quantum dots. First the timescales at which the magnetic polaron forms and the polarization saturates are different by more than an order of magnitude, and second, the magnetic polaron energy exhibited step-like behavior as the strength of the externally applied magnetic field is increased. The field dependent MP formation energy that is observed experimentally is explained as due to the breaking of the antiferromagnetic coupling of Mn dimers within the QDs. This model is further verified by the observation of quantized behavior in the Zeeman energy splitting. Through the use of magneto

  10. FXR LIA Optimization - Time-resolved OTR Emittance Measurement

    Energy Technology Data Exchange (ETDEWEB)

    Jacob, J; Ong, M; Wargo, P; LeSage, G

    2005-07-21

    The Flash X-Ray Radiography (FXR) facility at Lawrence Livermore National Laboratory utilizes a high current, long pulse linear induction accelerator to produce high doses of x-ray radiation. Accurate characterization of the transverse beam emittance is required in order to facilitate accelerator modeling and tuning efforts and, ultimately, to optimize the final focus spot size, yielding higher resolution radiographs. In addition to conventional magnet scan, pepper-pot, and multiple screen techniques, optical transition radiation (OTR) has been proven as a useful emittance measurement diagnostic and is particularly well suited to the FXR accelerator. We shall discuss the time-resolved emittance characterization of an induction linac electron beam using OTR, and we will present our experimental apparatus and analysis software. We shall also develop the theoretical background of beam emittance and transition radiation.

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

    Science.gov (United States)

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

    2016-10-01

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

  12. Pose estimation using time-resolved inversion of diffuse light.

    Science.gov (United States)

    Raviv, Dan; Barsi, Christopher; Naik, Nikhil; Feigin, Micha; Raskar, Ramesh

    2014-08-25

    We present a novel approach for evaluation of position and orientation of geometric shapes from scattered time-resolved data. Traditionally, imaging systems treat scattering as unwanted and are designed to mitigate the effects. Instead, we show here that scattering can be exploited by implementing a system based on a femtosecond laser and a streak camera. The result is accurate estimation of object pose, which is a fundamental tool in analysis of complex scenarios and plays an important role in our understanding of physical phenomena. Here, we experimentally show that for a given geometry, a single incident illumination point yields enough information for pose estimation and tracking after multiple scattering events. Our technique can be used for single-shot imaging behind walls or through turbid media.

  13. Multidimensional Time-Resolved Spectroscopy of Vibrational Coherence in Biopolyenes

    Science.gov (United States)

    Buckup, Tiago; Motzkus, Marcus

    2014-04-01

    Multidimensional femtosecond time-resolved vibrational coherence spectroscopy allows one to investigate the evolution of vibrational coherence in electronic excited states. Methods such as pump-degenerate four-wave mixing and pump-impulsive vibrational spectroscopy combine an initial ultrashort laser pulse with a nonlinear probing sequence to reinduce vibrational coherence exclusively in the excited states. By carefully exploiting specific electronic resonances, one can detect vibrational coherence from 0 cm-1 to over 2,000 cm-1 and map its evolution. This review focuses on the observation and mapping of high-frequency vibrational coherence for all-trans biological polyenes such as β-carotene, lycopene, retinal, and retinal Schiff base. We discuss the role of molecular symmetry in vibrational coherence activity in the S1 electronic state and the interplay of coupling between electronic states and vibrational coherence.

  14. Time-Resolved Infrared (TRIR) Studies of Oxycarbonylnitrenes.

    Science.gov (United States)

    Chavez, Tyler A; Liu, Yonglin; Toscano, John P

    2016-08-05

    N-Ethyloxycarbonyl-S,S-dibenzothiphene sulfilimine and N-t-butyloxycarbonyl-S,S-dibenzothiphene sulfilimine have been utilized as precursors to ethoxycarbonylnitrene and t-butyloxycarbonylnitrene. B3LYP/6-31G(d) calculations predict triplet ground states for both oxycarbonylnitrenes, albeit by small margins. Triplet ethoxycarbonylnitrene and triplet t-butyloxycarbonylnitrene have been observed following photolysis of these sulfilimine precursors by time-resolved infrared (TRIR) spectroscopy. Kinetic studies show that ethoxycarbonylnitrene reacts with solvents such as acetonitrile and cyclohexane, while t-butyloxycarbonylnitrene undergoes an intramolecular insertion reaction to produce 5,5-dimethyl oxazolidinone. Product analysis following photolysis of N-t-butyloxycarbonyl-S,S-dibenzothiphene sulfilimine confirms that the oxazolidinone is the major product with an estimated yield of 90%. The products from these two nitrenes are derived from the corresponding singlet nitrene, either directly or via thermal repopulation of the singlet from the lower-energy triplet nitrene.

  15. Towards time-resolved serial crystallography in a microfluidic device.

    Science.gov (United States)

    Pawate, Ashtamurthy S; Šrajer, Vukica; Schieferstein, Jeremy; Guha, Sudipto; Henning, Robert; Kosheleva, Irina; Schmidt, Marius; Ren, Zhong; Kenis, Paul J A; Perry, Sarah L

    2015-07-01

    Serial methods for crystallography have the potential to enable dynamic structural studies of protein targets that have been resistant to single-crystal strategies. The use of serial data-collection strategies can circumvent challenges associated with radiation damage and repeated reaction initiation. This work utilizes a microfluidic crystallization platform for the serial time-resolved Laue diffraction analysis of macroscopic crystals of photoactive yellow protein (PYP). Reaction initiation was achieved via pulsed laser illumination, and the resultant electron-density difference maps clearly depict the expected pR(1)/pR(E46Q) and pR(2)/pR(CW) states at 10 µs and the pB1 intermediate at 1 ms. The strategies presented here have tremendous potential for extension to chemical triggering methods for reaction initiation and for extension to dynamic, multivariable analyses.

  16. 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.

  17. Multidimensional time-resolved spectroscopy of vibrational coherence in biopolyenes.

    Science.gov (United States)

    Buckup, Tiago; Motzkus, Marcus

    2014-01-01

    Multidimensional femtosecond time-resolved vibrational coherence spectroscopy allows one to investigate the evolution of vibrational coherence in electronic excited states. Methods such as pump-degenerate four-wave mixing and pump-impulsive vibrational spectroscopy combine an initial ultrashort laser pulse with a nonlinear probing sequence to reinduce vibrational coherence exclusively in the excited states. By carefully exploiting specific electronic resonances, one can detect vibrational coherence from 0 cm(-1) to over 2,000 cm(-1) and map its evolution. This review focuses on the observation and mapping of high-frequency vibrational coherence for all-trans biological polyenes such as β-carotene, lycopene, retinal, and retinal Schiff base. We discuss the role of molecular symmetry in vibrational coherence activity in the S1 electronic state and the interplay of coupling between electronic states and vibrational coherence.

  18. Nonselective and polarization effects in time-resolved optogalvanic spectroscopy

    Science.gov (United States)

    Zhechev, D.; Steflekova, V.

    2016-02-01

    Three interfering effects in optogalvanic (OG) spectroscopy are identified in a hollow cathode discharge (HCD) - OG detector. The laser beam is found to generate two nonselective processes, namely photoelectron emission (PE) from the cathode surface with a sub-breakdown bias applied, and nonresonant space ionization. The convolution of these galvanic contributions was determined experimentally as an instrumental function and a deconvolution procedure to determine the actual OG signal was developed. Specific plasma conductance is detected dependent on the polarization of the laser beam irradiating. Linearly/circularly polarized light beam is found to induce OG signals differ in amplitude (and their shape parameters in the time-resolved OG signals (TROGS)). The phenomena coherence and specific conductance are found to be in causal relationship. The additional conductance due to coherent states of atoms manifests itself as an intrinsic instrumental property of OG detector.

  19. Time-resolved fluoroimmunoassay for bactericidal/permeability-increasing protein

    Directory of Open Access Journals (Sweden)

    J.-O. Häggblom

    1996-01-01

    Full Text Available Bactericidal/permeability-increasing protein (BPI is a cationic antimicrobial protein produced by polymorphonuclear leukocytes, that specifically interacts with and kills Gram-negative bacteria. BPl competes with lipopolysaccharide-binding protein (LBP secreted by liver cells into blood plasma for binding to lipopolysaccharide (LPS and thus reduces the proinflammatory effects of LPS. We have developed a time-resolved fluoroimmunoassay for BPI and measured the concentration of BPI in human serum and plasma samples. The assay is based on a rabbit antibody against recombinant BPI. This antibody specifically adheres to polymorphonuclear leukocytes in immunostained human tissues. The difference in the serum concentration of BPI between unselected hospitalized patients with and without an infection was statistically significant. The mean concentration of BPI in serum samples was 28.3 μg/l (range 1.64–132, S.D. 26.8, n = 83. In contrast, there was no difference between the two groups in the BPI levels in plasma samples. For all individuals tested, BPI levels were consistently higher in plasma samples compared to the matched serum samples. The mean concentration of BPI in plasma samples was 52.3 μg/l (range 0.9–403, S.D. 60.6, n = 90. There was a positive correlation between the concentration of BPI and the white blood cell count as well as between the BPI concentration and C-reactive protein (CRP in serum samples. In conclusion, the present study demonstrates that BPI can be quantified reliably by time-resolved fluoroimmunoassay in human serum samples.

  20. Probing the reactivity of photoinitiators for free radical polymerization: time-resolved infrared spectroscopic study of benzoyl radicals.

    Science.gov (United States)

    Colley, Christopher S; Grills, David C; Besley, Nicholas A; Jockusch, Steffen; Matousek, Pavel; Parker, Anthony W; Towrie, Michael; Turro, Nicholas J; Gill, Peter M W; George, Michael W

    2002-12-18

    A series of substituted benzoyl radicals has been generated by laser flash photolysis of alpha-hydroxy ketones, alpha-amino ketones, and acyl and bis(acyl)phosphine oxides, all of which are used commercially as photoinitiators in free radical polymerizations. The benzoyl radicals have been studied by fast time-resolved infrared spectroscopy. The absolute rate constants for their reaction with n-butylacrylate, thiophenol, bromotrichloromethane and oxygen were measured in acetonitrile solution. The rate constants of benzoyl radical addition to n-butylacrylate range from 1.3 x 10(5) to 5.5 x 10(5) M(-1) s(-1) and are about 2 orders of magnitude lower than for the n-butylacrylate addition to the counterradicals that are produced by alpha-cleavage of the investigated ketones. Density functional theoretical calculations have been performed in order to rationalize the observed reactivities of the initiating radicals. Calculations of the phosphorus-centered radicals generated by photolysis of an acyl and bis(acyl)phosphine oxide suggest that P atom Mulliken spin populations are an indicator of the relative reactivities of the phosphorus-centered radicals. The alpha-cleavage of (2,4,6-trimethylbenzoyl)phosphine oxide was studied by picosecond pump-probe and nanosecond step-scan time-resolved infrared spectroscopy. The results support a mechanism in which the alpha-cleavage occurs from the triplet excited state that has a lifetime less than or equal to the singlet excited state.

  1. Transient Lattice Response to the Interaction between Pulse-Laser and Semiconductors Probed by Time-Resolved X-Ray Diffraction

    Science.gov (United States)

    Kishimura, Hiroaki; Kawano, Hidetaka; Hironaka, Yoichiro; Nakamura, Kazutaka G.; Kondo, Ken-ichi

    2004-07-01

    Time-resolved X-ray diffraction has been performed on laser irradiated Si and Ge crystals. In the case of Si, the lattice expansion due to laser heating is observed. On the other hand, the compression wave is propagated into a Ge crystal. The maximum compression of Ge is about 4 %, which is larger than the Hugoniot elastic limit (HEL). The results suggest that Ge is not compressed hydrostatically, but compressed uniaxially at 7.5 GPa in a picosecond time scale. The strain profiles inside the crystals are obtained as the calculated rocking curves represent well the experiment.

  2. Time resolved PIV and flow visualization of 3D sheet cavitation

    Energy Technology Data Exchange (ETDEWEB)

    Foeth, E.J.; Doorne, C.W.H. van; Terwisga, T. van [Delft University of Technology, Laboratory of Ship Hydromechanics, Delft (Netherlands); Wieneke, B. [LaVision GmbH, Goettingen (Germany)

    2006-04-15

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

  3. Time-Resolved Luminescence Nanothermometry with Nitrogen-Vacancy Centers in Nanodiamonds.

    Science.gov (United States)

    Tzeng, Yan-Kai; Tsai, Pei-Chang; Liu, Hsiou-Yuan; Chen, Oliver Y; Hsu, Hsiang; Yee, Fu-Goul; Chang, Ming-Shien; Chang, Huan-Cheng

    2015-06-10

    Measuring temperature in nanoscale spatial resolution either at or far from equilibrium is of importance in many scientific and technological applications. Although negatively charged nitrogen-vacancy (NV(-)) centers in diamond have recently emerged as a promising nanometric temperature sensor, the technique has been applied only under steady state conditions so far. Here, we present a three-point sampling method that allows real-time monitoring of the temperature changes over ±100 K and a pump-probe-type experiment that enables the study of nanoscale heat transfer with a temporal resolution of better than 10 μs. The utility of the time-resolved luminescence nanothermometry was demonstrated with 100 nm fluorescent nanodiamonds spin-coated on a glass substrate and submerged in gold nanorod solution heated by a near-infrared laser, and the validity of the measurements was verified with finite-element numerical simulations. The combined theoretical and experimental approaches will be useful to implement time-resolved temperature sensing in laser processing of materials and even for devices in operation at the nanometer scale.

  4. Sub-picosecond time resolved infrared spectroscopy of high-spin state formation in Fe(II) spin crossover complexes

    DEFF Research Database (Denmark)

    Døssing, Anders Rørbæk; Wolf, Matthias M. N.; Gross, Ruth

    2008-01-01

      The photoinduced low-spin (S = 0) to high-spin (S = 2) transition of the iron(II) spin-crossover systems [Fe(btpa)](PF6)2 and [Fe(b(bdpa))](PF6)2 in solution have been studied for the first time by means of ultrafast transient infrared spectroscopy at room temperature. Negative and positive...... absorption cross sections. The simulated infrared difference spectra are dominated by an increase of the absorption cross section upon high-spin state formation in accordance with the experimental infrared spectra....... infrared difference bands between 1000 and 1065 cm-1 that appear within the instrumental system response time of 350 fs after excitation at 387 nm display the formation of the vibrationally unrelaxed and hot high-spin 5T2 state. Vibrational relaxation is observed and characterized by the time constants 9...

  5. In-depth quantification by using multispectral time-resolved diffuse optical tomography

    Science.gov (United States)

    Zouaoui, Judy; Hervé, Lionel; Di Sieno, Laura; Planat-Chrétien, Anne; Berger, Michel; Dalla Mora, Alberto; Pifferi, Antonio; Derouard, Jacques; Dinten, Jean-Marc

    2015-07-01

    Near-infrared diffuse optical tomography (DOT) is a medical imaging which gives the distribution of the optical properties of biological tissues. To obtain endogenous chromophore features in the depth of a scattering medium, a multiwavelength/time-resolved (MW/TR) DOT setup was used. Reconstructions of the three-dimensional maps of chromophore concentrations of probed media were obtained by using a data processing technique which manages Mellin-Laplace Transforms of their MW/TR optical signals and those of a known reference medium. The point was to put a constraint on the medium absorption coefficient by using a material basis composed of a given set of chromophores of known absorption spectra. Experimental measurements were conducted by injecting the light of a picosecond near- infrared laser in the medium of interest and by collecting, for several wavelengths and multiple positions, the backscattered light via two fibers (with a source-detector separation of 15 mm) connected to fast-gated single-photon avalanche diodes (SPAD) and coupled to a time-correlated single-photon counting (TCSPC) system. Validations of the method were performed in simulation in the same configuration as the experiments for different combination of chromophores. Evaluation of the technique in real conditions was investigated on liquid phantoms composed of an homogenous background and a 10 mm depth inclusion formed of combination of intralipid and inks scanned at 30 positions and at three wavelengths. Both numerical and preliminary phantom experiments confirm the potential of this method to determine chromophore concentrations in the depth of biological tissues.

  6. New method for measuring time-resolved spectra of lanthanide emission using square-wave excitation

    Energy Technology Data Exchange (ETDEWEB)

    Qin, Feng [Condensed Matter Science and Technology Institute, Harbin Institute of Technology, Harbin 150080 (China); Zhao, Hua; Cai, Wei, E-mail: weicai@hit.edu.cn [School of Materials Science and Engineering, Harbin Institute of Technology, Harbin 150001 (China); Duan, Qianqian [College of Information Engineering, Taiyuan University of Technology, Taiyuan 030024 (China); Zhang, Zhiguo, E-mail: zhangzhiguo@hit.edu.cn [Condensed Matter Science and Technology Institute, Harbin Institute of Technology, Harbin 150080 (China); Laboratory of Sono- and Photo-Theranostic Technologies, Harbin Institute of Technology, Harbin 150080 (China); Cao, Wenwu, E-mail: dzk@psu.edu [Condensed Matter Science and Technology Institute, Harbin Institute of Technology, Harbin 150080 (China); Laboratory of Sono- and Photo-Theranostic Technologies, Harbin Institute of Technology, Harbin 150080 (China); Materials Research Institute, The Pennsylvania State University, University Park, Pennsylvania 16802 (United States)

    2013-11-15

    A method using modulated continuous wave (CW) visible laser to measure time-resolved fluorescence spectra of trivalent rare-earth ions has been developed. Electro-optic modulator was used to modulate the CW pumping laser with a rise time of 2 μs. CW Nd{sup 3+} lasers were used as examples to present the method. Upconversion dynamic process of Ho{sup 3+} was studied utilizing a 532 nm CW laser. Quantum cutting dynamic process from Tb{sup 3+} to Yb{sup 3+} was analyzed by a 473 nm CW laser. This method can be applied to any CW laser such as He-Ne laser, Ar{sup +} laser, Kr{sup +} laser, Ti:sapphire laser, etc.

  7. Development of ultrafast time-resolved dual-comb spectroscopy

    Directory of Open Access Journals (Sweden)

    Akifumi Asahara

    2017-04-01

    Full Text Available Ultrafast time-resolved dual-comb spectroscopy (TR-DCS has been demonstrated, which enables direct observations of transient responses of complex optical spectra by combining dual-comb spectroscopy with the pump–probe method. TR-DCS achieves two-dimensional spectroscopy with a wide dynamic range for both the temporal and frequency axes. As a demonstration, we investigated the femtosecond relaxation dynamics of a photo-excited InGaAs saturable absorber in the near-infrared frequency region. The transient response of the interferogram was successfully obtained, and both the amplitude and phase spectra of the dynamic complex transmittance were independently deduced without using the Kramers-Kronig relations. A high phase resolution in the order of milliradian was achieved by suppressing the effect from the slow phase drift caused in the experimental system. Our proof-of-principle experiment promotes a pathway to coherent, highly accurate, and multi-dimensional pump–probe spectroscopy using the optical frequency comb technology.

  8. 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...... of bringing the data from measurement to analysis. Bridging the experimental design and challenges of the experiments from X-ray synchrotrons to the newly available X-ray Free Electron Laser sources (XFEL).LCLS in California is the first XFEL to come online and delivers intense 30fs X-ray pulses, orders...... of magnitude shorter than the 100ps X-ray pulses available from synchroton sources. This increase in time-resolution allows for the use of X-ray techniques in a completely new time-domain, where coherent photo-induced changes in structure can be studied on their intrinsic time-scale. Measurements on Rh2(dimen...

  9. Time-resolved infrared spectroscopic techniques as applied to Channelrhodopsin

    Directory of Open Access Journals (Sweden)

    Eglof eRitter

    2015-07-01

    Full Text Available Among optogenetic tools, channelrhodopsins, the light gated ion channels of the plasma membrane from green algae, play the most important role. Properties like channel selectivity, timing parameters or color can be influenced by the exchange of selected amino acids. Although widely used, in the field of neurosciences for example, there is still little known about their photocycles and the mechanism of ion channel gating and conductance. One of the preferred methods for these studies is infrared spectroscopy since it allows observation of proteins and their function at a molecular level and in near-native environment. The absorption of a photon in channelrhodopsin leads to retinal isomerization within femtoseconds, the conductive states are reached in the microsecond time scale and the return into the fully dark-adapted state may take more than minutes. To be able to cover all these time regimes, a range of different spectroscopical approaches are necessary. This mini-review focuses on time-resolved applications of the infrared technique to study channelrhodopsins and other light triggered proteins. We will discuss the approaches with respect to their suitability to the investigation of channelrhodopsin and related proteins.

  10. 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.

