Reversible Energy Transfer and Fluorescence Decay in Solid Solutions

NASA Astrophysics Data System (ADS)

Shealy, David L.; Hoover, Richard B.; Gabardi, David R.

1988-07-01

The article deals with the influence of reversible excitation energy transfer on the fluorescence decay in systems with random distribution of molecules. On the basis of a hopping model, we have obtained an expression for the Laplace transform of the decay function and an expression for the average decay time. The case of dipole-dipole interaction is discussed in detail.

Ultrafast fluorescence quenching dynamics of Atto655 in the presence of N-acetyltyrosine and N-acetyltryptophan in aqueous solution: proton-coupled electron transfer versus electron transfer.

PubMed

Zhang, Ying; Yuan, Shuwei; Lu, Rong; Yu, Anchi

2013-06-20

We studied the ultrafast fluorescence quenching dynamics of Atto655 in the presence of N-acetyltyrosine (AcTyr) and N-acetyltryptophan (AcTrp) in aqueous solution with femtosecond transient absorption spectroscopy. We found that the charge-transfer rate between Atto655 and AcTyr is about 240 times smaller than that between Atto655 and AcTrp. The pH value and D2O dependences of the excited-state decay kinetics of Atto655 in the presence of AcTyr and AcTrp reveal that the quenching of Atto655 fluorescence by AcTyr in aqueous solution is via a proton-coupled electron-transfer (PCET) process and that the quenching of Atto655 fluorescence by AcTrp in aqueous solution is via an electron-transfer process. With the version of the semiclassical Marcus ET theory, we derived that the electronic coupling constant for the PCET reaction between Atto655 and AcTyr in aqueous solution is 8.3 cm(-1), indicating that the PCET reaction between Atto655 and AcTyr in aqueous solution is nonadiabatic.

Site-Dependent Fluorescence Decay of Malachite Green Doped in Onion Cell

NASA Astrophysics Data System (ADS)

Nakatsuka, Hiroki; Sekine, Masaya; Suzuki, Yuji; Hattori, Toshiaki

1999-03-01

Time-resolved fluorescence measurements of malachite green dye moleculesdoped in onion cells were carried out.The fluorescence decay time was dependent on the individual cell and on theposition of the dye in a cell, which reflect the microscopic dynamics of each boundsite.Upon cooling, the decay time increased and this increase was accelerated ataround the freezing point of the onion cell.

PREFACE: Ultrafast biophotonics Ultrafast biophotonics

NASA Astrophysics Data System (ADS)

Gu, Min; Reid, Derryck; Ben-Yakar, Adela

2010-08-01

The use of light to explore biology can be traced to the first observations of tissue made with early microscopes in the mid-seventeenth century, and has today evolved into the discipline which we now know as biophotonics. This field encompasses a diverse range of activities, each of which shares the common theme of exploiting the interaction of light with biological material. With the rapid advancement of ultrafast optical technologies over the last few decades, ultrafast lasers have increasingly found applications in biophotonics, to the extent that the distinctive new field of ultrafast biophotonics has now emerged, where robust turnkey ultrafast laser systems are facilitating cutting-edge studies in the life sciences to take place in everyday laboratories. The broad spectral bandwidths, precision timing resolution, low coherence and high peak powers of ultrafast optical pulses provide unique opportunities for imaging and manipulating biological systems. Time-resolved studies of bio-molecular dynamics exploit the short pulse durations from such lasers, while other applications such as optical coherence tomography benefit from the broad optical bandwidths possible by using super-continuum generation and additionally allowing for high speed imaging with speeds as high as 47 000 scans per second. Continuing progress in laser-system technology is accelerating the adoption of ultrafast techniques across the life sciences, both in research laboratories and in clinical applications, such as laser-assisted in situ keratomileusis (LASIK) eye surgery. Revolutionizing the field of optical microscopy, two-photon excitation fluorescence (TPEF) microscopy has enabled higher spatial resolution with improved depth penetration into biological specimens. Advantages of this nonlinear optical process include: reduced photo-interactions, allowing for extensive imaging time periods; simultaneously exciting multiple fluorescent molecules with only one excitation wavelength; and

Tumor detection in mice by measurement of fluorescence decay time matrices

NASA Astrophysics Data System (ADS)

Cubeddu, R.; Pifferi, A.; Taroni, P.; Valentini, G.; Canti, G.

1995-12-01

An intensified CCD video camera has been used to measure the spatial distribution of the fluorescence decay time in tumor-bearing mice sensitized with hematoporphyrin derivative. Mice were injected with five doses of sensitizer, ranging from 0.1 to 10 mg / kg body weight. For any drug dose the decay time of the exogenous fluorescence in the tumor is always significantly longer than in normal tissues. The image created by associating a gray-shade scale to the decay time matrix of each mouse permits a reliable and precise detection of the neoplasia.