  11. Fielding of a Time-Resolved Tomographic Diagnostic

    Energy Technology Data Exchange (ETDEWEB)

    Daniel Frayer, Brian Cox, Wendi Dreesen, Douglas Johnson, Mike Jones, Morris Kaufman

    2008-09-11

    A diagnostic instrument has been developed for the acquisition of high-speed time-resolved images at the Dual-Axis Radiographic Hydrodynamic Test (DARHT) Facility at Los Alamos National Laboratory. The instrument was developed in order to create time histories of the electron beam. Four discrete optical subsystems view Cerenkov light generated at an x-ray target inside of a vacuum envelope. Each system employs cylindrical optics to image light in one direction and collapse light in the orthogonal direction. Each of the four systems images and collapses in unique axes, thereby capturing unique information. Light along the imaging axis is relayed via optical fiber to streak cameras. A computer is used to reconstruct the original image from the four optically collapsed images. Due to DARHT’s adverse environment, the instrument can be operated remotely to adjust optical parameters and contains a subsystem for remote calibration. The instrument was deployed and calibrated, and has been used to capture and reconstruct images. Matters of alignment, calibration, control, resolution, and adverse conditions will be discussed.

  12. A Clinical Tissue Oximeter Using NIR Time-Resolved Spectroscopy.

    Science.gov (United States)

    Fujisaka, Shin-ichi; Ozaki, Takeo; Suzuki, Tsuyoshi; Kamada, Tsuyoshi; Kitazawa, Ken; Nishizawa, Mitsunori; Takahashi, Akira; Suzuki, Susumu

    2016-01-01

    The tNIRS-1, a new clinical tissue oximeter using NIR time-resolved spectroscopy (TRS), has been developed. The tNIRS-1 measures oxygenated, deoxygenated and total hemoglobin and oxygen saturation in living tissues. Two-channel TRS measurements are obtained using pulsed laser diodes (LD) at three wavelengths, multi-pixel photon counters (MPPC) for light detection, and time-to-digital converters (TDC) for time-of-flight photon measurements. Incorporating advanced semiconductor devices helped to make the design of this small-size, low-cost and low-power TRS instrument possible. In order to evaluate the correctness and reproducibility of measurement data obtained with the tNIRS-1, a study using blood phantoms and healthy volunteers was conducted to compare data obtained from a conventional SRS device and data from an earlier TRS system designed for research purposes. The results of the study confirmed the correctness and reproducibility of measurement data obtained with the tNIRS-1. Clinical evaluations conducted in several hospitals demonstrated a high level of usability in clinical situations and confirmed the efficacy of measurement data obtained with the tNIRS-1.

  13. Time-resolved two-photon photoemission from metal surfaces

    CERN Document Server

    Weinelt, M

    2002-01-01

    The Rydberg-like series of image-potential states is a prototype system for loosely bound electrons at a metal surface. The electronic structure and the femtosecond dynamics of these states is studied by high-resolution energy-and time-resolved two-photon photoemission spectroscopy. The electron trapped in the image potential moves virtually freely laterally to the surface where it is subject to inelastic and quasielastic scattering processes which cause decay of population and phase relaxation. The influence of surface corrugation on these processes has been investigated for adsorbates on Cu(001) and stepped Cu(117) and Cu(119) surfaces which are vicinal to Cu(001). The dynamics depend on both the distance of the electron in front of the surface and the parallel momentum. For CO molecules on Cu(001) inelastic scattering into bulk states and adsorbate-induced resonances determine the decay rate. For small numbers of Cu adatoms on Cu(001) and the vicinal surfaces the decay rate of image-potential states is sig...

  14. Direct observation of intersystem crossing in a thermally activated delayed fluorescence copper complex in the solid state.

    Science.gov (United States)

    Bergmann, Larissa; Hedley, Gordon J; Baumann, Thomas; Bräse, Stefan; Samuel, Ifor D W

    2016-01-01

    Intersystem crossing in thermally activated delayed fluorescence (TADF) materials is an important process that controls the rate at which singlet states convert to triplets; however, measuring this directly in TADF materials is difficult. TADF is a significant emerging technology that enables the harvesting of triplets as well as singlet excited states for emission in organic light emitting diodes. We have observed the picosecond time-resolved photoluminescence of a highly luminescent, neutral copper(I) complex in the solid state that shows TADF. The time constant of intersystem crossing is measured to be 27 picoseconds. Subsequent overall reverse intersystem crossing is slow, leading to population equilibration and TADF with an average lifetime of 11.5 microseconds. These first measurements of intersystem crossing in the solid state in this class of mononuclear copper(I) complexes give a better understanding of the excited-state processes and mechanisms that ensure efficient TADF.

  15. Time-resolved microrheology of actively remodeling actomyosin networks

    Science.gov (United States)

    Silva, Marina Soares e.; Stuhrmann, Björn; Betz, Timo; Koenderink, Gijsje H.

    2014-07-01

    Living cells constitute an extraordinary state of matter since they are inherently out of thermal equilibrium due to internal metabolic processes. Indeed, measurements of particle motion in the cytoplasm of animal cells have revealed clear signatures of nonthermal fluctuations superposed on passive thermal motion. However, it has been difficult to pinpoint the exact molecular origin of this activity. Here, we employ time-resolved microrheology based on particle tracking to measure nonequilibrium fluctuations produced by myosin motor proteins in a minimal model system composed of purified actin filaments and myosin motors. We show that the motors generate spatially heterogeneous contractile fluctuations, which become less frequent with time as a consequence of motor-driven network remodeling. We analyze the particle tracking data on different length scales, combining particle image velocimetry, an ensemble analysis of the particle trajectories, and finally a kymograph analysis of individual particle trajectories to quantify the length and time scales associated with active particle displacements. All analyses show clear signatures of nonequilibrium activity: the particles exhibit random motion with an enhanced amplitude compared to passive samples, and they exhibit sporadic contractile fluctuations with ballistic motion over large (up to 30 μm) distances. This nonequilibrium activity diminishes with sample age, even though the adenosine triphosphate level is held constant. We propose that network coarsening concentrates motors in large clusters and depletes them from the network, thus reducing the occurrence of contractile fluctuations. Our data provide valuable insight into the physical processes underlying stress generation within motor-driven actin networks and the analysis framework may prove useful for future microrheology studies in cells and model organisms.

  16. Microsecond Time-Resolved Circular Dichroism of Rhodopsin Photointermediates†

    Science.gov (United States)

    Thomas, Yiren Gu; Szundi, Istvan; Lewis, James W.; Kliger, David S.

    2009-01-01

    Time-resolved circular dichroism measurements, over a spectral range from 300 to 700 nm, were made at delays of 5, 100 and 500 μs after room temperature photoexcitation of bovine rhodopsin in lauryl maltoside suspension. The purpose was to provide more structural information about intermediate states in the activation of rhodopsin and other G protein-coupled receptors. In particular, information was sought about photointermediates that are isochromic or nearly isochromic in their unpolarized absorbance. The circular dichroism spectrum of lumirhodopsin, obtained after correcting the 5 μs difference CD data for the rhodopsin bleached, was in reasonable agreement with the lumirhodopsin CD spectrum obtained previously by thermal trapping at -76°C. Similarly, the metarhodopsin II spectrum obtained at 500 μs delay was also in agreement with the results of previous work on the temperature trapped form of metarhodopsin II. However, the CD of the mixture formed at 100 μs delay after photoexcitation, whose only visible absorbing component is lumirhodopsin, could not be accounted for near 480 nm in terms of the initially formed, 5 μs lumirhodopsin CD spectrum. Thus, the CD spectrum of lumirhodopsin changes on the time scale from 5 to 100 μs, showing reduced rotational strength in its visible band, possibly associated with either a process responsible for a small spectral shift that occurs in the lumirhodopsin absorbance spectrum at earlier times or the Schiff base deprotonation-reprotonation which occurs during equilibration of lumirhodopsin with the Meta I380 photointermediate. Either explanation suggests a chromophore conformation change closely associated with deprotonation which could be the earliest direct trigger of activation. PMID:19905009

  17. Miniaturized time-resolved Raman spectrometer for planetary science based on a fast single photon avalanche diode detector array.

    Science.gov (United States)

    Blacksberg, Jordana; Alerstam, Erik; Maruyama, Yuki; Cochrane, Corey J; Rossman, George R

    2016-02-01

    We present recent developments in time-resolved Raman spectroscopy instrumentation and measurement techniques for in situ planetary surface exploration, leading to improved performance and identification of minerals and organics. The time-resolved Raman spectrometer uses a 532 nm pulsed microchip laser source synchronized with a single photon avalanche diode array to achieve sub-nanosecond time resolution. This instrument can detect Raman spectral signatures from a wide variety of minerals and organics relevant to planetary science while eliminating pervasive background interference caused by fluorescence. We present an overview of the instrument design and operation and demonstrate high signal-to-noise ratio Raman spectra for several relevant samples of sulfates, clays, and polycyclic aromatic hydrocarbons. Finally, we present an instrument design suitable for operation on a rover or lander and discuss future directions that promise great advancement in capability.

  18. Isomerization and fluorescence depolarization of merocyanine 540 in polyacrylic acid. Effect of H

    Indian Academy of Sciences (India)

    Dipankar Sukul; Sobhan Sen; Partha Dutta; Kankan Bhattacharyya

    2002-10-01

    Dynamics of isomerization and fluorescence depolarization of merocyanine 540 (MC540) in an aqueous solution of polyacrylic acid (PAA) have been studied using picosecond time resolved fluorescence spectroscopy. It is observed that the dynamics of isomerization and depolarization are sensitive enough to monitor the uncoiling of PAA at high H (> 6). At low H (< 3), when the polymer remains in a hypercoiled form, polymer bound MC540 experiences very high microscopic friction and, hence, the isomerization and depolarization processes are very slow. At high H (> 6) a polyanion is formed and the polymer assumes an extended configuration due to electrostatic repulsion. At high H (> 6), the anionic probe MC540 is expelled from the polyanion to bulk water and the dynamics of isomerization and fluorescence depolarization become faster by 12 and 5 times respectively, compared to those at low H.

  19. Time Resolved Resonance Raman Conference Royal Institution, London United Kingdom,

    Science.gov (United States)

    1983-01-01

    polar molecules. The rejection of fluorescence which is practically inherent _s most if not all resonance Raman experiments was discussed is great ...presented may be devided into two sections. 1) chemical processes presented in the rorninq and 2) biological in the afternoon. The resonance Raman spectra

  20. Optoelectronic Picosecond Detection of Synchrotron X-rays

    Energy Technology Data Exchange (ETDEWEB)

    Durbin, Stephen M. [Purdue Univ., West Lafayette, IN (United States)

    2017-08-04

    The goal of this research program was to develop a detector that would measure x-ray time profiles with picosecond resolution. This was specifically aimed for use at x-ray synchrotrons, where x-ray pulse profiles have Gaussian time spreads of 50-100 ps (FWHM), so the successful development of such a detector with picosecond resolution would permit x-ray synchrotron studies to break through the pulse width barrier. That is, synchrotron time-resolved studies are currently limited to pump-probe studies that cannot reveal dynamics faster than ~50 ps, whereas the proposed detector would push this into the physically important 1 ps domain. The results of this research effort, described in detail below, are twofold: 1) the original plan to rely on converting electronic signals from a semiconductor sensor into an optical signal proved to be insufficient for generating signals with the necessary time resolution and sensitivity to be widely applicable; and 2) an all-optical method was discovered whereby the x-rays are directly absorbed in an optoelectronic material, lithium tantalate, which can then be probed by laser pulses with the desired picosecond sensitivity for detection of synchrotron x-rays. This research program has also produced new fundamental understanding of the interaction of x-rays and optical lasers in materials that has now created a viable path for true picosecond detection of synchrotron x-rays.

  1. 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

  2. Time-Resolved Spectroscopy of Active Binary Stars

    Science.gov (United States)

    Brown, Alexander

    2000-01-01

    This NASA grant covered EUVE observing and data analysis programs during EUVE Cycle 5 GO observing. The research involved a single Guest Observer project 97-EUVE-061 "Time-Resolved Spectroscopy of Active Binary Stars". The grant provided funding that covered 1.25 months of the PI's salary. The activities undertaken included observation planning and data analysis (both temporal and spectral). This project was awarded 910 ksec of observing time to study seven active binary stars, all but one of which were actually observed. Lambda-And was observed on 1997 Jul 30 - Aug 3 and Aug 7-14 for a total of 297 ksec; these observations showed two large complex flares that were analyzed by Osten & Brown (1999). AR Psc, observed for 350 ksec on 1997 Aug 27 - Sep 13, showed only relatively small flares that were also discussed by Osten & Brown (1999). EUVE observations of El Eri were obtained on 1994 August 24-28, simultaneous with ASCA X-ray spectra. Four flares were detected by EUVE with one of these also observed simultaneously, by ASCA. The other three EUVE observations were of the stars BY Dra (1997 Sep 22-28), V478 Lyr (1998 May 18-27), and sigma Gem (1998 Dec 10-22). The first two stars showed a few small flares. The sigma Gem data shows a beautiful complete flare with a factor of ten peak brightness compared to quiescence. The flare rise and almost all the decay phase are observed. Unfortunately no observations in other spectral regions were obtained for these stars. Analysis of the lambda-And and AR Psc observations is complete and the results were published in Osten & Brown (1999). Analysis of the BY Dra, V478 Lyr and sigma Gem EUVE data is complete and will be published in Osten (2000, in prep.). The El Eri EUV analysis is also completed and the simultaneous EUV/X-ray study will be published in Osten et al. (2000, in prep.). Both these latter papers will be submitted in summer 2000. All these results will form part of Rachel Osten's PhD thesis.

  3. Time-resolved optical spectroscopy measurements of shocked liquid deuterium

    Science.gov (United States)

    Bailey, J. E.; Knudson, M. D.; Carlson, A. L.; Dunham, G. S.; Desjarlais, M. P.; Hanson, D. L.; Asay, J. R.

    2008-10-01

    Time-resolved optical spectroscopy has been used to measure the shock pressure steadiness, emissivity, and temperature of liquid deuterium shocked to 22-90 GPa. The shock was produced using magnetically accelerated flyer plate impact, and spectra were acquired with a suite of four fiber-optic-coupled spectrometers with streak camera detectors. The shock pressure changes by an average of -1.2% over the 10-30 ns cell transit time, determined from the relative changes in the shock front self-emission with time. The shock front reflectivity was measured from 5140Å and 5320Å laser light reflected from the D2 shock. The emissivity inferred from the reflectivity measurements was in reasonably good agreement with quantum molecular dynamics simulation predictions. The spectral radiance wavelength dependence was found to agree well (average normalized χ2=1.6 ) with a Planckian multiplied by the emissivity. The shock front temperature was determined from the emissivity and the wavelength-dependent shock self-emission. Thirty-seven temperature measurements spanning the 22-90 GPa range were accumulated. The large number of temperature measurements enables a comparison of the scatter in the data with expectations for a Gaussian distribution. This facilitates determination of uncertainties that incorporate both apparatus contributions and otherwise unquantified systematic effects that cause self-emission variations from one experiment to another. Agreement between temperatures determined from the absolute spectral radiance and from the relative shape of the spectrum further substantiates the absence of systematic biases. The weighted mean temperature uncertainties were as low as ±3-4% , enabling the discrimination between competing models for the D2 equation of state (EOS). The temperature results agree well with models that predict a maximum compression of ˜4.4 . Softer models that predict approximately sixfold compression are inconsistent with the data to a very high

  4. A versatile assay for the accurate, time-resolved determination of cellular viability.

    Science.gov (United States)

    Amano, Toyoki; Hirasawa, Ken ichi; O'Donohue, Michael J; Pernolle, Jean Claude; Shioi, Yuzo

    2003-03-01

    A convenient and versatile method for the accurate, time-resolved determination of cellular viability has been developed. The conventional viability indicator fluorescein diacetate (FDA), which is converted to the fluorescent compound fluorescein in living cells, was employed as a viability probe. Fluorescence emission from cells was measured using a spectrofluorimeter equipped with a magnetic stirrer. Using this assay cell suspensions exhibiting densities in the range 0.5 x 10(5) to 2.0 x 10(5) cells displayed a linear response when FDA concentrations less than 12 micro M were employed. To calibrate the method, viability standards were elaborated using different proportions of living and dead cells, and a correlation coefficient for the viability of tobacco BY-2 suspensions was calculated as 0.998. This viability assay was also found to be applicable to Chlamydomonas reinhardtii and Arabidopsis thaliana cultured cells. Using this cell viability assay, kinetic analyses of cell death could be performed. Using the proteinaceous elicitor from Phytophthora cryptogea, cryptogein, to induce cell death in tobacco cell suspensions, values for the maximum velocity of death induction rate (V(max)) and the LD50 (half-maximal velocity or k(1/2)) were calculated as 17.2 (% death/h) and 65 nM, respectively.

  5. In vivo flow cytometry and time-resolved near-IR angiography and lymphography

    Science.gov (United States)

    Galanzha, Ekaterina I.; Tuchin, Valery V.; Brock, Robert W.; Zharov, Vladimir P.

    2007-05-01

    Integration of photoacoustic and photothermal techniques with high-speed, high-resolution transmission and fluorescence microscopy shows great potential for in vivo flow cytometry and indocyanine green (ICG) near-infrared (IR) angiography of blood and lymph microvessels. In particular, the capabilities of in vivo flow cytometry using rat mesentery and nude mouse ear models are demonstrated for real-time quantitative detection of circulating and migrating individual blood and cancer cells in skin, mesentery, lymph nodes, liver, kidney; studying vascular dynamics with a focus on lymphatics; monitoring cell traffic between blood and lymph systems; high-speed imaging of cell deformability in flow; and label-free real-time monitoring of single cell extravasation from blood vessel lumen into tissue. As presented, the advantages of ICG IR-angiography include estimation of time resolved dye dynamics (appearance and clearance) in blood and lymph microvessels using fluorescent and photoacoustic modules of the integrated technique. These new approaches are important for monitoring and quantifying metastatic and apoptotic cells; comparative measurements of plasma and cell velocities; analysis of immune responses; monitoring of circulating macromolecules, chylomicrons, bacteria, viruses and nanoparticles; molecular imaging. In the future, we believe that the integrated technique presented will have great potential for translation to early disease diagnoses (e.g. cancer) or assessment of innovative therapeutic interventions in humans.

  6. Femtosecond time-resolved energy transfer from CdSe nanoparticles to phthalocyanines

    Science.gov (United States)

    Dayal, S.; Królicki, R.; Lou, Y.; Qiu, X.; Berlin, J. C.; Kenney, M. E.; Burda, C.

    2006-07-01

    The first real-time observation of the early events during energy transfer from a photoexcited CdSe nanoparticle to an attached phthalocyanine molecule are presented in terms of a femtosecond spectroscopic pump-probe study of the energy transfer in conjugates of CdSe nanoparticles (NPs) and silicon phthalocyanines (Pcs) with 120 fs time resolution. Four different silicon phthalocyanines have been conjugated to CdSe NPs. All of these have proven potential for photodynamic therapy (PDT). In such NP-Pc conjugates efficient energy transfer (ET) from CdSe NPs to Pcs occurs upon selective photoexcitation of the NP moiety. Spectral analysis as well as time-resolved fluorescence up-conversion measurements revealed the structure and dynamics of the investigated conjugates. Femtosecond transient differential absorption (TDA) spectroscopy was used for the investigation of the non-radiative carrier and ET dynamics. The formation of excitons, trapped carriers states, as well as stimulated emission was monitored in the TDA spectra and the corresponding lifetimes of these states were recorded. The time component for energy transfer was found to be between 15 and 35 ps. The ET efficiencies are found to be 20-70% for the four Pc conjugates, according to fluorescence quenching experiments. Moreover, as a result of the conjugation between NP and the Pcs the photoluminescence efficiency of the Pc moieties in the conjugates do not strictly follow the quantum yields of the bare phthalocyanines.

  7. Time Resolved Measurements of Primary Biogenic Aerosol Particles in Amazonia

    Science.gov (United States)

    Wollny, A. G.; Garland, R.; Pöschl, U.

    2009-04-01

    Biogenic aerosols are ubiquitous in the Earth's atmosphere and they influence atmospheric chemistry and physics, the biosphere, climate, and public health. They play an important role in the spread of biological organisms and reproductive materials, and they can cause or enhance human, animal, and plant diseases. Moreover, they influence the Earth's energy budget by scattering and absorbing radiation, and they can initiate the formation of clouds and precipitation as cloud condensation and ice nuclei. The composition, abundance, and origin of biogenic aerosol particles and components are, however, still not well understood and poorly quantified. Prominent examples of primary biogenic aerosol particles, which are directly emitted from the biosphere to the atmosphere, are pollen, bacteria, fungal spores, viruses, and fragments of animals and plants. During the Amazonian Aerosol Characterization Experiment (AMAZE-08) a large number of aerosol and gas-phase measurements were taken on a remote site close to Manaus, Brazil, during a period of five weeks in February and March 2008. This presented study is focused on data from an ultraviolet aerodynamic particle sizer (UVAPS, TSI inc.) that has been deployed for the first time in Amazonia. In this instrument, particle counting and aerodynamic sizing over the range of 0.5-20 µm are complemented by the measurement of UV fluorescence at 355 nm (excitation) and 420-575 nm (emission), respectively. Fluorescence at these wavelengths is characteristic for reduced pyridine nucleotides (e.g., NAD(P)H) and for riboflavin, which are specific for living cells. Thus particles exhibiting fluorescence signals can be regarded as "viable aerosols" or "fluorescent bioparticles" (FBAP), and their concentration can be considered as lower limit for the actual abundance of primary biogenic aerosol particles. Data from the UVAPS were averaged over 5 minute time intervals. The presence of bioparticles in the observed size range has been

  8. 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.