The Origin of Fluorescence from Graphene Oxide

PubMed Central

Shang, Jingzhi; Ma, Lin; Li, Jiewei; Ai, Wei; Yu, Ting; Gurzadyan, Gagik G.

2012-01-01

Time-resolved fluorescence measurements of graphene oxide in water show multiexponential decay kinetics ranging from 1 ps to 2 ns. Electron-hole recombination from the bottom of the conduction band and nearby localized states to wide-range valance band is suggested as origin of the fluorescence. Excitation wavelength dependence of the fluorescence was caused by relative intensity changes of few emission species. By introducing the molecular orbital concept, the dominant fluorescence was found to originate from the electronic transitions among/between the non-oxidized carbon regions and the boundary of oxidized carbon atom regions, where all three kinds of functionalized groups C-O, C = O and O = C-OH were participating. In the visible spectral range, the ultrafast fluorescence of graphene oxide was observed for the first time. PMID:23145316

Bright and ultra-fast scintillation from a semiconductor?

PubMed Central

Derenzo, Stephen E.; Bourret-Courshesne, Edith; Bizarri, Gregory; Canning, Andrew

2015-01-01

Semiconductor scintillators are worth studying because they include both the highest luminosities and shortest decay times of all known scintillators. Moreover, many semiconductors have the heaviest stable elements (Tl, Hg, Pb, Bi) as a major constituent and a high ion pair yield that is proportional to the energy deposited. We review the scintillation properties of semiconductors activated by native defects, isoelectronic impurities, donors and acceptors with special emphasis on those that have exceptionally high luminosities (e.g. ZnO:Zn, ZnS:Ag,Cl, CdS:Ag,Cl) and those that have ultra-fast decay times (e.g. ZnO:Ga; CdS:In). We discuss underlying mechanisms that are consistent with these properties and the possibilities for achieving (1) 200,000 photons/MeV and 1% fwhm energy resolution for 662 keV gamma rays, (2) ultra-fast (ns) decay times and coincident resolving times of 30 ps fwhm for time-of-flight positron emission tomography, and (3) both a high luminosity and an ultra-fast decay time from the same scintillator at cryogenic temperatures. PMID:26855462

Maximum entropy analysis of polarized fluorescence decay of (E)GFP in aqueous solution

NASA Astrophysics Data System (ADS)

Novikov, Eugene G.; Skakun, Victor V.; Borst, Jan Willem; Visser, Antonie J. W. G.

2018-01-01

The maximum entropy method (MEM) was used for the analysis of polarized fluorescence decays of enhanced green fluorescent protein (EGFP) in buffered water/glycerol mixtures, obtained with time-correlated single-photon counting (Visser et al 2016 Methods Appl. Fluoresc. 4 035002). To this end, we used a general-purpose software module of MEM that was earlier developed to analyze (complex) laser photolysis kinetics of ligand rebinding reactions in oxygen binding proteins. We demonstrate that the MEM software provides reliable results and is easy to use for the analysis of both total fluorescence decay and fluorescence anisotropy decay of aqueous solutions of EGFP. The rotational correlation times of EGFP in water/glycerol mixtures, obtained by MEM as maxima of the correlation-time distributions, are identical to the single correlation times determined by global analysis of parallel and perpendicular polarized decay components. The MEM software is also able to determine homo-FRET in another dimeric GFP, for which the transfer correlation time is an order of magnitude shorter than the rotational correlation time. One important advantage utilizing MEM analysis is that no initial guesses of parameters are required, since MEM is able to select the least correlated solution from the feasible set of solutions.

A new approach to interpretation of heterogeneity of fluorescence decay in complex biological systems

NASA Astrophysics Data System (ADS)

Wlodarczyk, Jakub; Kierdaszuk, Borys

2005-08-01

Decays of tyrosine fluorescence in protein-ligand complexes are described by a model of continuous distribution of fluorescence lifetimes. Resulted analytical power-like decay function provides good fits to highly complex fluorescence kinetics. Moreover, this is a manifestation of so-called Tsallis q-exponential function, which is suitable for description of the systems with long-range interactions, memory effect, as well as with fluctuations of the characteristic lifetime of fluorescence. The proposed decay functions were applied to analysis of fluorescence decays of tyrosine in a protein, i.e. the enzyme purine nucleoside phosphorylase from E. coli (the product of the deoD gene), free in aqueous solution and in a complex with formycin A (an inhibitor) and orthophosphate (a co-substrate). The power-like function provides new information about enzyme-ligand complex formation based on the physically justified heterogeneity parameter directly related to the lifetime distribution. A measure of the heterogeneity parameter in the enzyme systems is provided by a variance of fluorescence lifetime distribution. The possible number of deactivation channels and excited state mean lifetime can be easily derived without a priori knowledge of the complexity of studied system. Moreover, proposed model is simpler then traditional multi-exponential one, and better describes heterogeneous nature of studied systems.