  9. Fluorescence property of photosystem II protein complexes bound to a gold nanoparticle.

    Science.gov (United States)

    Tahara, Kazuki; Mohamed, Ahmed; Kawahara, Kousuke; Nagao, Ryo; Kato, Yuki; Fukumura, Hiroshi; Shibata, Yutaka; Noguchi, Takumi

    2017-03-08

    Development of an efficient photo-anode system for water oxidation is key to the success of artificial photosynthesis. We previously assembled photosystem II (PSII) proteins, which are an efficient natural photocatalyst for water oxidation, on a gold nanoparticle (GNP) to prepare a PSII-GNP conjugate as an anode system in a light-driven water-splitting nano-device (Noji et al., J. Phys. Chem. Lett., 2011, 2, 2448-2452). In the current study, we characterized the fluorescence property of the PSII-GNP conjugate by static and time-resolved fluorescence measurements, and compared with that of free PSII proteins. It was shown that in a static fluorescence spectrum measured at 77 K, the amplitude of a major peak at 683 nm was significantly reduced and a red shoulder at 693 nm disappeared in PSII-GNP. Time-resolved fluorescence measurements showed that picosecond components at 683 nm decayed faster by factors of 1.4-2.1 in PSII-GNP than in free PSII, explaining the observed quenching of the major fluorescence peak. In addition, a nanosecond-decay component arising from a 'red chlorophyll' at 693 nm was lost in time-resolved fluorescence of PSII-GNP, probably due to a structural perturbation of this chlorophyll by interaction with GNP. Consistently with these fluorescence properties, degradation of PSII during strong-light illumination was two times slower in PSII-GNP than in free PSII. The enhanced durability of PSII is an advantageous property of the PSII-GNP conjugate in the development of an artificial photosynthesis device.

  10. Excited state dynamics in SO2. I. Bound state relaxation studied by time-resolved photoelectron-photoion coincidence spectroscopy.

    Science.gov (United States)

    Wilkinson, Iain; Boguslavskiy, Andrey E; Mikosch, Jochen; Bertrand, Julien B; Wörner, Hans Jakob; Villeneuve, David M; Spanner, Michael; Patchkovskii, Serguei; Stolow, Albert

    2014-05-28

    The excited state dynamics of isolated sulfur dioxide molecules have been investigated using the time-resolved photoelectron spectroscopy and time-resolved photoelectron-photoion coincidence techniques. Excited state wavepackets were prepared in the spectroscopically complex, electronically mixed (B̃)(1)B1/(Ã)(1)A2, Clements manifold following broadband excitation at a range of photon energies between 4.03 eV and 4.28 eV (308 nm and 290 nm, respectively). The resulting wavepacket dynamics were monitored using a multiphoton ionisation probe. The extensive literature associated with the Clements bands has been summarised and a detailed time domain description of the ultrafast relaxation pathways occurring from the optically bright (B̃)(1)B1 diabatic state is presented. Signatures of the oscillatory motion on the (B̃)(1)B1/(Ã)(1)A2 lower adiabatic surface responsible for the Clements band structure were observed. The recorded spectra also indicate that a component of the excited state wavepacket undergoes intersystem crossing from the Clements manifold to the underlying triplet states on a sub-picosecond time scale. Photoelectron signal growth time constants have been predominantly associated with intersystem crossing to the (c̃)(3)B2 state and were measured to vary between 750 and 150 fs over the implemented pump photon energy range. Additionally, pump beam intensity studies were performed. These experiments highlighted parallel relaxation processes that occurred at the one- and two-pump-photon levels of excitation on similar time scales, obscuring the Clements band dynamics when high pump beam intensities were implemented. Hence, the Clements band dynamics may be difficult to disentangle from higher order processes when ultrashort laser pulses and less-differential probe techniques are implemented.

  11. Protein structural dynamics revealed by time-resolved X-ray solution scattering.

    Science.gov (United States)

    Kim, Jong Goo; Kim, Tae Wu; Kim, Jeongho; Ihee, Hyotcherl

    2015-08-18

    One of the most important questions in biological science is how a protein functions. When a protein performs its function, it undergoes regulated structural transitions. In this regard, to better understand the underlying principle of a protein function, it is desirable to monitor the dynamic evolution of the protein structure in real time. To probe fast and subtle motions of a protein in physiological conditions demands an experimental tool that is not only equipped with superb spatiotemporal resolution but also applicable to samples in solution phase. Time-resolved X-ray solution scattering (TRXSS), discussed in this Account, fits all of those requirements needed for probing the movements of proteins in aqueous solution. The technique utilizes a pump-probe scheme employing an optical pump pulse to initiate photoreactions of proteins and an X-ray probe pulse to monitor ensuing structural changes. The technical advances in ultrafast lasers and X-ray sources allow us to achieve superb temporal resolution down to femtoseconds. Because X-rays scatter off all atomic pairs in a protein, an X-ray scattering pattern provides information on the global structure of the protein with subangstrom spatial resolution. Importantly, TRXSS is readily applicable to aqueous solution samples of proteins with the aid of theoretical models and therefore is well suited for investigating structural dynamics of protein transitions in physiological conditions. In this Account, we demonstrate that TRXSS can be used to probe real-time structural dynamics of proteins in solution ranging from subtle helix movement to global conformational change. Specifically, we discuss the photoreactions of photoactive yellow protein (PYP) and homodimeric hemoglobin (HbI). For PYP, we revealed the kinetics of structural transitions among four transient intermediates comprising a photocycle and, by applying structural analysis based on ab initio shape reconstruction, showed that the signaling of PYP involves

  12. Low-temperature and time-resolved spectroscopic characterization of the LOV2 domain of Avena sativa phototropin 1

    Science.gov (United States)

    Gauden, Magdalena; Crosson, Sean; van Stokkum, I. H. M.; van Grondelle, Rienk; Moffat, Keith; Kennis, John T. M.

    2004-09-01

    The phototropins are plant blue-light receptors that base their light-dependent action on the reversible formation of a covalent bond between a flavin mononucleotide (FMN) cofactor and a conserved cysteine residue in light, oxygen or voltage (LOV) domains. The spectroscopic properties of the LOV2 domain of phototropin 1 of Avena sativa (oat) have been investigated by means of low-temperature absorption and fluorescence spectroscopy and by time-resolved fluorescence spectroscopy. The low-temperature absorption spectrum of the LOV2 domain showed a fine structure around 473 nm, indicating heterogeneity in the flavin binding pocket. The fluorescence quantum yield of the flavin cofactor increased from 0.13 to 0.41 upon cooling the sample from room temperature to 77 K. A pronounced phosphorescence emission around 600 nm was observed in the LOV2 domain between 77 and 120 K, allowing for an accurate positioning of the flavin triplet state in the LOV2 domain at 16900 cm-1. Fluorescence from the cryotrapped covalent adduct state was extremely weak, with a fluorescence spectrum showing a maximum at 440 nm. Time-resolved fluorescence experiments utilizing a synchroscan streak camera revealed a singlet-excited state lifetime of the LOV2 domain of 2.4 ns. FMN dissolved in aqueous solution showed a pH-dependent lifetime ranging between 2.9 ns at pH 2.0 to 4.7 ns at pH 8.0. No spectral shifting of the flavin emission was observed in the LOV2 domain nor in FMN in aqueous solution.

  13. Simultaneous Quantification of Anticardiolipin IgG and IgM by Time Resolved Fluoroimmunoassay

    Science.gov (United States)

    Liu, Jie; Li, Mei; Ye, Yan; Chen, Yu

    2016-01-01

    The autoimmune disease antiphospholipid syndrome (APS) is characterized by the presence of anticardiolipin antibodies (aCL), along with anti-β2-glycoprotein I (β2GPI) antibodies and lupus anticoagulant (LA). In this study, we developed a time-resolved fluoroimmunoassay (TRFIA) system for simultaneous quantification of aCL IgG and IgM. A 96-well microtiter plate precoated with the complex of cardiolipin from bovine heart and bovine β2GPI was incubated with the anticardiolipin IgG and IgM standard substance or serum, and the conjugate of Eu3+-labeled anti-human IgG and Sm3+-labeled anti-human IgM was pipetted to the wells to form a tipical double-antibody-sandwich immunoreactions; finally the fluorescent intensity of Eu3+ and Sm3+ was detected to reflect the quantity of anticardiolipin IgG and IgM. This assay showed a good relationship between fluorescence intensities and the concentration of anticardiolipin antibody(aCL) IgG and IgM, with a low-end sensitivity of 0.1 U/ml for IgG and 0.1 U/ml for IgM, respectively. The intra- and inter-assay coefficients of variation (CV) of the calibrators was 3.0% and 4.51% for IgG, and 2.76% and 4.45% for IgM. The average recovery was 100.38% for aCL IgG and 100.45% for aCL IgM. For serum samples, the results of our method showed a good correlation with those obtained with ELISA kit. Simultaneous detection of aCL-IgG and aCL-IgM in the same reaction well can optimize assay performance by avoiding potential influence of different reaction conditions-timing, and well-to-well difference in concentration and characteristics of cardiolipin antigen. The results of a combo aCL-IgG and aCL-IgM assay for the same sample are more consistent and more reliable. This dual-label time-resolved fluoroimmunoassay is sensitive for detecting aCL IgG and IgM across a wide concentration range with stable reagents and may assist in the clinical diagnosis of antiphospholipid syndrome. PMID:27661084

  14. Time-resolved lidar fluorosensor for sea pollution detection

    Science.gov (United States)

    Ferrario, A.; Pizzolati, P. L.; Zanzottera, E.

    1986-01-01

    A contemporary time and spectral analysis of oil fluorescence is useful for the detection and the characterization of oil spills on the sea surface. Nevertheless the fluorosensor lidars, which were realized up to now, have only partial capability to perform this double analysis. The main difficulties are the high resolution required (of the order of 1 nanosecond) and the complexity of the detection system for the recording of a two-dimensional matrix of data for each laser pulse. An airborne system whose major specifications were: time range, 30 to 75 ns; time resolution, 1 ns; spectral range, 350 to 700 nm; and spectral resolution, 10 nm was designed and constructed. The designed system of a short pulse ultraviolet laser source and a streak camera based detector are described.

  15. Integrated electronics for time-resolved array of single-photon avalanche diodes

    Science.gov (United States)

    Acconcia, G.; Crotti, M.; Rech, I.; Ghioni, M.

    2013-12-01

    The Time Correlated Single Photon Counting (TCSPC) technique has reached a prominent position among analytical methods employed in a great variety of fields, from medicine and biology (fluorescence spectroscopy) to telemetry (laser ranging) and communication (quantum cryptography). Nevertheless the development of TCSPC acquisition systems featuring both a high number of parallel channels and very high performance is still an open challenge: to satisfy the tight requirements set by the applications, a fully parallel acquisition system requires not only high efficiency single photon detectors but also a read-out electronics specifically designed to obtain the highest performance in conjunction with these sensors. To this aim three main blocks have been designed: a gigahertz bandwidth front-end stage to directly read the custom technology SPAD array avalanche current, a reconfigurable logic to route the detectors output signals to the acquisition chain and an array of time measurement circuits capable of recording the photon arrival times with picoseconds time resolution and a very high linearity. An innovative architecture based on these three circuits will feature a very high number of detectors to perform a truly parallel spatial or spectral analysis and a smaller number of high performance time-to-amplitude converter offering very high performance and a very high conversion frequency while limiting the area occupation and power dissipation. The routing logic will make the dynamic connection between the two arrays possible in order to guarantee that no information gets lost.

  16. A time-resolved spectroscopy and density functional theory study of the solvent dependent photochemistry of fenofibric acid.

    Science.gov (United States)

    Li, Ming-De; Ma, Jiani; Su, Tao; Liu, Mingyue; Phillips, David Lee

    2013-02-07

    The solvent dependent photochemistry of fenofibric acid (FA) was studied by femtosecond transient absorption and nanosecond time-resolved resonance Raman experiments and density functional theory calculations. In acetonitrile-rich solution, a typical nπ* triplet state FA ((3)FA) is formed through a highly efficient intersystem crossing and then the (3)FA species undergoes some reaction with water to generate a ketyl radical intermediate at low water concentrations. In contrast, nπ* (3)FA changes from a reaction with water to generate a ketyl radical intermediate at lower water concentrations to a decarboxylation reaction with the assistance of water molecules to produce a biradical intermediate at higher water concentrations in water-rich solutions. The decarboxylation reaction leads to the formation of the FA carbanion in 50% phosphate buffer solution and the FA carbanion is observed on the picosecond to nanosecond time scale and the cleavage of the FA carbanion gives rise to the enolate 3(-) anion at later nanosecond delay times. As regards fenofibrate (FB), it only exhibits a benzophenone-like photochemistry, which consists of some reaction with water to generate a ketyl radical intermediate, being observed in the different aqueous solutions.

  17. Measurement and analysis of thermal conductivity of isotopically controlled silicon layers by time-resolved X-ray scattering

    Energy Technology Data Exchange (ETDEWEB)

    Eon, S.; Frieling, R.; Bracht, H. [Institute for Materials Physics, University of Muenster, 48149 Muenster (Germany); Plech, A. [Institute for Photon Science and Synchrotron Radiation (IPS), 76344 Eggenstein-Leopoldshafen (Germany)

    2016-11-15

    Nanostructuring is considered to be an efficient way to tailor phonon scattering and to reduce the thermal conductivity while keeping good electronic properties. This can be ideally realized by mass modulation of chemical identical elements. In this work, we report measurements of the crossplane thermal conductivity of isotopically modulated {sup 28}Si/{sup 30}Si multilayer structures and of isotopically pure {sup 28}Si layers by means of time-resolved X-ray scattering. Compared to earlier investigations, an improved measurement technique has been applied to determine the cooling behavior of a top gold metal layer after laser excitation with picosecond time resolution until thermal equilibration is established. Detailed analysis of the cooling behavior not only confirms a reduced thermal conductivity of {sup 28}Si/{sup 30}Si multilayer structures compared to natural and isotopically enriched {sup 28}Si layers but also provides evidence of direct laser heating of the Si layer. This and extrinsic effects affecting the cooling behavior of the gold layer are taken into account to determine the thermal conductivity by means of the pump-and-probe measurement technique. (copyright 2016 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  18. High-speed multi-jets printing using laser forward transfer: time-resolved study of the ejection dynamics.

    Science.gov (United States)

    Biver, Emeric; Rapp, Ludovic; Alloncle, Anne-Patricia; Serra, Pere; Delaporte, Philippe

    2014-07-14

    This paper extends the current understanding of the laser-induced forward transfer (LIFT) process to the multi-jets ejection problem. LIFT has already been used to print micrometer-sized droplets from a liquid donor substrate with single pulse experiments. Here we study the dynamics of the high-speed multi-jets formation from silver nanoparticles ink films with a time-resolved imaging technique. A galvanometric mirrors head controls the spacing between adjacent pulses by scanning the focused beam of a high repetition rate UV picosecond laser along an ink-coated donor substrate. The laser pulses interact with the liquid film and generate cavitation bubbles that propel the ink away from the substrate and form the jets. When the spacing between consecutive pulses is substantially higher than the maximum diameter of the bubbles, there is no interaction between adjacent jets, and these remain unperturbed. However, when the pulses are brought closer significant jet-jet interaction takes place, which results in a clear deviation from the single jet dynamics. Thus, the cavitation bubbles acquire different shapes, the ink is ejected faster and along different directions depending on the spacing between the pulses, and each bubble alters the evolution of the previous one and shifts away from it.

  19. Study of Heat Transfer Dynamics from Gold Nanorods to the Environment via Time-Resolved Infrared Spectroscopy.

    Science.gov (United States)

    Nguyen, Son C; Zhang, Qiao; Manthiram, Karthish; Ye, Xingchen; Lomont, Justin P; Harris, Charles B; Weller, Horst; Alivisatos, A Paul

    2016-02-23

    Studying the local solvent surrounding nanoparticles is important to understanding the energy exchange dynamics between the particles and their environment, and there is a need for spectroscopic methods that can dynamically probe the solvent region that is in nearby contact with the nanoparticles. In this work, we demonstrate the use of time-resolved infrared spectroscopy to track changes in a vibrational mode of local water on the time scale of hundreds of picoseconds, revealing the dynamics of heat transfer from gold nanorods to the local water environment. We applied this probe to a prototypical plasmonic photothermal system consisting of organic CTAB bilayer capped gold nanorods, as well as gold nanorods coated with varying thicknesses of inorganic mesoporous-silica. The heat transfer time constant of CTAB capped gold nanorods is about 350 ps and becomes faster with higher laser excitation power, eventually generating bubbles due to superheating in the local solvent. Silica coating of the nanorods slows down the heat transfer and suppresses the formation of superheated bubbles.

  20. Probing the NO2 --> NO+O transition state via time resolved unimolecular decomposition

    Science.gov (United States)

    Ionov, S. I.; Brucker, G. A.; Jaques, C.; Chen, Y.; Wittig, C.

    1993-09-01

    Time resolved, subpicosecond resolution measurements of photoinitiated NO2 unimolecular decomposition rates are reported for expansion cooled and room temperature samples. The molecules are excited by 375-402 nm tunable subpicosecond pulses having bandwidths ≥20 cm-1 to levels which are known to be thorough admixtures of the 2B2 electronically excited state and the 2A1 ground electronic state. Subsequent decomposition is probed by a 226 nm subpicosecond pulse that excites laser-induced fluorescence (LIF) in the NO product. When increasing the amount of excitation over the dissociation threshold, an uneven, ``step-like'' increase of the decomposition rate vs energy is observed for expansion cooled samples. The steps are spaced by ˜100 cm-1 and can be assigned ad hoc to bending at the transition state. Relying on experimental estimates for the near threshold density of states, we point out that simple transition state theory predictions give rates that are consistent with these measured values. The rates are sufficiently rapid to question the assumption of rapid intramolecular vibrational redistribution, which is implicit in transition state theories. In contrast to expansion cooled samples, room temperature samples exhibit a smooth variation of the reaction rate vs photon energy. By comparing rates for rotationally cold and room temperature NO2, the ON-O bond is estimated to be ˜40% longer in the transition state than in the parent molecule.

  1. Time-Resolved Luminescence Nanothermometry with Nitrogen-Vacancy Centers in Nanodiamonds

    Science.gov (United States)

    Tsai, Pei-Chang; Chen, Oliver Y.; Tzeng, Yan-Kai; Liu, Hsiou-Yuan; Hsu, Hsiang; Huang, Shaio-Chih; Chen, Jeson; Yee, Fu-Ghoul; Chang, Huan-Cheng; Chang, Ming-Shien

    2016-05-01

    Measuring thermal properties with nanoscale spatial resolution either at or far from equilibrium is gaining importance in many scientific and engineering applications. Although negatively charged nitrogen-vacancy (NV-) centers in diamond have recently emerged as promising nanometric temperature sensors, most previous measurements were performed under steady state conditions. Here we employ a three-point sampling method which not only enables real-time detection of temperature changes over +/-100 K with a sensitivity of 2 K/(Hz)1/2, but also allows the study of nanometer scale heat transfer with a temporal resolution of better than 1 μs with the use of a pump-probe-type experiment. In addition to temperature sensing, we further show that nanodiamonds conjugated with gold nanorods, as optically-activated dual-functional nanoheaters and nanothermometers, are useful for highly localized hyperthermia treatment. We experimentally demonstrated time-resolved fluorescence nanothermometry, and the validity of the measurements was verified with finite-element numerical simulations. The approaches provided here will be useful for probing dynamical thermal properties on nanodevices in operation.