Fluorescence decay of naphthalene studied in an electrostatic storage ring, the Mini-Ring

NASA Astrophysics Data System (ADS)

Martin, S.; Matsumoto, J.; Kono, N.; Ji, M.-C.; Brédy, R.; Bernard, J.; Cassimi, A.; Chen, L.

2017-10-01

The cooling of naphthalene cations (C10H8)+ has been studied in a compact electrostatic ion storage ring, the Mini-Ring. A nano second laser pulse of 532 nm (2.33 eV) was used to probe the internal energy distribution every millisecond during the storage time up to 5 ms. The evolution of the internal energy distribution of the stored ions was simulated with a model taking into account the dissociation and the radiative decay processes. Calculated decay curves were fitted to the corresponding laser induced neutral decays. For a laser power of 200 μJ/pulse, a good agreement between experiment and modeling was found using an initial Gaussian energy distribution centered to 5.9 eV and a fluorescence decay rate varying from 200 to 300 s-1 in the energy range from 6 to 7 eV. This fast decay was attributed to the delayed Poincaré fluorescence process.

The Analysis of Fluorescence Decay by a Method of Moments

PubMed Central

Isenberg, Irvin; Dyson, Robert D.

1969-01-01

The fluorescence decay of the excited state of most biopolymers, and biopolymer conjugates and complexes, is not, in general, a simple exponential. The method of moments is used to establish a means of analyzing such multi-exponential decays. The method is tested by the use of computer simulated data, assuming that the limiting error is determined by noise generated by a pseudorandom number generator. Multi-exponential systems with relatively closely spaced decay constants may be successfully analyzed. The analyses show the requirements, in terms of precision, that data must meet. The results may be used both as an aid in the design of equipment and in the analysis of data subsequently obtained. PMID:5353139

The role of different structural motifs in the ultrafast dynamics of second generation protein stains.

PubMed

Chatterjee, Soumit; Karuso, Peter; Boulangé, Agathe; Peixoto, Philippe A; Franck, Xavier; Datta, Anindya

2013-12-05

Engineering the properties of fluorescent probes through modifications of the fluorophore structure has become a subject of interest in recent times. By doing this, the photophysical and photochemical properties of the modified fluorophore can be understood and this can guide the design and synthesis of better fluorophores for use in biotechnology. In this work, the electronic spectra and fluorescence decay kinetics of four analogues of the fluorescent natural product epicocconone were investigated. Epicocconone is unique in that the native state is weakly green fluorescent, whereas the enamine formed reversibly with proteins is highly emissive in the red. It was found that the ultrafast dynamics of the analogues depends profoundly on the H-bonding effect of solvents and solvent viscosity though solvent polarity also plays a role. Comparing the steady state and time-resolved data, the weak fluorescence of epicocconone in its native state is most likely due to the photoisomerization of the hydrocarbon side chain, while the keto enol moiety also has a role to play in determining the fluorescence quantum yield. This understanding is expected to aid the design of better protein stains from the same family.

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

PubMed

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

2007-03-22

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

Ultrafast photoelectron spectroscopy of small molecule organic films

NASA Astrophysics Data System (ADS)

Read, Kendall Laine

As research in the field of ultrafast optics has produced shorter and shorter pulses, at an ever-widening range of frequencies, ultrafast spectroscopy has grown correspondingly. In particular, ultrafast photoelectron spectroscopy allows direct observation of electrons in transient or excited states, regardless of the eventual relaxation mechanisms. High-harmonic conversion of 800nm, femtosecond, Ti:sapphire laser pulses allows excite/probe spectroscopy down into atomic core level states. To this end, an ultrafast, X-UV photoelectron spectroscopic system is described, including design considerations for the high-harmonic generation line, the time of flight detector, and the subsequent data collection electronics. Using a similar experimental setup, I have performed several ultrafast, photoelectron excited state decay studies at the IBM, T. J. Watson Research Center. All of the observed materials were electroluminescent thin film organics, which have applications as the emitter layer in organic light emitting devices. The specific materials discussed are: Alq, BAlq, DPVBi, and Alq doped with DCM or DMQA. Alq:DCM is also known to lase at low photoexcitation thresholds. A detailed understanding of the involved relaxation mechanisms is beneficial to both applications. Using 3.14 eV excite, and 26.7 eV probe, 90 fs laser pulses, we have observed the lowest unoccupied molecular orbital (LUMO) decay rate over the first 200 picoseconds. During this time, diffusion is insignificant, and all dynamics occur in the absence of electron transport. With excitation intensities in the range of 100μJ/cm2, we have modeled the Alq, BAlq, and DPVBi decays via bimolecular singlet-singlet annihilation. At similar excitations, we have modeled the Alq:DCM decay via Förster transfer, stimulated emission, and excimeric formation. Furthermore, the Alq:DCM occupied to unoccupied molecular orbital energy gap was seen to shrink as a function of excite-to-probe delay, in accordance with the

Conformational Control of Ultrafast Molecular Rotor Property: Tuning Viscosity Sensing Efficiency by Twist Angle Variation.