  2. Eu-Chelate Construct Ultrasensitive Time-Resolved Fluoroimmunoassay-Assay of Pepsinogen I

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    Eu-chelate were used to construct a two-site sandwich-type assay for pepsinogen I (PGI) with time-resolved fluoroimmunoassay (TRFIA) as a detection technique. On the noncompetitive assay, captured monoclonal antibodies (McAbs) coated on wells were directed against a specific antigenic site on the PGI. Another McAbs, called as labeling McAbs, were prepared with the Eu-chelate of N-(p-isothiocyanatobenzyl)-diethylenetriamine-N, N, N, N-tetraacetic acid and directed against a different antigenic site on the PGI. The fluorescence counts of bound Eu3 +-McAbs were measured with the auto DELFIA1235 system. The PGI in sera from healthy volunteers were determined by PGI-TRFIA. The within-run and between-run CVs of the PGI-TRFIA were 1.9% and 4.7%, respectively, and the recovery rate was 102.65%. The cross-reacting rate with pepsinogen Ⅱ was negligible. The linear correlation of PGI-TRFIA and radioimmunassay measurePGI. The availability of a highly sensitive, reliable, and convenient method for quantifying PGI will allow investigations into the possible diagnostic value of this analyte in various clinical conditions, including gastric carcinoma, duodenal ulcer, gastritis and severe atrophic gastritis.

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

    Science.gov (United States)

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

    2017-03-06

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

  4. Temperature-driven oxidation behavior on pure iron surface investigated by time-resolved EXAFS measurements

    Energy Technology Data Exchange (ETDEWEB)

    Doh, S.J.; Lee, J.M.; Je, J.H. [POSTECH, Pohang (Korea, Republic of); Noh, D.Y. [K-JIST, Kwangju (Korea, Republic of). Dept. of Materials Science and Engineering

    1998-12-31

    The surface-front oxidation mechanism of iron was investigated by time-resolved, glancing-angle Fe K-edge fluorescence EXAFS measurements at various oxidation temperatures of 200--700 C. The glancing angle was chosen according to the depth of the oxide layer, roughly 1,500--2,000 {angstrom}. The oxidation behavior under rapid heating (up to 600 C within 10 minutes) was compared with the slowly heated oxidation process using the Quick-EXAFS measurements. In the slowly heated process, Fe{sub 3}O{sub 4} was the dominating phase at a relatively low temperature (300--400 C) initially. However, at a relatively high temperature (above 600 C), the Fe{sub 2}O{sub 3} and FeO crystalline phases are gradually enriched as the successive oxidation process involving intrusive oxygen proceeded. Remarkably under a prolonged heat treatment above 600 C, the stable FeO phase that exists in a deep-lying interface structure and Fe{sub 2}O{sub 3} phase eventually dominates the thick front-surface structure. In a quickly heated process, however, Fe{sub 3}O{sub 4} phase is less dominating, which is contradictory to the commonly accepted oxidation models. The EXAFS results are discussed in conjunction with the x-ray diffraction features under the same heat treatment conditions.

  5. Time-resolved detection of surface plasmon polaritons with a scanning tunneling microscope

    DEFF Research Database (Denmark)

    Keil, Ulrich Dieter Felix; Ha, T.; Jensen, Jacob Riis;

    1998-01-01

    We present the time-resolved detection of surface plasmon polaritons with an STM. The results indicate that the time resolved signal is due to rectification of coherently superimposed plasmon voltages. The comparison with differential reflectivity measurements shows that the tip itself influences...

  6. Time-resolved Monte Carlo Simulation of Propagation of Photons Through Layered Tissues

    Institute of Scientific and Technical Information of China (English)

    CHEN Min(陈敏); CHEN Jianwen(陈建文); GAO Hongyi(高鸿奕); XU Zhizhan(徐志展)

    2002-01-01

    The propagation of photons through layered tissues is discussed using time resolved Monte Carlo method. The effects of the absorption coefficient, scattering coefficient and anisotropy coefficient on the shape of time resolved transmission are investigated. The energy attenuation of light in layered tissues is also achieved for the infinitesimal-width light and infinite-width light, respectively.

  7. A multi-analytical investigation of semi-conductor pigments with time-resolved spectroscopy and imaging

    Science.gov (United States)

    Nevin, A.; Cesaratto, A.; D'Andrea, C.; Valentini, Gianluca; Comelli, D.

    2013-05-01

    We present the non-invasive study of historical and modern Zn- and Cd-based pigments with time-resolved fluorescence spectroscopy, fluorescence multispectral imaging and fluorescence lifetime imaging (FLIM). Zinc oxide and Zinc sulphide are semiconductors which have been used as white pigments in paintings, and the luminescence of these pigments from trapped states is strongly dependent on the presence of impurities and crystal defects. Cadmium sulphoselenide pigments vary in hue from yellow to deep red based on their composition, and are another class of semiconductor pigments which emit both in the visible and the near infrared. The Fluorescence lifetime of historical and modern pigments has been measured using both an Optical Multichannel Analyser (OMA) coupled with a Nd:YAG nslaser, and a streak camera coupled with a ps-laser for spectrally-resolved fluorescence lifetime measurements. For Znbased pigments we have also employed Fluorescence Lifetime Imaging (FLIM) for the measurement of luminescence. A case study of FLIM applied to the analysis of the painting by Vincent Van Gogh on paper - "Les Bretonnes et le pardon de Pont-Aven" (1888) is presented. Through the integration of complementary, portable and non-invasive spectroscopic techniques, new insights into the optical properties of Zn- and Cd-based pigments have been gained which will inform future analysis of late 19th] and early 20th C. paintings.

  8. Global analysis of time-resolved fluorescence microspectroscopy and applications in biomolecular studies

    NARCIS (Netherlands)

    Laptenok, S.

    2009-01-01

    Understanding the properties of biomolecular networks is of central importance in life sciences. Optical microscopy has been very useful to determine the sub-cellular localisation of proteins but it cannot reveal whether proteins interact with one another. Micro-spectroscopic techniques (combining m

  9. Sensitive Listeria spp. immunoassay based on europium(III) nanoparticulate labels using time-resolved fluorescence.

    Science.gov (United States)

    Jaakohuhta, Sinikka; Härmä, Harri; Tuomola, Mika; Lövgren, Timo

    2007-03-20

    Listeria spp. are Gram-positive rod shaped bacteria found universally in the environment. Pathogenic Listeria monocytogenes is seldom harmful to healthy adults, but can cause serious disease, listeriosis, especially to pregnant women, neonates, and elderly or immunocompromised people. Conventional methods for screening Listeria in food samples are time consuming and laborious, involving the use of a range of liquid media and plate cultures. In the current study, the total analysis time was shortened by employing a sensitive Listeria assay, which was able to detect the bacteria in low concentrations. Sensitivity of the sandwich immunoassay was substantially improved by utilizing europium(III)-chelate containing latex nanoparticles as tracers. Each 107 nm nanoparticle contained approximately 31000 europium(III)-chelates which enhanced the specific activity of the label. The sensitive nanoparticulate immunoassay developed for Listeria spp. was performed in one-step and two-step formats. One-step assay was notably faster, 15 min, and simpler to execute having analytical sensitivity of 300 CFU/ml and a dynamic range of three orders of magnitude. The sensitivity, 20 CFU/ml, of the 4 h two-step assay clearly exceeded that of the one-step assay, and the dynamic range was nearly five orders of magnitude. Food and environmental samples were measured against a commercial L. monocytogenes immunoassay with good correlation. The developed sensitive assay enabled shorter sample enrichment times and, therefore, faster analysis of Listeria spp. Obviously the detection of several other bacteria can also be enhanced by applying the nanoparticle assay technology.

  10. Sensitive Assay of Human Alpha-fetoprotein by Time-resolved Fluorescence

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Alpha-fetoprotein (AFP) produced mainly in the yolk sac and the liver is the major protein in the fetal circulation during early postnatal life. AFP measurements are used in the diagnosis and monitoring AFP producing tumors in the liver, germ cells and the gastrointestinal. In addition, AFP marked increases are found in fetal illness, such as neural tube defects. In this study, a sensitive

  11. Quantitative Estimation of Component Amplitude in Multiexponential Data: Application to Time-Resolved Fluorescence Spectroscopy

    Science.gov (United States)

    1989-07-01

    and sale. DELSIATOONRDIGSHDL Distribution unlimited. PERFORMING ORGANIZATION REPORT NUMBER($) S. MONITORING ORGANIZATION REPORT NUMBER(S) 0 rmONR...Technical Report No. 15 (N NAME OF PERFORMING ORGANIZATION T6t) OFFICE SYMBOL 7a NAME OF MONITORING ORGANIZATION University of Utah j (if applicable...Physics, Model 375). The pulse rate of the dye laser output was maintained at 400 kHz by a cavity dumper (Spectra Physics, Model 454). The 604 nm emission

  12. Design and electronic structure of new styryl dye bases: steady-state and time-resolved spectroscopic studies.

    Science.gov (United States)

    Bashmakova, N V; Shaydyuk, Ye O; Levchenko, S M; Masunov, A E; Przhonska, O V; Bricks, J L; Kachkovsky, O D; Slominsky, Yu L; Piryatinski, Yu P; Belfield, K D; Bondar, M V

    2014-06-26

    A comprehensive investigation of the electronic structure and fast relaxation processes in the excited states of new styryl base-type derivatives was performed using steady-state, pico-, and femtosecond time-resolved spectroscopic techniques. Linear photophysical parameters of new compounds, including steady-state absorption, fluorescence, and excitation anisotropy spectra, were obtained in a number of organic solvents at room temperature. A detailed analysis of the fluorescence lifetimes and ultrafast relaxation processes in the electronically excited state of the styryl bases revealed an important role of solvate dynamics and donor-acceptor strength of the molecular structures in the formation of their excited state absorption spectra. Experimental data were in good agreement with quantum chemical calculations at the time dependent density functional theory level, combined with a polarizable continuum model.

  13. Standoff Time-Resolved Laser-Based Spectroscopy Tools for Sample Characterization and Biosignature Detection

    Science.gov (United States)

    Gasda, P. J.; Acosta-Maeda, T.; Lucey, P. G.; Misra, A. K.; Sharma, S. K.; Taylor, J.

    2014-12-01

    The NASA Mars2020 rover will be searching for signs of past habitability and past life on Mars. Additionally, the rover mission will prepare a cache of highly significant samples for a future sample return mission. NASA requires these samples to be well characterized; the instruments on the rover must be capable of fine-scale in situ mineralogical or elemental analysis with emphasis on biosignature detection or characterization. We have been developing multiple standoff laser-based instruments at the University of Hawaii, Manoa that are capable of fine-scale in situ chemical analysis and biosignatures detection. By employing a time-resolved spectroscopy, we can perform elemental analysis with Laser-Induced Breakdown Spectroscopy (LIBS), mineral and organic analysis with Raman spectroscopy, and biosignature detection with Laser-Induced Fluorescence (LIF). Each of these techniques share the same optics and detection equipment, allowing us to integrate them into a single, compact instrument. High time-resolution (~100 ns/pulse) is the key to this instrument; with it, the detector only records data when the signal is the brightest. Spectra can be taken during the day, LIBS can be measured without a plasma light background, and the Raman signal can be separated from the mineral fluorescence signal. Since bio-organics have very short fluorescence lifetimes, the new instrument can be used to unambiguously detect bio-organics. The prototype uses a low power (0.5 mJ/pulse) 532 nm laser with a detection limit of laser spot and a camera to produce LIF images of wide area (25 cm area from 2 m distance with 2 mm/pixel resolution). The Biofinder can quickly assess the area around the rover (at 10 frames/s) by imaging sample cores, drill holes, or outcrops, and then allow the slower but more precise instruments on the rover to characterize the regions of interest. Either of these prototypes would be ideally suited for future NASA missions, including human exploration missions

  14. 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....

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

    Science.gov (United States)

    Peng, Qiming; Li, Xianjie; Li, Feng

    2012-12-01

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

  16. Time-resolved photoelectron spectroscopy of non-adiabatic dynamics in polyatomic molecules

    CERN Document Server

    Stolow, Albert

    2015-01-01

    This review article discusses advances in the use of time-resolved photoelectron spectroscopy for the study of non-adiabatic processes in molecules. A theoretical treatment of the experiments is presented together with a number of experimental examples.

  17. Sudden Polarization in the Twisted, Phantom State of Tetraphenylethylene Detected by Time-Resolved Microwave

    NARCIS (Netherlands)

    Schuddeboom, Wouter; Jonker, Stephan A.; Warman, John M.; Haas, Matthijs P. de; Vermeulen, Martien J.W.; Jager, Wolter F.; Lange, Ben de; Fessenden, Richard W.; Feringa, Bernard

    1993-01-01

    Photoexcitation of the symmetrical molecules tetraphenylethylene and tetra-p-methoxyphenylethylene dissolved in saturated hydrocarbon solvents results in a transient increase in the dielectric loss of the solutions as monitored using the nanosecond time-resolved microwave conductivity (TRMC)

  18. SUDDEN POLARIZATION IN THE TWISTED, PHANTOM STATE OF TETRAPHENYLETHYLENE DETECTED BY TIME-RESOLVED MICROWAVE CONDUCTIVITY

    NARCIS (Netherlands)

    SCHUDDEBOOM, W; JONKER, SA; WARMAN, JM; DEHAAS, MP; VERMEULEN, MJW; JAGER, WF; DELANGE, B; FERINGA, BL; FESSENDEN, RW

    1993-01-01

    Photoexcitation of the symmetrical molecules tetraphenylethylene and tetra-p-methoxyphenylethylene dissolved in saturated hydrocarbon solvents results in a transient increase in the dielectric loss of the solutions as monitored using the nanosecond time-resolved microwave conductivity (TRMC)

  19. Origin of pronounced differences in 77 K fluorescence of the green alga Chlamydomonas reinhardtii in state 1 and 2.

    Science.gov (United States)

    Ünlü, Caner; Polukhina, Iryna; van Amerongen, Herbert

    2016-04-01

    In response to changes in the reduction state of the plastoquinone pool in its thylakoid membrane, the green alga Chlamydomonas reinhardtti is performing state transitions: remodelling of its thylakoid membrane leads to a redistribution of excitations over photosystems I and II (PSI and PSII). These transitions are accompanied by marked changes in the 77 K fluorescence spectrum, which form the accepted signature of state transitions. The changes are generally thought to reflect a redistribution of light-harvesting complexes (LHCs) over PSII (fluorescing below 700 nm) and PSI (fluorescing above 700 nm). Here we studied the picosecond fluorescence properties of C. reinhardtti over a broad range of wavelengths with very low excitation intensities (0.2 nJ per laser pulse). Cells were directly used for time-resolved fluorescence measurements at 77 K without further treatment, such as medium exchange with glycerol. It is observed that upon going from state 1 (relatively more fluorescence below 700 nm) to state 2 (relatively more fluorescence above 700 nm), a large part of the fluorescence of LHC/PSII becomes substantially quenched in concurrence with LHC detachment from PSII, whereas the absolute amount of PSI fluorescence hardly changes. These results are in agreement with the recent proposal that the amount of LHC moving from PSII to PSI upon going from state 1 to state 2 is rather limited (Unlu et al. Proc Natl Acad Sci USA 111 (9):3460-3465, 2014).

  20. Time-resolved temperature and O atom measurements in nanosecond pulse discharges in combustible mixtures

    Science.gov (United States)

    Lanier, Suzanne; Bowman, Sherrie; Burnette, David; Adamovich, Igor V.; Lempert, Walter R.

    2014-11-01

    The paper presents results of time-resolved rotational temperature measurements, by pure rotational coherent anti-Stokes Raman spectroscopy and absolute O atom number density measurements, by two-photon absorption laser induced fluorescence. The experiments were conducted in nanosecond pulse discharges in H2-O2-Ar and C2H4-O2-Ar mixtures, initially at room temperature, operated at a high pulse repetition rate of 40 kHz, in a plane-to-plane double dielectric barrier geometry at a pressure of 40 Torr. Intensified charge-coupled device images show that O2-Ar and H2-O2-Ar plasmas remain diffuse and volume-filling during the entire burst. Images taken in C2H4-O2-Ar plasma demonstrate significant discharge filamentation and constriction along the center plane and in the corners of the test section. The experimental results demonstrate high accuracy of pure rotational psec CARS for thermometry measurements at low partial pressures of oxygen in nonequilibrium plasmas. The results are compared with kinetic modeling calculations, using two different H2-O2 chemistry and C2H4-O2 chemistry mechanisms. In H2-O2-Ar mixtures, the kinetic modeling predictions are in fairly good agreement with the data, predicting temperature rise and O atom accumulation in long discharge bursts, up to 450 pulses. The results show that adding hydrogen to the mixture results in an additional temperature rise, due to its partial oxidation by radicals generated in the plasma, essentially without chain branching. In C2H4-O2-Ar mixtures, the model consistently underpredicts both temperature and O atom number density. The most likely reason for the difference between the experimental data and model predictions is discharge filamentation developing when ethylene is added to the O2-Ar mixture, at fairly low temperatures.

  1. Time-resolved digital holographic microscopy of laser-induced forward transfer process.

    Science.gov (United States)

    Ma, H; Venugopalan, V

    2014-03-01

    We develop a method for time-resolved digital holographic microscopy to obtain time-resolved 3-D deformation measurements of laser induced forward transfer (LIFT) processes. We demonstrate nanometer axial resolution and nanosecond temporal resolution of our method which is suitable for measuring dynamic morphological changes in LIFT target materials. Such measurements provide insight into the early dynamics of the LIFT process and a means to examine the effect of laser and material parameters on LIFT process dynamics.

  2. Deflecting cavity dynamics for time-resolved machine studies of SXFEL user facility

    CERN Document Server

    Song, Minghao; Liu, Bo; Wang, Dong

    2016-01-01

    Radio frequency deflectors are widely used for time-resolved electron beam energy, emittance and radiation profile measurements in modern free electron laser facilities. In this paper, we present the beam dynamics aspects of the deflecting cavity of SXFEL user facility, which is located at the exit of the undulator. With a targeted time resolution around 10 fs, it is expected to be an important tool for time-resolved commissioning and machine studies for SXFEL user facility.

  3. Standing surface acoustic waves in LiNbO3 studied by time resolved X-ray diffraction at Petra III

    Directory of Open Access Journals (Sweden)

    T. Reusch

    2013-07-01

    Full Text Available We have carried out time resolved stroboscopic diffraction experiments on standing surface acoustic waves (SAWs of Rayleigh type on a LiNbO3 substrate. A novel timing system has been developed and commissioned at the storage ring Petra III of Desy, allowing for phase locked stroboscopic diffraction experiments applicable to a broad range of timescales and experimental conditions. The combination of atomic structural resolution with temporal resolution on the picosecond time scale allows for the observation of the atomistic displacements for each time (or phase point within the SAW period. A seamless transition between dynamical and kinematic scattering regimes as a function of the instantaneous surface amplitude induced by the standing SAW is observed. The interpretation and control of the experiment, in particular disentangling the diffraction effects (kinematic to dynamical diffraction regime from possible non-linear surface effects is unambiguously enabled by the precise control of phase between the standing SAW and the synchrotron bunches. The example illustrates the great flexibility and universality of the presented timing system, opening up new opportunities for a broad range of time resolved experiments.

  4. Dynamics of dipole- and valence bound anions in iodide-adenine binary complexes: A time-resolved photoelectron imaging and quantum mechanical investigation.

    Science.gov (United States)

    Stephansen, Anne B; King, Sarah B; Yokoi, Yuki; Minoshima, Yusuke; Li, Wei-Li; Kunin, Alice; Takayanagi, Toshiyuki; Neumark, Daniel M

    2015-09-14

    Dipole bound (DB) and valence bound (VB) anions of binary iodide-adenine complexes have been studied using one-color and time-resolved photoelectron imaging at excitation energies near the vertical detachment energy. The experiments are complemented by quantum chemical calculations. One-color spectra show evidence for two adenine tautomers, the canonical, biologically relevant A9 tautomer and the A3 tautomer. In the UV-pump/IR-probe time-resolved experiments, transient adenine anions can be formed by electron transfer from the iodide. These experiments show signals from both DB and VB states of adenine anions formed on femto- and picosecond time scales, respectively. Analysis of the spectra and comparison with calculations suggest that while both the A9 and A3 tautomers contribute to the DB signal, only the DB state of the A3 tautomer undergoes a transition to the VB anion. The VB anion of A9 is higher in energy than both the DB anion and the neutral, and the VB anion is therefore not accessible through the DB state. Experimental evidence of the metastable A9 VB anion is instead observed as a shape resonance in the one-color photoelectron spectra, as a result of UV absorption by A9 and subsequent electron transfer from iodide into the empty π-orbital. In contrast, the iodide-A3 complex constitutes an excellent example of how DB states can act as doorway state for VB anion formation when the VB state is energetically available.

  5. Time-resolved photoluminescence measurements of InGaAs/ InP multiple-quantum-well structures at 1.3-µm wavelengths by use of germanium single-photon avalanche photodiodes.

    Science.gov (United States)

    Buller, G S; Fancey, S J; Massa, J S; Walker, A C; Cova, S; Lacaita, A

    1996-02-20

    A commercially available germanium avalanche photodiode operating in the single-photon-counting mode has been used to perform time-resolved photoluminescence measurements on InGaAs/lnP multiple-quantum-well structures. Photoluminescence in the spectral region of 1.3-1.48 µm was detected with picosecond timing accuracy by use of the time-correlated single-photon counting technique. The carrier dynamics were monitored for excess photogenerated carrier densities in the range 10(18)-10(15) cm(-3). The recombination time is compared for similar InGaAs-based quantum-well structures grown by use of different epitaxial processes.

  6. Picosecond laser filamentation in air

    Science.gov (United States)

    Schmitt-Sody, Andreas; Kurz, Heiko G.; Bergé, Luc; Skupin, Stefan; Polynkin, Pavel

    2016-09-01

    The propagation of intense picosecond laser pulses in air in the presence of strong nonlinear self-action effects and air ionization is investigated experimentally and numerically. The model used for numerical analysis is based on the nonlinear propagator for the optical field coupled to the rate equations for the production of various ionic species and plasma temperature. Our results show that the phenomenon of plasma-driven intensity clamping, which has been paramount in femtosecond laser filamentation, holds for picosecond pulses. Furthermore, the temporal pulse distortions in the picosecond regime are limited and the pulse fluence is also clamped. In focused propagation geometry, a unique feature of picosecond filamentation is the production of a broad, fully ionized air channel, continuous both longitudinally and transversely, which may be instrumental for many applications including laser-guided electrical breakdown of air, channeling microwave beams and air lasing.

  7. [A method for time-resolved laser-induced breakdown spectroscopy measurement].

    Science.gov (United States)

    Pan, Cong-Yuan; Han, Zhen-Yu; Li, Chao-Yang; Yu, Yun-Si; Wang, Sheng-Bo; Wang, Qiu-Ping

    2014-04-01

    Laser-Induced Breakdown Spectroscopy (LIBS) is strongly time related. Time-resolved LIBS measurement is an important technique for the research on laser induced plasma evolution and self-absorption of the emission lines. Concerning the temporal characteristics of LIBS spectrum, a method is proposed in the present paper which can achieve micros-scale time-resolved LIBS measurement by using general ms-scale detector. By setting different integration delay time of the ms-scale spectrum detector, a series of spectrum are recorded. And the integration delay time interval should be longer than the worst temporal precision. After baseline correction and spectrum fitting, the intensity of the character line was obtained. Calculating this intensity with differential method at a certain time interval and then the difference value is the time-resolved line intensity. Setting the plasma duration time as X-axis and the time-resolved line intensity as Y-axis, the evolution curve of the character line intensity can be plotted. Character line with overlap-free and smooth background should be a priority to be chosen for analysis. Using spectrometer with ms-scale integration time and a control system with temporal accuracy is 0.021 micros, experiments carried out. The results validate that this method can be used to characterize the evolution of LIBS characteristic lines and can reduce the cost of the time-resolved LIBS measurement system. This method makes high time-resolved LIBS spectrum measurement possible with cheaper system.

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

    Science.gov (United States)

    Moffat, Keith

    2014-07-17

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

  9. The primary photophysics of the Avena sativa phototropin 1 LOV2 domain observed with time-resolved emission spectroscopy.

    Science.gov (United States)

    van Stokkum, Ivo H M; Gauden, Magdalena; Crosson, Sean; van Grondelle, Rienk; Moffat, Keith; Kennis, John T M

    2011-01-01

    The phototropins are blue-light receptors that base their light-dependent action on the reversible formation of a covalent bond between a flavin mononucleotide (FMN) cofactor and a conserved cysteine in light, oxygen or voltage (LOV) domains. The primary reactions of the Avena sativa phototropin 1 LOV2 domain were investigated by means of time-resolved and low-temperature fluorescence spectroscopy. Synchroscan streak camera experiments revealed a fluorescence lifetime of 2.2 ns in LOV2. A weak long-lived component with emission intensity from 600 to 650 nm was assigned to phosphorescence from the reactive FMN triplet state. This observation allowed determination of the LOV2 triplet state energy level at physiological temperature at 16600 cm(-1). FMN dissolved in aqueous solution showed pH-dependent fluorescence lifetimes of 2.7 ns at pH 2 and 3.9-4.1 ns at pH 3-8. Here, too, a weak phosphorescence band was observed. The fluorescence quantum yield of LOV2 increased from 0.13 to 0.41 upon cooling the sample from 293 to 77 K. A pronounced phosphorescence emission around 600 nm was observed in the LOV2 domain between 77 and 120 K in the steady-state emission.

  10. 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.

  11. Time-resolved photoluminescence spectroscopy and imaging: new approaches to the analysis of cultural heritage and its degradation.

    Science.gov (United States)

    Nevin, Austin; Cesaratto, Anna; Bellei, Sara; D'Andrea, Cosimo; Toniolo, Lucia; Valentini, Gianluca; Comelli, Daniela

    2014-04-02

    Applications of time-resolved photoluminescence spectroscopy (TRPL) and fluorescence lifetime imaging (FLIM) to the analysis of cultural heritage are presented. Examples range from historic wall paintings and stone sculptures to 20th century iconic design objects. A detailed description of the instrumentation developed and employed for analysis in the laboratory or in situ is given. Both instruments rely on a pulsed laser source coupled to a gated detection system, but differ in the type of information they provide. Applications of FLIM to the analysis of model samples and for the in-situ monitoring of works of art range from the analysis of organic materials and pigments in wall paintings, the detection of trace organic substances on stone sculptures, to the mapping of luminescence in late 19th century paintings. TRPL and FLIM are employed as sensors for the detection of the degradation of design objects made in plastic. Applications and avenues for future research are suggested.

  12. Time-Resolved Photoluminescence Spectroscopy and Imaging: New Approaches to the Analysis of Cultural Heritage and Its Degradation

    Directory of Open Access Journals (Sweden)

    Austin Nevin

    2014-04-01

    Full Text Available Applications of time-resolved photoluminescence spectroscopy (TRPL and fluorescence lifetime imaging (FLIM to the analysis of cultural heritage are presented. Examples range from historic wall paintings and stone sculptures to 20th century iconic design objects. A detailed description of the instrumentation developed and employed for analysis in the laboratory or in situ is given. Both instruments rely on a pulsed laser source coupled to a gated detection system, but differ in the type of information they provide. Applications of FLIM to the analysis of model samples and for the in-situ monitoring of works of art range from the analysis of organic materials and pigments in wall paintings, the detection of trace organic substances on stone sculptures, to the mapping of luminescence in late 19th century paintings. TRPL and FLIM are employed as sensors for the detection of the degradation of design objects made in plastic. Applications and avenues for future research are suggested.

  13. Radiative lifetime measurements of some Tm I and Tm II levels by time-resolved laser spectroscopy

    Science.gov (United States)

    Tian, Yanshan; Wang, Xinghao; Yu, Qi; Li, Yongfan; Gao, Yang; Dai, Zhenwen

    2016-04-01

    Radiative lifetimes of 88 levels of Tm I in the energy range 22 791.176-48 547.98 cm-1 and 29 levels of Tm II in the range 27 294.79-65 612.85 cm-1 were measured by time-resolved laser-induced fluorescence spectroscopy in laser-ablation plasma. The lifetime values obtained are in the range from 15.4 to 7900 ns for Tm I and from 36.5 to 1000 ns for Tm II. To the best of our knowledge, 77 lifetimes of Tm I and 22 lifetimes of Tm II are reported for the first time. Good agreements between the present results and the previous experimental values were achieved for both Tm I and Tm II.

  14. Radiative lifetime measurements of odd-parity highly-excited levels of Sn I by time-resolved laser spectroscopy

    Institute of Scientific and Technical Information of China (English)

    Xu Jia-Xin; Feng Yan-Yan; Sun Gui-Juan; Dai Zhen-Wen

    2009-01-01

    Natural radiative lifetimes of five higher-lying odd-parity levels 5pTs 3p1o,5p5d 1p1o,5p6d 3F2o,3D1o and 3F3o in neutral tin are measured by the time-resolved laser-induced fluorescence (TR-LIF) technique and the atomic beam method. All these lifetimes are not longer than 100 ns and they are found to be shorter than the lifetimes of evenparity levels in the same energy region. The results reported in this paper provide important transition parameters for highly-excited atomic Sn,which may be useful for theoretically calculating excited heavy atoms.

  15. Mechanism of intramolecular charge transfer in DNA helix as probed by the use of the fluorescent 2-aminopurine

    Institute of Scientific and Technical Information of China (English)

    ZHANG Huijuan; WANG Peng; WANG Xuefei; FENG Juan; XU Sichuan; AI Xicheng; ZHANG Xingkang; ZHANG Jianping

    2004-01-01

    As a structural analogue of adenine, 2-aminopurine (2Ap) is often used as a fluorescent probe to study the intramolecular charge transfer reaction in DNA. We have designed and synthesized a series of model DNA helix with the variation in the distance between the 2Ap probe and the GGG sequence, and have investigated, by means of picosecond time-resolved fluorescence spectroscopy, the effect of the length of the bridge (consisting of a number of transfer dynamics. The fluorescence dynamics of 2Ap exhibited three exponential decay components, the one with a time constant of a few hundred picoseconds is assigned to the intramolecular charge transfer from GGG to 2Ap. Within 2.4 nm of the donor-acceptor separation,the rate of charge transfer decreased exponentially upon increasing the separation, from which the decay factor ,β is determined to be 1.3 nm-1. Beyond 2.4 nm, however, the rate started to increase, this abnormal behavior of charge transfer is interpreted in terms of the match of electronic energies between the I-bridge and the donor/acceptor couple.

  16. Ultrafast fluorescence of photosynthetic crystals and light-harvesting complexes

    NARCIS (Netherlands)

    Oort, van B.F.

    2008-01-01

    This thesis focuses on the study of photosynthetic pigment protein complexes using time resolved fluorescence techniques. Fluorescence spectroscopy often requires attaching fluorescent labels to the proteins under investigation. With photosynthetic proteins this is not necessary, because these

  17. Ultrafast fluorescence of photosynthetic crystals and light-harvesting complexes

    NARCIS (Netherlands)

    Oort, van B.F.

    2008-01-01

    This thesis focuses on the study of photosynthetic pigment protein complexes using time resolved fluorescence techniques. Fluorescence spectroscopy often requires attaching fluorescent labels to the proteins under investigation. With photosynthetic proteins this is not necessary, because these prote

  18. Ultrafast fluorescence of photosynthetic crystals and light-harvesting complexes

    NARCIS (Netherlands)

    Oort, van B.F.

    2008-01-01

    This thesis focuses on the study of photosynthetic pigment protein complexes using time resolved fluorescence techniques. Fluorescence spectroscopy often requires attaching fluorescent labels to the proteins under investigation. With photosynthetic proteins this is not necessary, because these prote

  19. A New Approach of Oil Spill Detection Using Time-Resolved LIF Combined with Parallel Factors Analysis for Laser Remote Sensing

    Directory of Open Access Journals (Sweden)

    Deqing Liu

    2016-08-01

    Full Text Available In hope of developing a method for oil spill detection in laser remote sensing, a series of refined and crude oil samples were investigated using time-resolved fluorescence in conjunction with parallel factors analysis (PARAFAC. The time resolved emission spectra of those investigated samples were taken by a laser remote sensing system on a laboratory basis with a detection distance of 5 m. Based on the intensity-normalized spectra, both refined and crude oil samples were well classified without overlapping, by the approach of PARAFAC with four parallel factors. Principle component analysis (PCA has also been operated as a comparison. It turned out that PCA operated well in classification of broad oil type categories, but with severe overlapping among the crude oil samples from different oil wells. Apart from the high correct identification rate, PARAFAC has also real-time capabilities, which is an obvious advantage especially in field applications. The obtained results suggested that the approach of time-resolved fluorescence combined with PARAFAC would be potentially applicable in oil spill field detection and identification.

  20. A New Approach of Oil Spill Detection Using Time-Resolved LIF Combined with Parallel Factors Analysis for Laser Remote Sensing.

    Science.gov (United States)

    Liu, Deqing; Luan, Xiaoning; Guo, Jinjia; Cui, Tingwei; An, Jubai; Zheng, Ronger

    2016-08-23

    In hope of developing a method for oil spill detection in laser remote sensing, a series of refined and crude oil samples were investigated using time-resolved fluorescence in conjunction with parallel factors analysis (PARAFAC). The time resolved emission spectra of those investigated samples were taken by a laser remote sensing system on a laboratory basis with a detection distance of 5 m. Based on the intensity-normalized spectra, both refined and crude oil samples were well classified without overlapping, by the approach of PARAFAC with four parallel factors. Principle component analysis (PCA) has also been operated as a comparison. It turned out that PCA operated well in classification of broad oil type categories, but with severe overlapping among the crude oil samples from different oil wells. Apart from the high correct identification rate, PARAFAC has also real-time capabilities, which is an obvious advantage especially in field applications. The obtained results suggested that the approach of time-resolved fluorescence combined with PARAFAC would be potentially applicable in oil spill field detection and identification.

  1. Apparatus and Techniques for Time-resolved Synchrotron X-ray Diffraction using Diamond Anvil Cells

    Science.gov (United States)

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

    2015-12-01

    Complementary advances in synchrotron sources, x-ray optics, area detectors, and sample environment control have recently made possible many time-resolved experimental techniques for studying materials at extreme pressure and temperature conditions. The High Pressure Collaborative Access Team (HPCAT) at the Advanced Photon Source has made a sustained effort to assemble a powerful collection of high-pressure apparatus for time-resolved research, and considerable time has been invested in developing techniques for collecting high-quality time-resolved x-ray scattering data. Herein we present key aspects of the synchrotron beamline and ancillary equipment, including source considerations, rapid (de)compression apparatus, high frequency imaging detectors, and software suitable for processing large volumes of data. A number of examples are presented, including fast equation of state measurements, compression rate dependent synthesis of metastable states in silicon and germanium, and ultrahigh compression rates using a piezoelectric driven diamond anvil cell.

  2. Understanding optically stimulated charge movement in quartz and feldspar using time-resolved measurements

    DEFF Research Database (Denmark)

    Ankjærgaard, Christina

    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...... and the conduction band in determining charge transport. It is suggested that unlike quartz, the excited state lifetime does not play an important role in our measurements. Finally, it is shown that one of these routes favors production if a least fading signal (due to quantum mechanical tunnelling) in feldspars...... 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...

  3. Capturing molecular structural dynamics by 100 ps time-resolved X-ray absorption spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Sato, Tokushi [Department of Materials Science, Tokyo Institute of Technology, 2-12-1-H61 Ohokayama, Meguro-ku, Tokyo 152-8551 (Japan); Non-Equilibrium Dynamics Project, ERATO, Japan Science and Technology Agency, 1-1 Oho, Tsukuba, Ibaraki 305-0801 (Japan); Nozawa, Shunsuke; Ichiyanagi, Kohei [Non-Equilibrium Dynamics Project, ERATO, Japan Science and Technology Agency, 1-1 Oho, Tsukuba, Ibaraki 305-0801 (Japan); Tomita, Ayana [Department of Materials Science, Tokyo Institute of Technology, 2-12-1-H61 Ohokayama, Meguro-ku, Tokyo 152-8551 (Japan); Non-Equilibrium Dynamics Project, ERATO, Japan Science and Technology Agency, 1-1 Oho, Tsukuba, Ibaraki 305-0801 (Japan); Chollet, Matthieu [Department of Materials Science, Tokyo Institute of Technology, 2-12-1-H61 Ohokayama, Meguro-ku, Tokyo 152-8551 (Japan); Ichikawa, Hirohiko [Non-Equilibrium Dynamics Project, ERATO, Japan Science and Technology Agency, 1-1 Oho, Tsukuba, Ibaraki 305-0801 (Japan); Fujii, Hiroshi [Institute for Molecular Science and Okazaki Institute for Integrative Bioscience, Myodaiji, Okazaki 444-8787 (Japan); Adachi, Shin-ichi [Non-Equilibrium Dynamics Project, ERATO, Japan Science and Technology Agency, 1-1 Oho, Tsukuba, Ibaraki 305-0801 (Japan); High Energy Accelerator Research Organization, 1-1 Oho, Tsukuba, Ibaraki 305-0801 (Japan); Koshihara, Shin-ya, E-mail: skoshi@cms.titech.ac.jp [Department of Materials Science, Tokyo Institute of Technology, 2-12-1-H61 Ohokayama, Meguro-ku, Tokyo 152-8551 (Japan); Non-Equilibrium Dynamics Project, ERATO, Japan Science and Technology Agency, 1-1 Oho, Tsukuba, Ibaraki 305-0801 (Japan); High Energy Accelerator Research Organization, 1-1 Oho, Tsukuba, Ibaraki 305-0801 (Japan); Frontier Research Center, Tokyo Institute of Technology, 2-12-1 Ohokayama, Meguro-ku, Tokyo 152-8551 (Japan)

    2009-01-01

    An experimental set-up for time-resolved X-ray absorption spectroscopy with 100 ps time resolution at beamline NW14A at the Photon Factory Advanced Ring is presented. An experimental set-up for time-resolved X-ray absorption spectroscopy with 100 ps time resolution at beamline NW14A at the Photon Factory Advanced Ring is presented. The X-ray positional active feedback to crystals in a monochromator combined with a figure-of-merit scan of the laser beam position has been utilized as an essential tool to stabilize the spatial overlap of the X-ray and laser beams at the sample position. As a typical example, a time-resolved XAFS measurement of a photo-induced spin crossover reaction of the tris(1,10-phenanthrorine)iron(II) complex in water is presented.

  4. Recent advances in 3D time-resolved contrast-enhanced MR angiography.

    Science.gov (United States)

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

    2015-07-01

    Contrast-enhanced magnetic resonance angiography (CE-MRA) was first introduced for clinical studies approximately 20 years ago. Early work provided 3-4 mm spatial resolution with acquisition times in the 30-second range. Since that time there has been continuing effort to provide improved spatial resolution with reduced acquisition time, allowing high resolution 3D time-resolved studies. The purpose of this work is to describe how this has been accomplished. Specific technical enablers have been: improved gradients allowing reduced repetition times, improved k-space sampling and reconstruction methods, parallel acquisition, particularly in two directions, and improved and higher count receiver coil arrays. These have collectively made high-resolution time-resolved studies readily available for many anatomic regions. Depending on the application, ∼1 mm isotropic resolution is now possible with frame times of several seconds. Clinical applications of time-resolved CE-MRA are briefly reviewed. © 2015 Wiley Periodicals, Inc.

  5. Extracting Time-Resolved Information from Time-Integrated Laser-Induced Breakdown Spectra

    Directory of Open Access Journals (Sweden)

    Emanuela Grifoni

    2014-01-01

    Full Text Available Laser-induced breakdown spectroscopy (LIBS data are characterized by a strong dependence on the acquisition time after the onset of the laser plasma. However, time-resolved broadband spectrometers are expensive and often not suitable for being used in portable LIBS instruments. In this paper we will show how the analysis of a series of LIBS spectra, taken at different delays after the laser pulse, allows the recovery of time-resolved spectral information. The comparison of such spectra is presented for the analysis of an aluminium alloy. The plasma parameters (electron temperature and number density are evaluated, starting from the time-integrated and time-resolved spectra, respectively. The results are compared and discussed.

  6. Disentangling Multichannel Photodissociation Dynamics in Acetone by Time-Resolved Photoelectron-Photoion Coincidence Spectroscopy.

    Science.gov (United States)

    Maierhofer, Paul; Bainschab, Markus; Thaler, Bernhard; Heim, Pascal; Ernst, Wolfgang E; Koch, Markus

    2016-08-18

    For the investigation of photoinduced dynamics in molecules with time-resolved pump-probe photoionization spectroscopy, it is essential to obtain unequivocal information about the fragmentation behavior induced by the laser pulses. We present time-resolved photoelectron-photoion coincidence (PEPICO) experiments to investigate the excited-state dynamics of isolated acetone molecules triggered by two-photon (269 nm) excitation. In the complex situation of different relaxation pathways, we unambiguously identify three distinct pump-probe ionization channels. The high selectivity of PEPICO detection allows us to observe the fragmentation behavior and to follow the time evolution of each channel separately. For channels leading to fragment ions, we quantitatively obtain the fragment-to-parent branching ratio and are able to determine experimentally whether dissociation occurs in the neutral molecule or in the parent ion. These results highlight the importance of coincidence detection for the interpretation of time-resolved photochemical relaxation and dissociation studies if multiple pathways are present.

  7. Time resolved single molecule spectroscopy of semiconductor quantum dot/conjugated organic hybrid nanostructures

    Science.gov (United States)

    Odoi, Michael Yemoh

    Single molecule studies on CdSe quantum dots functionalized with oligo-phenylene vinylene ligands (CdSe-OPV) provide evidence of strong electronic communication that facilitate charge and energy transport between the OPV ligands and the CdSe quantum dot core. This electronic interaction greatly modify, the photoluminescence properties of both bulk and single CdSe-OPV nanostructure thin film samples. Size-correlated wide-field fluorescence imaging show that blinking suppression in single CdSe-OPV is linked to the degree of OPV coverage (inferred from AFM height scans) on the quantum dot surface. The effect of the complex electronic environment presented by photoexcited OPV ligands on the excited state property of CdSe-OPV is measured with single photon counting and photon-pair correlation spectroscopy techniques. Time-tagged-time-resolved (TTTR) single photon counting measurements from individual CdSe-OPV nanostructures, show excited state lifetimes an order of magnitude shorter relative to conventional ZnS/CdSe quantum dots. Second-order intensity correlation measurements g(2)(tau) from individual CdSe-OPV nanostructures point to a weak multi-excitonic character with a strong wavelength dependent modulation depth. By tuning in and out of the absorption of the OPV ligands we observe changes in modulation depth from g(2) (0) ≈ 0.2 to 0.05 under 405 and 514 nm excitation respectively. Defocused images and polarization anisotropy measurements also reveal a well-defined linear dipole emission pattern in single CdSe-OPV nanostructures. These results provide new insights into to the mechanism behind the electronic interactions in composite quantum dot/conjugated organic composite systems at the single molecule level. The observed intensity flickering , blinking suppression and associated lifetime/count rate and antibunching behaviour is well explained by a Stark interaction model. Charge transfer from photo-excitation of the OPV ligands to the surface of the Cd

  8. Time-resolved electron transport in quantum-dot systems; Zeitaufgeloester Elektronentransport in Quantendotsystemen

    Energy Technology Data Exchange (ETDEWEB)

    Croy, Alexander

    2010-06-30

    In this thesis the time-resolved electron transport in quantum dot systems was studied. For this two different formalisms were presented: The nonequilibrium Green functions and the generalized quantum master equations. For both formalisms a propagation method for the numerical calculation of time-resolved expectation values, like the occupation and the electron current, was developed. For the demonstration of the propagation method two different question formulations were considered. On the one hand the stochastically driven resonant-level model was studied. On the other hand the pulse-induced transport through a double quantum dot was considered.

  9. 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.

  10. Time resolved ESR spectroscopy. ESR pulse radiolysis equipment with microsecond time resolution

    Energy Technology Data Exchange (ETDEWEB)

    Beckert, D.; Mehler, K. (Akademie der Wissenschaften der DDR, Leipzig. Zentralinstitut fuer Isotopen- und Strahlenforschung)

    1983-01-01

    Time resolved ESR experiments allow the study of the chemical kinetics as well as spin dynamics of free radicals in the liquid phase. Starting from the physical and chemical requirements the experimental parameters of a universal time resolved ESR spectrometer are derived. The main components of the ESR pulse radiolysis equipment are described and their technical parameters are discussed. By two experimental examples it is shown that at a time resolution of 0.3 ..mu..s a sensitivity of c/sub min/ = 10/sup -6/ mol dm/sup -3/ for simple radical spectra can be achieved.

  11. TRIASSIC: the Time-Resolved Industrial Alpha-Source Scanning Induced Current microscope

    Science.gov (United States)

    Pallone, Arthur

    Time-resolved ion beam induced current (TRIBIC) microscopy yields useful information such as carrier mobility and lifetimes in semiconductors and defect locations in devices; however, traditional TRIBIC uses large, expensive particle accelerators that require specialized training to operate and maintain. The time-resolved industrial alpha-source scanning induced current (TRIASSIC) microscope transforms TRIBIC by replacing the particle accelerator facility with an affordable, tabletop instrument suitable for use in research and education at smaller colleges and universities. I will discuss the development of, successes with, setbacks to and future directions for TRIASSIC.

  12. Time-resolved detection of relative intensity squeezed nanosecond pulses in a 87Rb vapor

    CERN Document Server

    Agha, Imad H; Messin, Gaetan; Grangier, Philippe

    2010-01-01

    We present experimental studies on the generation and detection of pulsed, relative-intensity squeezed light in a warm rubidium vapor. The noise correlations between a pulsed probe beam and its conjugate -generated through nearly-degenerate four-wave mixing in a double-lambda system- are studied via time-resolved balanced detection. We observe -0.96 dB of time-resolved relative intensity squeezing with 50 nanosecond pulses at 1 MHz repetition rate. (-1.34 dB corrected for loss).

  13. Time-resolved detection of relative intensity squeezed nanosecond pulses in a Rb87 vapor

    CERN Document Server

    Agha, Imad H; Glorieux, Quentin; Coudreau, Thomas; Grangier, Philippe; Messin, Gaetan

    2011-01-01

    We present theoretical and experimental results on the generation and detection of pulsed, relative-intensity squeezed light in a hot Rb87 vapor. The intensity noise correlations between a pulsed probe beam and its conjugate, generated through nearly-degenerate four-wave mixing in a double-lambda system, are studied numerically and measured experimentally via time-resolved balanced detection. We predict and observe about -1 dB of time-resolved relative intensity squeezing with 50 nanosecond pulses at 1 MHz repetition rate. (-1.34 dB corrected for loss).

  14. 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....

  15. A time-resolved infrared vibrational spectroscopic study of the photo-dynamics of crystalline materials.

    Science.gov (United States)

    Towrie, Mike; Parker, Anthony W; Ronayne, Kate L; Bowes, Katharine F; Cole, Jacqueline M; Raithby, Paul R; Warren, John E

    2009-01-01

    Time-resolved infrared vibrational spectroscopy is a structurally sensitive probe of the excited-state properties of matter. The technique has found many applications in the study of molecules in dilute solution phase but has rarely been applied to crystalline samples. We report on the use of a sensitive pump-probe time-resolved infrared spectrometer and sample handling techniques for studies of the ultrafast excited-state dynamics of crystalline materials. The charge transfer excited states of crystalline metal carbonyls and the proton transfer of dihydroxyquinones are presented and compared with the solution phase.

  16. Combined single-pulse holography and time-resolved laser schlieren for flow visualization

    Science.gov (United States)

    Burner, A. W.; Goad, W. K.

    1981-01-01

    A pulsed ruby laser and continuous-wave argon ion laser were used in a combined setup at the Langley Expansion Tube for single pulse holography and time resolved laser schlieren with a common optical axis. The systems can be operated simultaneously for a single run. For a single frame, the pulsed holographic setup offers the options of shadowgraph, Schlieren, and interferometry from the reconstructed hologram as well as the advantage of post-run sensitivity adjustments. For flow establishment studies the time resolved laser Schlieren provides visualization of the flow field every 12.5 microns for up to 80 frames with an exposure time per frame of 5.4 microns.

  17. Time-resolved Rocking Curve Measurement Method using Laboratory X-ray Source

    OpenAIRE

    林, 雄二郎; 佐藤, 真伸; 古賀, 三井; 佃, 昇; 蔵元, 英一

    2005-01-01

    Fast x-ray detectors and fast signal processing devices have enabled to measure time dependence of x-ray diffraction intensity. Using a fast x-ray detection system, we have developed a time-resolved measurement method of rocking curves with a laboratory x-ray source. The method has been demonstrated for time-resolved rocking curves from an ultrasound-vibrated silicon crystal in MHz range. The measured rocking curves have been consistent with simulated curves based on the dynamical diffraction...

  18. Picosecond laser filamentation in air

    CERN Document Server

    Schmitt-Sody, Andreas; Bergé, L; Skupin, S; Polynkin, Pavel

    2016-01-01

    The propagation of intense picosecond laser pulses in air in the presence of strong nonlinear self-action effects and air ionization is investigated experimentally and numerically. The model used for numerical analysis is based on the nonlinear propagator for the optical field coupled with the rate equations for the production of various ionic species and plasma temperature. Our results show that the phenomenon of plasma-driven intensity clamping, which is paramount in femtosecond laser filamentation, holds for picosecond pulses. Furthermore, the temporal pulse distortions are limited and the pulse fluence is also clamped. The resulting unique feature of the picosecond filamentation regime is the production of a broad, fully ionized air channel, continuous both longitudinally and transversely, which may be instrumental for numerous applications.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1999-07-19

    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.

  20. Compact cryogenic Kerr microscope for time-resolved studies of electron spin transport in microstructures

    NARCIS (Netherlands)

    Rizo, P. J.; Pugzlys, A.; Liu, J.; Reuter, D.; Wieck, A. D.; van der Wal, C. H.; van Loosdrecht, P. H. M.; Pugžlys, A.

    2008-01-01

    A compact cryogenic Kerr microscope for operation in the small volume of high-field magnets is described. It is suited for measurements both in Voigt and Faraday configurations. Coupled with a pulsed laser source, the microscope is used to measure the time-resolved Kerr rotation response of

  1. Time-resolved proton polarisation (TPP) images tyrosyl radical sites in bovine liver catalase.

    Science.gov (United States)

    Zimmer, Oliver; Jouve, Hélène M.; Stuhrmann, Heinrich B.

    2017-05-01

    A differentiation between dynamic polarised protons close to tyrosyl radical sites in catalase and those of the bulk is achieved by time-resolved polarised neutron scattering. Three radical sites, all of them being close to the molecular centre and the heme, appear to be equally possible. Among these is tyr-369 the radial site of which had previously been proven by EPR.

  2. Phase separation during silica gel formation followed by time-resolved SAXS

    Energy Technology Data Exchange (ETDEWEB)

    Gommes, Cedric J. [Universite de Liege, Laboratoire de Genie Chimique, Bat B6a, Allee du 6 aout 3, B-4000 Sart Tilman Liege (Belgium)]. E-mail: cedric.gommes@ulg.ac.be; Blacher, Silvia [Universite de Liege, Laboratoire de Genie Chimique, Bat B6a, Allee du 6 aout 3, B-4000 Sart Tilman Liege (Belgium); Goderis, Bart [Katholieke Universiteit Leuven, Laboratorium voor Macromoleculaire Structuurchemie, Celestijnenlann 200F, B-3001 Heverlee (Belgium); Pirard, Jean-Paul [Universite de Liege, Laboratoire de Genie Chimique, Bat B6a, Allee du 6 aout 3, B-4000 Sart Tilman Liege (Belgium)

    2005-08-15

    Time-resolved small angle X-ray scattering data are collected during the formation of silica gels from the base catalyzed polymerization of tetraethoxysilane in ethanol with 3-(2-aminoethylamino)propyltrimethoxysilane and 3-aminopropyltriethoxysilane as additives. It is shown that a polymerization-induced spinodal demixing occurs during the gel formation.

  3. Time-resolved diffusing wave spectroscopy applied to dynamic heterogeneity imaging

    CERN Document Server

    Cheikh, M; Ettori, D; Tinet, E; Avrillier, S; Tualle, J M; Cheikh, Monia; Nghiem, Ha Lien; Ettori, Dominique; Tinet, Eric; Avrillier, Sigrid; Tualle, Jean-Michel

    2006-01-01

    We report in this paper what is to our knowledge the first observation of a time-resolved diffusing wave spectroscopy signal recorded by transillumination through a thick turbid medium: the DWS signal is measured for a fixed photon transit time, which opens the possibility of improving the spatial resolution. This technique could find biomedical applications, especially in mammography.

  4. 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.

  5. Time-resolved electron spectrum diagnostics for a free-electron laser

    NARCIS (Netherlands)

    Gillespie, W. A.; MacLeod, A. M.; Martin, P. F.; van der Meer, A. F. G.; van Amersfoort, P. W.

    1996-01-01

    Time-resolved electron-beam diagnostics have been developed for use with free-electron lasers (FELs) and associated electron sources, based on the techniques of secondary electron emission and optical transition radiation (OTR). The 32-channel OTR detector forms part of a high-resolution (0.18%) ele

  6. Computer simulation of time-resolved optical imaging of objects hidden in turbid media

    NARCIS (Netherlands)

    Michielsen, K.; Raedt, H. De; Przeslawski, J.; Garcia, N.

    1998-01-01

    We review research on time-resolved optical imaging of objects hidden in strongly scattering media, with emphasis on the application to breast cancer detection. A method is presented to simulate the propagation of light in turbid media. Based on a numerical algorithm to solve the time-dependent diff

  7. Space and Time Resolved Spectroscopy during the Preparation of Hydrogenation Catalyst Bodies

    NARCIS (Netherlands)

    Espinosa Alonso, L.|info:eu-repo/dai/nl/304837342

    2009-01-01

    The development of space and time resolved spectroscopic methods to image space and time dependent heterogeneities in catalyst bodies during preparation is of paramount importance for the development of more efficient and sustainable chemical processes. There are a large number of physicochemical

  8. Pseudo-bimolecular [2+2] cycloaddition studied by time-resolved photoelectron spectroscopy

    DEFF Research Database (Denmark)

    Brogaard, Rasmus Y; Boguslavskiy, Andrey E; Schalk, Oliver

    2011-01-01

    The first study of pseudo-bimolecular cycloaddition reaction dynamics in the gas phase is presented. We used femtosecond time-resolved photoelectron spectroscopy (TRPES) to study the [2+2] photocycloaddition in the model system pseudo-gem-divinyl[2.2]paracyclophane. From X-ray crystal diffraction...

  9. Reduction of Guanosyl Radical by Cysteine and Cysteine-Glycine Studied by Time-Resolved CIDNP

    NARCIS (Netherlands)

    Morozova, O.B.; Kaptein, R.; Yurkovskaya, A.V.

    2012-01-01

    As a model for chemical DNA repair, reduction of guanosyl radicals in the reaction with cysteine or the dipeptide cysteine-glycine has been studied by time-resolved chemically induced dynamic nuclear polarization (CIDNP). Radicals were generated photochemically by pulsed laser irradiation of a solut

  10. Evolution of a Rippled Membrane during Phospholipase A2 Hydrolysis Studied by Time-Resolved AFM

    DEFF Research Database (Denmark)

    Leidy, Chad; Mouritsen, Ole G.; Jørgensen, Kent;

    2004-01-01

    The sensitivity of phospholipase A2 (PLA2) for lipid membrane curvature is explored by monitoring, through time-resolved atomic force microscopy, the hydrolysis of supported double bilayers in the ripple phase. The ripple phase presents a corrugated morphology. PLA2 is shown to have higher activi...

  11. Time-resolved magnetic circular dichroism spectroscopy of photolyzed carbonmonoxy cytochrome c oxidase (cytochrome aa3).

    Science.gov (United States)

    Goldbeck, R A; Dawes, T D; Einarsdóttir, O; Woodruff, W H; Kliger, D S

    1991-07-01

    Nanosecond time-resolved magnetic circular dichroism (TRMCD) and time-resolved natural circular dichroism (TRCD) measurements of photolysis products of the CO complex of eukaryotic cytochrome c oxidase (CcO-CO) are presented. TRMCD spectra obtained at 100 ns and 10 microseconds after photolysis are diagnostic of pentacoordinate cytochrome a3Fe2+, as would be expected for simple photodissociation. Other time-resolved spectroscopies (UV-visible and resonance Raman), however, show evidence for unusual Fea3(2+) coordination after CO photolysis (Woodruff, W. H., O. Einarsdóttir, R. B. Dyer, K. A. Bagley, G. Palmer, S. J. Atherton, R. A. Goldbeck, T. D. Dawes, and D. S. Kliger. 1991. Proc. Nat. Acad. Sci. U.S.A. 88:2588-2592). Furthermore, time-resolved IR experiments have shown that photodissociated CO binds to CuB+ prior to recombining with Fea3(2+) (Dyer, R. B., O. Einarsdóttir, P. M. Killough, J. J. López-Garriga, and W. H. Woodruff. 1989. J. Am. Chem. Soc. 111:7657-7659). A model of the CcO-CO photolysis cycle which is consistent with all of the spectroscopic results is presented. A novel feature of this model is the coordination of a ligand endogenous to the protein to the Fe axial site vacated by the photolyzed CO and the simultaneous breaking of the Fe-imidazole(histidine) bond.

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

    Energy Technology Data Exchange (ETDEWEB)

    Rutherford, Michael E.; Chapman, David J.; White, Thomas G. [Imperial College London, London (United Kingdom); Drakopoulos, Michael [Diamond Light Source, I12 Joint Engineering, Environmental, Processing (JEEP) Beamline, Didcot, Oxfordshire (United Kingdom); Rack, Alexander [European Synchrotron Radiation Facility, Grenoble (France); Eakins, Daniel E., E-mail: d.eakins@imperial.ac.uk [Imperial College London, London (United Kingdom)

    2016-03-24

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

  13. Chilling injury in stored nectarines and its detection by time-resolved reflectance spectroscopy

    NARCIS (Netherlands)

    Lurie, S.; Vanoli, M.; Dagar, A.; Weksler, A.; Eccher Zerbini, P.C.; Spinelli, L.; Torricelli, A.; Lovati, F.; Feng, R.; Rizzolo, A.

    2011-01-01

    Nectarine fruit after cold storage soften normally, but become dry instead of juicy and can develop flesh browning, bleeding and a gel-like or glassy formation of the flesh near the pit. An experiment was conducted to see if time-resolved reflectance spectroscopy could distinguish these internal dis

  14. Development of a visible-light-sensitized europium complex for time-resolved fluorometric application.

    Science.gov (United States)

    Jiang, Lina; Wu, Jing; Wang, Guilan; Ye, Zhiqiang; Zhang, Wenzhu; Jin, Dayong; Yuan, Jingli; Piper, James

    2010-03-15

    The time-resolved luminescence bioassay technique using luminescent lanthanide complexes as labels is a highly sensitive and widely used bioassay method for clinical diagnostics and biotechnology. A major drawback of the current technique is that the luminescent lanthanide labels require UV excitation (typically less than 360 nm), which can damage living biological systems and is holding back further development of time-resolved luminescence instruments. Herein we describe two approaches for preparing a visible-light-sensitized Eu(3+) complex in aqueous media for time-resolved fluorometric applications: a dissociation enhancement aqueous solution that can be excited by visible light for ethylenediaminetetraacetate (EDTA)-Eu(3+) detection and a visible-light-sensitized water-soluble Eu(3+) complex conjugated bovine serum albumin (BSA) for biolabeling and time-resolved luminescence bioimaging. In the first approach, a weakly acidic aqueous solution consisting of 4,4'-bis(1'',1'',1'',2'',2'',3'',3''-heptafluoro-4'',6''-hexanedion-6''-yl)-o-terphenyl (BHHT), 2-(N,N-diethylanilin-4-yl)-4,6-bis(3,5-dimethylpyrazol-1-yl)-1,3,5-triazine (DPBT), and Triton X-100 was prepared. This solution shows a strong luminescence enhancement effect for EDTA-Eu(3+) with a wide excitation wavelength range from UV to visible light (a maximum at 387 nm) and a long luminescence lifetime (520 micros), to provide a novel dissociation enhancement solution for time-resolved luminescence detection of EDTA-Eu(3+). In the second approach, a ternary Eu(3+) complex, 4,4'-bis(1'',1'',1'',2'',2'',3'',3''-heptafluoro-4'',6''-hexanedion-6''-yl)-chlorosulfo-o-terphenyl (BHHCT)-Eu(3+)-DPBT, was covalently bound to BSA to form a water-soluble BSA-BHHCT-Eu(3+)-DPBT conjugate. This biocompatible conjugate is of the visible-light excitable feature in aqueous media with a wide excitation wavelength range from UV to visible light (a maximum at 387 nm), a long luminescence lifetime (460 micros), and a higher

  15. Time-resolved contrast-enhanced MR angiography of spinal vascular malformations.

    Science.gov (United States)

    Amarouche, M; Hart, J L; Siddiqui, A; Hampton, T; Walsh, D C

    2015-02-01

    The diagnosis of spinal vascular malformations may be challenging on conventional MR imaging because neither the location of the signal abnormality in the spinal cord nor the level of the abnormal flow voids correlates with the level of the fistula. We conducted a retrospective evaluation of the utility of using a time-resolved imaging of contrast kinetics sequence in the diagnosis, characterization, and localization of spinal vascular malformations, comparing it with the criterion standard of spinal DSA. Fifty-five consecutive patients with a suspected diagnosis of spinal vascular malformation underwent time-resolved imaging of contrast kinetics followed by spinal DSA. All scans were performed on a 1.5T scanner by using a standard 8-channel spine coil and were reported by a neuroradiologist before the DSA was performed. Forty-seven lesions were confirmed on time-resolved imaging of contrast kinetics and classified as spinal dural arteriovenous fistulas (n = 33, with 1 patient having a type Ib fistula), perimedullary spinal cord arteriovenous fistulas (n = 10), and intramedullary arteriovenous malformations (n = 3). One patient had an extradural spinal vascular malformation. Time-resolved imaging of contrast kinetics identified the location of the arterial feeder to within 1 vertebral level in 27/33 patients (81.8%) with spinal dural arteriovenous fistulas and correctly predicted the side in 22/33 (66.6%) patients. Perimedullary spinal cord arteriovenous fistulas were erroneously considered to represent spinal dural arteriovenous fistulas before spinal DSA. The anatomy of the arterial supply to intramedullary arteriovenous malformations was also poorly characterized on time-resolved contrast-enhanced MR angiography. It has been our experience that time-resolved imaging of contrast kinetics is a useful confirmatory tool when a spinal vascular malformation is suspected on the basis of clinical and conventional MR imaging findings. As experience with the technique

  16. Time-resolved analytical methods for liquid/solid interfaces. Progress report, November 1, 1993--October 31, 1994

    Energy Technology Data Exchange (ETDEWEB)

    Harris, J.M.

    1994-10-31

    A number of chemical phenomena that occur at the boundaries between insulating solids and liquids (adsorption, partition, monolayer self-assembly, catalysis, and chemical reactions) are important to energy-related analytical chemistry. These phenomena are central to the development and understanding of chromatographic methods, solid-phase extraction techniques, immobilized analytical reagents, and optical sensors. The goal of this program, therefore, is to develop surface-sensitive spectroscopies by which chemical kinetics at liquid/solid interfaces can be observed on time-scales from nanoseconds to seconds. In the second year of this program, the authors have used temperature-jump relaxation measurements to monitor adsorption/desorption kinetics at liquid/solid interfaces using Joule heating to compare the adsorption of ions from solution onto C1- and C4-derivatized silica surfaces. They completed a study of rate of migration of covalently-attached ligands on silica surfaces; from the temperature-dependence of the migration, the large energy barrier to migration was estimated. Surface heterogeneity of adsorption sites on silica was characterized by time-resolve fluorescence, and the chemical origins investigated by Si{sup 29} NMR spectroscopy. Surface-enhance Raman and fluorescence spectroscopies were modified to study adsorption and binding to silica surfaces. Molecular dynamics simulations were started to help better understand kinetic barriers to adsorption; ESR probe measurements were launched to measure and compare the chain mobility of silica-attached alkyl ligands.

  17. Improvement in fingerprint detection using Tb(III)-dipicolinic acid complex doped nanobeads and time resolved imaging.

    Science.gov (United States)

    Hauser, Frank M; Knupp, Gerd; Officer, Simon

    2015-08-01

    This paper deals with the synthesis and application of lanthanide complex doped nanobeads used as a luminescent fingerprint powder. Due to their special optical properties, namely a long emission lifetime, sharp emission profiles and large Stokes shifts, luminescent lanthanide complexes are useful for discriminating against signals from background emissions. This is a big advantage because latent fingerprints placed on multicoloured fluorescent surfaces are difficult to develop with conventional powders. The complex of 2,6-dipicolinic acid (DPA) and terbium ([Tb(DPA)3](3-)) is used for this purpose. Using the Stöber process, this complex is incorporated into a silica matrix forming nanosized beads (230-630nm). It is shown that the [Tb(DPA)3](3-) is successfully incorporated into the beads and that these beads exhibit the wanted optical properties of the complex. A phenyl functionalisation is applied to increase the lipophilicity of the beads and finally the beads are used to develop latent fingerprints. A device for time resolved imaging was built to improve the contrast between developed fingerprint and different background signals, whilst still detecting the long lasting luminescence of the complex. The developed fingerprint powder is therefore promising to develop fingerprints on multicoloured fluorescent surfaces.

  18. Picosecond laser filamentation in air

    Science.gov (United States)

    2016-09-02

    LeibnizUniversityHannover,Welfengarten 1, D-30167Hannover, Germany 3 CEA-DAM,DIF, F-91297Arpajon, France 4 Univ.Bordeaux—CNRS—CEA,Centre Lasers ...optics.arizona.edu Keywords: laser filamentation, picosecond laser pulses, nonlinear propagation, optical ionization Abstract The propagation of intense

  19. Real-time tracking of CO migration and binding in the α and β subunits of human hemoglobin via 150-ps time-resolved Laue crystallography

    Energy Technology Data Exchange (ETDEWEB)

    Schotte, Friedrich; Cho, Hyun Sun [Laboratory of Chemical Physics, National Institute of Diabetes and Digestive and Kidney Diseases, National Institutes of Health, Bethesda, MD 20892-0520 (United States); Soman, Jayashree [Department of Biochemistry and Cell Biology, and W.M. Keck Center for Computational Biology, Rice University, Houston, TX 77251-1892 (United States); Wulff, Michael [European Synchrotron Radiation Facility, BP 220, 38043 Grenoble Cedex (France); Olson, John S. [Department of Biochemistry and Cell Biology, and W.M. Keck Center for Computational Biology, Rice University, Houston, TX 77251-1892 (United States); Anfinrud, Philip A., E-mail: anfinrud@nih.gov [Laboratory of Chemical Physics, National Institute of Diabetes and Digestive and Kidney Diseases, National Institutes of Health, Bethesda, MD 20892-0520 (United States)

    2013-08-30

    Highlights: ► 150-ps Time-resolved Laue crystallography has unveiled ligand dynamics in hemoglobin. ► Significant kinetic differences are observed in the α and β subunits of hemoglobin. ► The B-site lifetime is ∼1.6 ns in β, and ∼18 ns in α. ► The B-site location in β is ∼0.25 Å closer to the binding site than in α. ► The correlation between CO position and rebinding rate suggests distal control. - Abstract: We have developed the method of picosecond Laue crystallography and used this capability to probe ligand dynamics in tetrameric R-state hemoglobin (Hb). Time-resolved, 2 Å-resolution electron density maps of photolyzed HbCO reveal the time-dependent population of CO in the binding (A) and primary docking (B) sites of both α and β subunits from 100 ps to 10 μs. The proximity of the B site in the β subunit is about 0.25 Å closer to its A binding site, and its k{sub BA} rebinding rate (∼300 μs{sup −1}) is six times faster, suggesting distal control of the rebinding dynamics. Geminate rebinding in the β subunit exhibits both prompt and delayed geminate phases. We developed a microscopic model to quantitatively explain the observed kinetics, with three states for the α subunit and four states for the β subunit. This model provides a consistent framework for interpreting rebinding kinetics reported in prior studies of both HbCO and HbO{sub 2}.

  20. Low-pressure effective fluorescence lifetimes and photo-physical rate constants of one- and two-ring aromatics

    Science.gov (United States)

    Benzler, Thorsten; Faust, Stephan; Dreier, Thomas; Schulz, Christof

    2015-12-01

    One- and two-ring aromatics such as toluene and naphthalene are frequently used molecular tracer species in laser-induced fluorescence (LIF) imaging diagnostics. Quantifying LIF signal intensities requires knowledge of the photo-physical processes that determine the fluorescence quantum yield. Collision-induced and intramolecular energy transfer processes in the excited electronic state closely interact under practical conditions. They can be separated through experiments at variable low pressures. Effective fluorescence lifetimes of gaseous toluene, 1,2,4-trimethylbenzene, anisole, naphthalene, and 1-methylnaphthalene diluted in CO2 were measured after picosecond laser excitation at 266 nm and time-resolved detection of fluorescence intensities. Measurements in an optically accessible externally heated cell between 296 and 475 K and 0.010-1 bar showed that effective fluorescence lifetimes generally decrease with temperature, while the influence of the bath-gas pressure depends on the respective target species and temperature. The results provide non-radiative and fluorescence rate constants and experimentally validate the effect of photo-induced cooling.

  1. Time-resolved luminescence and singlet oxygen formation after illumination of the hypericin-low-density lipoprotein complex.

    Science.gov (United States)

    Gbur, Peter; Dedic, Roman; Chorvat, Dusan; Miskovsky, Pavol; Hala, Jan; Jancura, Daniel

    2009-01-01

    Time-resolved fluorescence and phosphorescence study of hypericin (Hyp) in complex with low-density lipoproteins (LDL) as well as the evolution of singlet oxygen formation and annihilation after illumination of Hyp/LDL complexes at room temperature are presented in this work. The observed shortening of the fluorescence lifetime of Hyp at high Hyp/LDL molar ratios (>25:1) proves the self-quenching of the excited singlet state of monomeric Hyp at these concentration ratios. The very short lifetime ( approximately 0.5 ns) of Hyp fluorescence at very high Hyp/LDL ratios (>150:1) suggests that at high local Hyp concentration inside LDL molecules fast and ultrafast nonradiative decay processes from excited singlet state of Hyp become more important. Contrary to the lifetime of the singlet excited state, the lifetime (its shorter component) of Hyp phosphorescence is not dependent on Hyp/LDL ratio in the studied concentration range. The amount of singlet oxygen produced as well as the integral intensity of Hyp phosphorescence after illumination of Hyp/LDL complexes resemble the dependence of the concentration of molecules of Hyp in monomeric state on Hyp/LDL until a concentration ratio of 60:1. This fact confirms that only monomeric Hyp is able to produce the excited triplet state of Hyp, which in aerobic conditions leads to singlet oxygen production. The value of singlet oxygen lifetime ( approximately 8 micros) after its formation from the excited triplet state of Hyp in LDL proves that molecules of singlet oxygen remain for a certain period of time inside LDL particles and are not immediately released to the aqueous surrounding. That Hyp exists in the complex with LDL in the monodeprotonated state is also demonstrated.

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

    Science.gov (United States)

    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

    2017-08-30

    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

  3. 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

  4. Laser Detection Of Latent Fingerprints: Tris(2,2'-Bipyridyl)Ruthenium(II) Chloride Hexahydrate As A Staining Dye For Time-Resolved Imaging

    Science.gov (United States)

    Menzel, E. R.

    1988-04-01

    The compound tris(2,2'-bipyridyl)ruthenium(II) chloride hexahydrate is suitable for laser detection of latent fingerprints on difficult surfaces such as wood and masking tape, as well as surfaces such as polyethylene, metal, etc. The fingerprint treatment can Involve either dusting with powder blended with this compound or by solution staining. The compound displays a strong d-n phosphorescence with a lifetime of about 10-6 and is thus very well suited for time-resolved imaging to suppress background fluorescence.

  5. Computational time-resolved and resonant x-ray scattering of strongly correlated materials

    Energy Technology Data Exchange (ETDEWEB)

    Bansil, Arun [Northeastern Univ., Boston, MA (United States)

    2016-11-09

    predominantly decays via Auger processes, thereby providing an internal time-scale, which limits intermediate-state processes to timescales of a few femtoseconds. Accordingly, a number of activities directed at modeling K-, L- and M-edge RIXS in correlated materials were also pursused by our CRT. Our research effort supported by this CMCSN grant substantially advanced the understanding of x-ray scattering processes in the time-domain as well as in the more conventional scattering channels, including time-resolved photoemission, and how such processes can be modeled realistically in complex correlated materials more generally. The modeling of relaxation processes involved in time-domain spectroscopies is important also for understanding photoinduced effects such as energy conversion in photosynthesis and solar cell applications, and thus impacts the basic science for energy needs.

  6. Sub-nanosecond time-resolved near-field scanning magneto-optical microscope.

    Science.gov (United States)

    Rudge, J; Xu, H; Kolthammer, J; Hong, Y K; Choi, B C

    2015-02-01

    We report on the development of a new magnetic microscope, time-resolved near-field scanning magneto-optical microscope, which combines a near-field scanning optical microscope and magneto-optical contrast. By taking advantage of the high temporal resolution of time-resolved Kerr microscope and the sub-wavelength spatial resolution of a near-field microscope, we achieved a temporal resolution of ∼50 ps and a spatial resolution of microscope, the magnetic field pulse induced gyrotropic vortex dynamics occurring in 1 μm diameter, 20 nm thick CoFeB circular disks has been investigated. The microscope provides sub-wavelength resolution magnetic images of the gyrotropic motion of the vortex core at a resonance frequency of ∼240 MHz.

  7. 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.)

  8. Noninvasive assessment of breast cancer risk using time-resolved diffuse optical spectroscopy

    Science.gov (United States)

    Taroni, Paola; Pifferi, Antonio; Quarto, Giovanna; Spinelli, Lorenzo; Torricelli, Alessandro; Abbate, Francesca; Villa, Anna; Balestreri, Nicola; Menna, Simona; Cassano, Enrico; Cubeddu, Rinaldo

    2010-11-01

    Breast density is a recognized strong and independent risk factor for breast cancer. We propose the use of time-resolved transmittance spectroscopy to estimate breast tissue density and potentially provide even more direct information on breast cancer risk. Time-resolved optical mammography at seven wavelengths (635 to 1060 nm) is performed on 49 subjects. Average information on breast tissue of each subject is obtained on oxy- and deoxyhemoglobin, water, lipids, and collagen content, as well as scattering amplitude and power. All parameters, except for blood volume and oxygenation, correlate with mammographic breast density, even if not to the same extent. A synthetic optical index proves to be quite effective in separating different breast density categories. Finally, the estimate of collagen content as a more direct means for the assessment of breast cancer risk is discussed.

  9. Time Resolved Experiments at the Frankfurt 14 GHz ECR Ion Source

    CERN Document Server

    Runkel, S; Hohn, O; Mironov, V; Shirkov, G D; Schempp, A; Schmidt-Böcking, H

    1999-01-01

    To investigate the basic production processes of highly charged ions and combined phenomena of an ECRIS plasma (e. g. influence of secondary electrons and plasma instabilities) time resolved experiments have been carried out at the Frankfurt 14 GHz ECRIS [1] (see also the contributions to this workshop by O. Hohn et al. and V. Mironov et al.). We report time resolved measurements of the extracted ion currents by pulsing the biased disk voltage [2]. The measurements have shown that the extracted ion currents respond too fast to explain the "biased disk effect" (i. e. the intensity increase of highly charged ions) by enhanced ion breeding. Furthermore the influence of the pulsed biased disk on plasma instabilities has been investigated. It has also been shown that this method can be used to extract pulsed ion beams from an ECRIS.

  10. 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......,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...... the non-adiabatic photodissociation of carbon disulphide demonstrate how the purely electronic rearrangements of the valence electrons can be projected from inherently coupled electronic-vibrational dynamics. Combined with ongoing efforts in molecular frame alignment(20) and orientation(21,22), TRMFPADs...

  11. Time-resolved X-ray scattering program at the Advanced Photon Source

    Energy Technology Data Exchange (ETDEWEB)

    Rodricks, B.

    1994-08-01

    The Time-Resolved Scattering Program`s goal is the development of instruments and techniques for time-resolved studies. This entails the development of wide bandpass and focusing optics, high-speed detectors, mechanical choppers, and components for the measurement and creation of changes in samples. Techniques being developed are pump-probe experiments, single-bunch scattering experiments, high-speed white and pink beam Laue scattering, and nanosecond to microsecond synchronization of instruments. This program will be carried out primarily from a white-beam, bend-magnet source, experimental station, 1-BM-B, that immediately follows the first optics enclosure (1-BM-A). This paper will describe the experimental station and instruments under development to carry out the program.

  12. Developments in time-resolved high pressure x-ray diffraction using rapid compression and decompression

    Energy Technology Data Exchange (ETDEWEB)

    Smith, Jesse S.; Sinogeikin, Stanislav V.; Lin, Chuanlong; Rod, Eric; Bai, Ligang; Shen, Guoyin [High Pressure Collaborative Access Team, Geophysical Laboratory, Carnegie Institution of Washington, Argonne, Illinois 60439 (United States)

    2015-07-15

    Complementary advances in high pressure research apparatus and techniques make it possible to carry out time-resolved high pressure research using what would customarily be considered static high pressure apparatus. This work specifically explores time-resolved high pressure x-ray diffraction with rapid compression and/or decompression of a sample in a diamond anvil cell. Key aspects of the synchrotron beamline and ancillary equipment are presented, including source considerations, rapid (de)compression apparatus, high frequency imaging detectors, and software suitable for processing large volumes of data. A number of examples are presented, including fast equation of state measurements, compression rate dependent synthesis of metastable states in silicon and germanium, and ultrahigh compression rates using a piezoelectric driven diamond anvil cell.

  13. Time-resolved LII signals from aggregates of soot particles levitated in room temperature air

    CERN Document Server

    Mitrani, James M

    2015-01-01

    We observed and modeled time-resolved laser-induced incandescence (LII) signals from soot aggregates. Time-resolved LII signals were observed from research-grade soot particles, levitated in room temperature air. We were able to measure sizes and structural properties of our soot particles ex situ, and use those measurements as input parameters when modeling the observed LII signals. We showed that at low laser fluences, aggregation significantly influences LII signals by reducing conductive cooling to the ambient air. At moderate laser fluences, laser-induced disintegration of aggregates occurs, so the effects of aggregation on LII signals are negligible. These results can be applied to extend LII for monitoring formation of soot and nanoparticle aggregates.

  14. Estimating wide-angle, spatially varying reflectance using time-resolved inversion of backscattered light.

    Science.gov (United States)

    Naik, Nikhil; Barsi, Christopher; Velten, Andreas; Raskar, Ramesh

    2014-05-01

    Imaging through complex media is a well-known challenge, as scattering distorts a signal and invalidates imaging equations. For coherent imaging, the input field can be reconstructed using phase conjugation or knowledge of the complex transmission matrix. However, for incoherent light, wave interference methods are limited to small viewing angles. On the other hand, time-resolved methods do not rely on signal or object phase correlations, making them suitable for reconstructing wide-angle, larger-scale objects. Previously, a time-resolved technique was demonstrated for uniformly reflecting objects. Here, we generalize the technique to reconstruct the spatially varying reflectance of shapes hidden by angle-dependent diffuse layers. The technique is a noninvasive method of imaging three-dimensional objects without relying on coherence. For a given diffuser, ultrafast measurements are used in a convex optimization program to reconstruct a wide-angle, three-dimensional reflectance function. The method has potential use for biological imaging and material characterization.

  15. Caveats in the interpretation of time-resolved photoionization measurements: A photoelectron imaging study of pyrrole

    Science.gov (United States)

    Crane, Stuart W.; Zawadzki, Magdalena M.; Thompson, James O. F.; Kotsina, Nikoleta; Ghafur, Omair; Townsend, Dave

    2016-12-01

    We report time-resolved photoelectron imaging studies of gas-phase pyrrole over the 267-240 nm excitation region, recorded in conjunction with a 300 nm probe. Of specific interest is the lowest-lying (3 s /π σ* ) state, which exhibits very weak oscillator strength but is thought to be excited directly at wavelengths ≤254 nm. We conclude, however, that the only significant contribution to our photoelectron data at all wavelengths investigated is from non-resonant ionization. Our findings do not rule out (3 s /π σ* ) state excitation (as appears to be confirmed by supporting time-resolved ion-yield measurements) but do potentially highlight important caveats regarding the use and interpretation of photoreactant ionization measurements to interrogate dynamical processes in systems exhibiting significant topological differences between the potential energy surfaces of the neutral and cation states.

  16. A direct electron detector for time-resolved MeV electron microscopy

    Energy Technology Data Exchange (ETDEWEB)

    Vecchione, T.; Denes, P.; Jobe, R. K.; Johnson, I. J.; Joseph, J. M.; Li, R. K.; Perazzo, A.; Shen, X.; Wang, X. J.; Weathersby, S. P.; Yang, J.; Zhang, D.

    2017-03-01

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

  17. Recent applications of multiwire proportional chambers for time resolved studies on muscle

    Science.gov (United States)

    Faruqi, A. R.; Huxley, H. E.; Kress, M.

    1986-12-01

    The use of multiwire proportional chambers has played an important role in recording time resolved data from vertebrate muscle under various physiological conditions from which we have selected two examples from recent work. The first example describes the measurement of the equatorial pattern along with measurements of the muscle sarcomere length showing that the delay in tension development relative to changes in the X-ray intensity are not due to "internal" shortening in the muscle. The second example describes time-resolved measurements on the thin filament activation process, studied with both a linear and an area detector. The results show clearly that changes in thin filament structure precede cross-bridge formation producing further strong evidence for the "steric blocking model" for muscle contraction.

  18. Mix and Inject: Reaction Initiation by Diffusion for Time-Resolved Macromolecular Crystallography

    Directory of Open Access Journals (Sweden)

    Marius Schmidt

    2013-01-01

    Full Text Available Time-resolved macromolecular crystallography unifies structure determination with chemical kinetics, since the structures of transient states and chemical and kinetic mechanisms can be determined simultaneously from the same data. To start a reaction in an enzyme, typically, an initially inactive substrate present in the crystal is activated. This has particular disadvantages that are circumvented when active substrate is directly provided by diffusion. However, then it is prohibitive to use macroscopic crystals because diffusion times become too long. With small micro- and nanocrystals diffusion times are adequately short for most enzymes and the reaction can be swiftly initiated. We demonstrate here that a time-resolved crystallographic experiment becomes feasible by mixing substrate with enzyme nanocrystals which are subsequently injected into the X-ray beam of a pulsed X-ray source.

  19. Following [FeFe] Hydrogenase Active Site Intermediates by Time-Resolved Mid-IR Spectroscopy.

    Science.gov (United States)

    Mirmohades, Mohammad; Adamska-Venkatesh, Agnieszka; Sommer, Constanze; Reijerse, Edward; Lomoth, Reiner; Lubitz, Wolfgang; Hammarström, Leif

    2016-08-18

    Time-resolved nanosecond mid-infrared spectroscopy is for the first time employed to study the [FeFe] hydrogenase from Chlamydomonas reinhardtii and to investigate relevant intermediates of the enzyme active site. An actinic 355 nm, 10 ns laser flash triggered photodissociation of a carbonyl group from the CO-inhibited state Hox-CO to form the state Hox, which is an intermediate of the catalytic proton reduction cycle. Time-resolved infrared spectroscopy allowed us to directly follow the subsequent rebinding of the carbonyl, re-forming Hox-CO, and determine the reaction half-life to be t1/2 ≈ 13 ± 5 ms at room temperature. This gives direct information on the dynamics of CO inhibition of the enzyme.

  20. Simultaneous reference and differential waveform acquisition in time-resolved terahertz spectroscopy

    DEFF Research Database (Denmark)

    Iwaszczuk, Krzysztof; Cooke, David; Fujiwara, Masazumi;

    2009-01-01

    We present a new method for data acquisition in time-resolved terahertz spectroscopy experiments. Our approach is based on simultaneous collection of reference and differential THz scans. Both the optical THz generation beam and the pump beam are modulated at two different frequencies...... that are not harmonic with respect to each other. Our method allows not only twice as fast data acquisition but also minimization of noise connected to slowly varying laser power fluctuations and timing instabilities. Our use of the nonlinear crystal N-benzyl-2-methyl-4-nitroaniline (BNA) enables time-resolved THz...... spectroscopy to beyond 5 THz, thereby highlighting that the presented method is especially valuable at higher frequencies where phase errors in the data acquisition become increasingly important....

  1. Time-resolved fuel injector flow characterisation based on 3D laser Doppler vibrometry

    CERN Document Server

    Crua, Cyril

    2015-01-01

    In order to enable investigations of the fuel flow inside unmodified injectors, we have developed a new experimental approach to measure time-resolved vibration spectra of diesel nozzles using a three dimensional laser vibrometer. The technique we propose is based on the triangulation of the vibrometer and fuel pressure transducer signals, and enables the quantitative characterisation of quasi-cyclic internal flows without requiring modifications to the injector, the working fluid, or limiting the fuel injection pressure. The vibrometer, which uses the Doppler effect to measure the velocity of a vibrating object, was used to scan injector nozzle tips during the injection event. The data were processed using a discrete Fourier transform to provide time-resolved spectra for valve-closed-orifice, minisac and microsac nozzle geometries, and injection pressures ranging from 60 to 160MPa, hence offering unprecedented insight into cyclic cavitation and internal mechanical dynamic processes. A peak was consistently f...

  2. Time-resolved optical transmission of pulsed laser-irradiated silicon

    Energy Technology Data Exchange (ETDEWEB)

    Lee, M.C.; Lo, H.W.; Aydinli, A.; Compaan, A.

    1980-10-20

    The time-resolved optical transmission of silicon has been observed at lambda = 1.15 microns during irradiation by an 8 nsec pulsed laser at 485 nm with several energy densities in the range of .25 to 1.2 J/sq cm. The transmission exhibits a sudden brief drop consistent with the rise and fall of the reflectivity enhancement. However, the transmission does not exhibit the strong absorption expected of molten silicon with a skin depth of approx. 100A.

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

    Science.gov (United States)

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

    2014-12-01

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

  4. Femtosecond Time-Resolved Resonance-Enhanced CARS of Gaseous Iodine at Room Temperature

    Institute of Scientific and Technical Information of China (English)

    HE Ping; FAN Rong-Wei; XIA Yuan-Qin; YU Xin; YAO Yong; CHEN De-Ying

    2011-01-01

    @@ Time-resolved resonance-enhanced coherent anti-Stokes Raman scattering(CARS)is applied to investigate molecular dynamics in gaseous iodine.40fs laser pulses are applied to create and monitor the high vibrational states of iodine at room temperature(corresponding to a vapor pressure as low as about 35 Pa)by femtosecond timeresolved CARS.Depending on the time delay between the probe pulse and the pump/Stokes pulse pairs, the high vibrational states both on the electronically ground states and the excited states can be detected as oscillations in the CARS transient signal.It is proved that the femtosecond time-resolved CARS technique is a promising candidate for investigating the molecular dynamics of a low concentration system and can be applied to environmental and atmospheric monitoring measurements.%Time-resolved resonance-enhanced coherent anti-Stokes Raman scattering (CARS) is applied to investigate molecular dynamics in gaseous iodine. 40 fs laser pulses are applied to create and monitor the high vibrational states of iodine at room temperature (corresponding to a vapor pressure as low as about 35 Pa) by femtosecond timeresolved CARS. Depending on the time delay between the probe pulse and the pump/Stokes pulse pairs, the high vibrational states both on the electronically ground states and the excited states can be detected as oscillations in the CARS transient signal. It is proved that the femtosecond time-resolved CARS technique is a promising candidate for investigating the molecular dynamics of a low concentration system and can be applied to environmental and atmospheric monitoring measurements.

  5. Time-resolved torsional relaxation of spider draglines by an optical technique.

    OpenAIRE

    Emile, Olivier; Le Floch, Albert; Vollrath, F.

    2007-01-01

    International audience; The sensitivity of the torsional pendulum demonstrates the self-shape-memory effect in different types of spider draglines. Here we report the time-resolved noncovalent bonds recovery in the protein structure. The torsional dynamics of such multilevel structure governed by reversible interactions are described in the frame of a nested model. Measurement of three different relaxation times confirms the existence of three energy storage levels in such two protein spidroi...

  6. Spectroscopic analysis of time-resolved emission from detonating thin film explosive samples

    Science.gov (United States)

    Kay, Jeffrey J.; Wixom, Ryan R.; Jilek, Brook A.; Knepper, Robert; Tappan, Alexander S.; Damm, David L.

    2017-01-01

    We report a series of time-resolved spectroscopic measurements that aim to characterize the reactions that occur during shock initiation of high explosives. The experiments employ time- and wavelength-resolved emission spectroscopy to analyze light emitted from detonating thin explosive films. This paper presents analysis of optical emission spectra from hexanitrostilbene (HNS) and pentaerythritol tetranitrate (PETN) thin film samples. Both vibrationally resolved and broadband emission features are observed in the spectra and area as electronic transitions of intermediate species.

  7. Time-resolved measurement of single pulse femtosecond laser-induced periodic surface structure formation

    OpenAIRE

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

    2015-01-01

    Time-resolved diffraction microscopy technique has been used to observe the formation of laser-induced periodic surface structures (LIPSS) from the interaction of a single femtosecond laser pulse (pump) with a nano-scale groove mechanically formed on a single-crystal Cu substrate. The interaction dynamics (0-1200 ps) was captured by diffracting a time-delayed, frequency-doubled pulse from nascent LIPSS formation induced by the pump with an infinity-conjugate microscopy setup. The LIPSS ripple...

  8. Analytical theory for the time-resolved dynamical Franz-Keldysh effect under circularly polarized light

    CERN Document Server

    Otobe, T

    2016-01-01

    We report here the analytical formula for the time-resolved dynamical Franz-Keldysh effect (Tr-DFKE) under circularly polarized light. We assume the Houston function as the time-dependent wave function of the parabolic two-band system. Our formula shows that the sub-cycle change of the optical properties disappears, which is a significant feature of the Tr-DFKE under linear polarized light and is different from the static Franz-Keldysh effect.

  9. Time-resolved photoresponse of nanometer-thick Nb/NiCu bilayers

    Science.gov (United States)

    Parlato, L.; Pepe, G. P.; Latempa, R.; De Lisio, C.; Altucci, C.; D'Acunto, P.; Peluso, G.; Barone, A.; Taneda, T.; Sobolewski, R.

    2005-07-01

    We present femtosecond optical time-resolved pump-probe investigations of superconducting hybrids structures consisting of Nb/NiCu bilayers with various thickness. Measurements performed on pure Nb and NiCu films are also given. The photoresponse experiments provide the quasiparticle relaxation times in bilayers of different thickness ratios. The study of the photoresponse as a function of the temperature reveals the spatial evolution of the superconductor order parameter across the bilayers.

  10. Comparative aerodynamic performance of flapping flight in two bat species using time-resolved wake visualization

    OpenAIRE

    Muijres, Florian T.; Johansson, L. Christoffer; Winter, York; Hedenström, Anders

    2011-01-01

    Bats are unique among extant actively flying animals in having very flexible wings, controlled by multi-jointed fingers. This gives the potential for fine-tuned active control to optimize aerodynamic performance throughout the wingbeat and thus a more efficient flight. But how bat wing performance scales with size, morphology and ecology is not yet known. Here, we present time-resolved fluid wake data of two species of bats flying freely across a range of flight speeds using stereoscopic digi...

  11. Singular value decomposition as a tool for background corrections in time-resolved XFEL scattering data

    DEFF Research Database (Denmark)

    Haldrup, Kristoffer

    2014-01-01

    The development of new X-ray light sources, XFELs, with unprecedented time and brilliance characteristics has led to the availability of very large datasets with high time resolution and superior signal strength. The chaotic nature of the emission processes in such sources as well as entirely novel...... on singular-value decomposition of no-signal subsets of acquired datasets in combination with model inputs and appears generally applicable to time-resolved X-ray diffuse scattering experiments....

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

    Science.gov (United States)

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

    2016-05-01

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

  13. Particle tracking during Ostwald ripening using time-resolved laboratory X-ray microtomography

    Energy Technology Data Exchange (ETDEWEB)

    Werz, T., E-mail: thomas.werz@uni-ulm.de [Ulm University, Institute of Micro and Nanomaterials, Albert-Einstein-Allee 47, 89081 (Germany); Baumann, M. [Ulm University, Institute of Micro and Nanomaterials, Albert-Einstein-Allee 47, 89081 (Germany); Wolfram, U. [Ulm University, Institute of Orthopaedic Research and Biomechanics, Helmholtzstrasse 14, 89081 (Germany); Krill, C.E. [Ulm University, Institute of Micro and Nanomaterials, Albert-Einstein-Allee 47, 89081 (Germany)

    2014-04-01

    Laboratory X-ray microtomography is investigated as a method for obtaining time-resolved images of microstructural coarsening of the semisolid state of Al–5 wt.% Cu samples during Ostwald ripening. Owing to the 3D imaging capability of tomography, this technique uniquely provides access to the growth rates of individual particles, thereby not only allowing a statistical characterization of coarsening—as has long been possible by conventional metallography—but also enabling quantification of the influence of local environment on particle boundary migration. The latter information is crucial to understanding growth kinetics during Ostwald ripening at high volume fractions of the coarsening phase. Automated image processing and segmentation routines were developed to close gaps in the network of particle boundaries and to track individual particles from one annealing step to the next. The particle tracking success rate places an upper bound of only a few percent on the likelihood of segmentation errors for any given particle. The accuracy of particle size trajectories extracted from the time-resolved tomographic reconstructions is correspondingly high. Statistically averaged coarsening data and individual particle growth rates are in excellent agreement with the results of prior experimental studies and with computer simulations of Ostwald ripening. - Highlights: • Ostwald ripening in Al–5 wt.% Cu measured by laboratory X-ray microtomography • Time-resolved measurement of individual particle growth • Automated segmentation routines developed to close gaps in particle boundary network • Particle growth/shrinkage rates deviate from LSW model prediction.

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

    Science.gov (United States)

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

    2016-08-22

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

  15. Applications of time-resolved terahertz spectroscopy in ultrafast carrier dynamics

    Institute of Scientific and Technical Information of China (English)

    Qingli Zhou; Xicheng Zhang

    2011-01-01

    1.Introduction Terahertz time-domain spectroscopy (THz-TDS)[1-3]is a powerful and coherent free-space technique in which nearly single-cycle electromagnetic pulse is generated and detected using femtosecond optical pulses.THz-TDS has been utilized as one of the important methods for material characterization in the past two decades.Because transmission or reflection of THz waves is sensitive to carrier density and mobility,an ultrafast THz-TDS system is required to provide time-resolved capability of material characterization in the THz region[4-6].In the past decade,one of the widely used time-resolved THz spectroscopy methods is optical-pump/THz probe (O/T)spectroscopy[3].%Three time-resolved terahertz (THz) spectroscopy methods (optical-pump/THz-probe spectroscopy, THz-pump/THz-probe spectroscopy, and THz-pump/optical-probe spectroscopy) are reviewed. These are used to characterize ultrafast dynamics in photo- or THz-excited semiconductors, superconductors, nanomateri-als, and other materials. In particular, the optical-pump/THz-probe spectroscopy is utilized to investigate carrier dynamics and the related intervalley scattering phenomena in semiconductors. The recent development of intense pulsed THz sources is expected to affect the research in nonlinear THz responses of various materials.

  16. Vibrational spectroscopy of the electronically excited state. 4. Nanosecond and picosecond time-resolved resonance Raman spectroscopy of carotenoid excited states

    Energy Technology Data Exchange (ETDEWEB)

    Dallinger, R.F.; Farquharson, S.; Woodruff, W.H.; Rodgers, M.A.J.

    1981-12-16

    Resonance Raman and electronic absorption spectra are reported for the S/sub 0/ and T/sub 1/ states of the carotenoids ..beta..-carotene, zeaxanthin, echinenone, canthaxanthin, dihydroxylycopene, astaxanthin, decapreno(C/sub 50/)-..beta..-carotene, ..beta..-apo-8'-carotenal, and ethyl ..beta..-apo-8'-carotenoate. The results reveal qualitatively similar ground-state spectra and similar frequency shifts in all observed resonance Raman modes between S/sub 0/ and T/sub 1/, regardless of carotenoid structure. Examinations of the relationship of the putative C--C and C==C frequencies in S/sub 0/ and T/sub 1/ reveals anomalous shifts to lower frequency in the ''single-bond'' mode upon electronic excitation. These shifts may be due to molecular distortions in the excited state which force changes in molecular motions comprising the observed modes. However, another possibility requiring no distortion is that the interaction (off-diagonal) force constants connecting the C--C and C==C modes change sign upon electronic excitation. This latter phenomenon may provide a unitary explanation for the ''anomalous'' frequency shifts in the C--C and C==C modes, both in the T/sub 1/ states of carotenoids and in the S/sub 1/ states of simpler polyenes, without postulating large, unpredicted structural changes upon excitation or general errors in existing vibrational or theoretical analyses. Resonance Raman and absorbance studies with 35-ps time resolution suggest that S/sub 1/ lifetime (of the /sup 1/B/sub u/ and/or the /sup 1/A/sub g/* states) of ..beta..-carotene in benzene is less than 1 ps.

  17. Prospective time-resolved LCA of fully electric supercap vehicles in Germany.

    Science.gov (United States)

    Zimmermann, Benedikt M; Dura, Hanna; Baumann, Manuel J; Weil, Marcel R

    2015-07-01

    The ongoing transition of the German electricity supply toward a higher share of renewable and sustainable energy sources, called Energiewende in German, has led to dynamic changes in the environmental impact of electricity over the last few years. Prominent scenario studies predict that comparable dynamics will continue in the coming decades, which will further improve the environmental performance of Germany's electricity supply. Life cycle assessment (LCA) is the methodology commonly used to evaluate environmental performance. Previous LCA studies on electric vehicles have shown that the electricity supply for the vehicles' operation is responsible for the major part of their environmental impact. The core question of this study is how the prospective dynamic development of the German electricity mix will affect the impact of electric vehicles operated in Germany and how LCA can be adapted to analyze this impact in a more robust manner. The previously suggested approach of time-resolved LCA, which is located between static and dynamic LCA, is used in this study and compared with several static approaches. Furthermore, the uncertainty issue associated with scenario studies is addressed in general and in relation to time-resolved LCA. Two scenario studies relevant to policy making have been selected, but a moderate number of modifications have been necessary to adapt the data to the requirements of a life cycle inventory. A potential, fully electric vehicle powered by a supercapacitor energy storage system is used as a generic example. The results show that substantial improvements in the environmental repercussions of the electricity supply and, consequentially, of electric vehicles will be achieved between 2020 and 2031 on the basis of the energy mixes predicted in both studies. This study concludes that although scenarios might not be able to predict the future, they should nonetheless be used as data sources in prospective LCA studies, because in many cases

  18. Comparison of TiO₂ and ZnO solar cells sensitized with an indoline dye: time-resolved laser spectroscopy studies of partial charge separation processes.

    Science.gov (United States)

    Sobuś, Jan; Burdziński, Gotard; Karolczak, Jerzy; Idígoras, Jesús; Anta, Juan A; Ziółek, Marcin

    2014-03-11

    Time-resolved laser spectroscopy techniques in the time range from femtoseconds to seconds were applied to investigate the charge separation processes in complete dye-sensitized solar cells (DSC) made with iodide/iodine liquid electrolyte and indoline dye D149 interacting with TiO2 or ZnO nanoparticles. The aim of the studies was to explain the differences in the photocurrents of the cells (3-4 times higher for TiO2 than for ZnO ones). Electrochemical impedance spectroscopy and nanosecond flash photolysis studies revealed that the better performance of TiO2 samples is not due to the charge collection and dye regeneration processes. Femtosecond transient absorption results indicated that after first 100 ps the number of photoinduced electrons in the semiconductor is 3 times higher for TiO2 than for ZnO solar cells. Picosecond emission studies showed that the lifetime of the D149 excited state is about 3 times longer for ZnO than for TiO2 samples. Therefore, the results indicate that lower performance of ZnO solar cells is likely due to slower electron injection. The studies show how to correlate the laser spectroscopy methodology with global parameters of the solar cells and should help in better understanding of the behavior of alternative materials for porous electrodes for DSC and related devices.

  19. G Protein-Coupled Receptor Signaling Analysis Using Homogenous Time-Resolved Förster Resonance Energy Transfer (HTRF® Technology

    Directory of Open Access Journals (Sweden)

    Lenea Nørskov-Lauritsen

    2014-02-01

    Full Text Available Studying multidimensional signaling of G protein-coupled receptors (GPCRs in search of new and better treatments requires flexible, reliable and sensitive assays in high throughput screening (HTS formats. Today, more than half of the detection techniques used in HTS are based on fluorescence, because of the high sensitivity and rich signal, but quenching, optical interferences and light scattering are serious drawbacks. In the 1990s the HTRF® (Cisbio Bioassays, Codolet, France technology based on Förster resonance energy transfer (FRET in a time-resolved homogeneous format was developed. This improved technology diminished the traditional drawbacks. The optimized protocol described here based on HTRF® technology was used to study the activation and signaling pathways of the calcium-sensing receptor, CaSR, a GPCR responsible for maintaining calcium homeostasis. Stimulation of the CaSR by agonists activated several pathways, which were detected by measuring accumulation of the second messengers D-myo-inositol 1-phosphate (IP1 and cyclic adenosine 3',5'-monophosphate (cAMP, and by measuring the phosphorylation of extracellular signal-regulated kinase 1 and 2 (ERK1/2. Here we show how an optimized HTRF® platform with numerous advantages compared to previous assays provides a substantial and robust mode of investigating GPCR signaling. It is furthermore discussed how these assays can be optimized and miniaturized to meet HTS requirements and for screening compound libraries.

  20. G protein-coupled receptor signaling analysis using homogenous time-resolved Förster resonance energy transfer (HTRF®) technology.

    Science.gov (United States)

    Nørskov-Lauritsen, Lenea; Thomsen, Alex Rojas Bie; Bräuner-Osborne, Hans

    2014-02-13

    Studying multidimensional signaling of G protein-coupled receptors (GPCRs) in search of new and better treatments requires flexible, reliable and sensitive assays in high throughput screening (HTS) formats. Today, more than half of the detection techniques used in HTS are based on fluorescence, because of the high sensitivity and rich signal, but quenching, optical interferences and light scattering are serious drawbacks. In the 1990s the HTRF® (Cisbio Bioassays, Codolet, France) technology based on Förster resonance energy transfer (FRET) in a time-resolved homogeneous format was developed. This improved technology diminished the traditional drawbacks. The optimized protocol described here based on HTRF® technology was used to study the activation and signaling pathways of the calcium-sensing receptor, CaSR, a GPCR responsible for maintaining calcium homeostasis. Stimulation of the CaSR by agonists activated several pathways, which were detected by measuring accumulation of the second messengers D-myo-inositol 1-phosphate (IP1) and cyclic adenosine 3',5'-monophosphate (cAMP), and by measuring the phosphorylation of extracellular signal-regulated kinase 1 and 2 (ERK1/2). Here we show how an optimized HTRF® platform with numerous advantages compared to previous assays provides a substantial and robust mode of investigating GPCR signaling. It is furthermore discussed how these assays can be optimized and miniaturized to meet HTS requirements and for screening compound libraries.