PubMed

Ghosh, Rajib; Kushwaha, Archana; Das, Dipanwita

2017-09-21

Fluorescent molecular rotors find widespread application in sensing and imaging of microscopic viscosity in complex chemical and biological media. Development of viscosity-sensitive ultrafast molecular rotor (UMR) relies upon the understanding of the excited-state dynamics and their implications for viscosity-dependent fluorescence signaling. Unraveling the structure-property relationship of UMR behavior is of significance toward development of an ultrasensitive fluorescence microviscosity sensor. Herein we show that the ground-state equilibrium conformation has an important role in the ultrafast twisting dynamics of UMRs and consequent viscosity sensing efficiency. Synthesis, photophysics, and ultrafast spectroscopic experiments in conjunction with quantum chemical calculation of a series of UMRs based on dimethylaniline donor and benzimidazolium acceptor with predefined ground-state torsion angle led us to unravel that the ultrafast torsional dynamics around the bond connecting donor and acceptor groups profoundly influences the molecular rotor efficiency. This is the first experimental demonstration of conformational control of small-molecule-based UMR efficiencies which can have wider implication toward development of fluorescence sensors based on the UMR principle. Conformation-controlled UMR efficiency has been shown to exhibit commensurate fluorescence enhancement upon DNA binding.

Ultrafast fluorescence imaging in vivo with conjugated polymer fluorophores in the second near-infrared window

NASA Astrophysics Data System (ADS)

Hong, Guosong; Zou, Yingping; Antaris, Alexander L.; Diao, Shuo; Wu, Di; Cheng, Kai; Zhang, Xiaodong; Chen, Changxin; Liu, Bo; He, Yuehui; Wu, Justin Z.; Yuan, Jun; Zhang, Bo; Tao, Zhimin; Fukunaga, Chihiro; Dai, Hongjie

2014-06-01

In vivo fluorescence imaging in the second near-infrared window (1.0-1.7 μm) can afford deep tissue penetration and high spatial resolution, owing to the reduced scattering of long-wavelength photons. Here we synthesize a series of low-bandgap donor/acceptor copolymers with tunable emission wavelengths of 1,050-1,350 nm in this window. Non-covalent functionalization with phospholipid-polyethylene glycol results in water-soluble and biocompatible polymeric nanoparticles, allowing for live cell molecular imaging at >1,000 nm with polymer fluorophores for the first time. Importantly, the high quantum yield of the polymer allows for in vivo, deep-tissue and ultrafast imaging of mouse arterial blood flow with an unprecedented frame rate of >25 frames per second. The high time-resolution results in spatially and time resolved imaging of the blood flow pattern in cardiogram waveform over a single cardiac cycle (~200 ms) of a mouse, which has not been observed with fluorescence imaging in this window before.

Ultrafast Nonradiative Decay and Excitation Energy Transfer by Carotenoids in Photosynthetic Light-Harvesting Proteins

NASA Astrophysics Data System (ADS)

Ghosh, Soumen

This dissertation investigates the photophysical and structural dynamics that allow carotenoids to serve as efficient excitation energy transfer donor to chlorophyll acceptors in photosynthetic light harvesting proteins. Femtosecond transient grating spectroscopy with optical heterodyne detection has been employed to follow the nonradiative decay pathways of carotenoids and excitation energy transfer to chlorophylls. It was found that the optically prepared S2 (11Bu+) state of beta-carotene decays in 12 fs fs to populate an intermediate electronic state, Sx, which then decays nonradiatively to the S 1 state. The ultrafast rise of the dispersion component of the heterodyne transient grating signal reports the formation of Sx intermediate since the rise of the dispersion signal is controlled by the loss of stimulated emission from the S2 state. These findings were extended to studies of peridinin, a carbonyl substituted carotenoid that serves as a photosynthetic light-harvesting chromophore in dinoflagellates. Numerical simulations using nonlinear response formalism and the multimode Brownian oscillator model assigned the Sx intermediate to a torsionally distorted structure evolving on the S2 potential surface. The decay of the Sx state is promoted by large amplitude out-of-plane torsional motions and is significantly retarded by solvent friction owing to the development of an intramolecular charge transfer character in peridinin. The slowing of the nonradiative decay allows the Sx state to transfer significant portion of the excitation energy to chlorophyll a acceptors in the peridinin-chlorophyll a protein. The results of heterodyne transient grating study on peridinin-chlorophyll a protein suggests two distinct energy transfer channels from peridinin to chlorophyll a: a 30 fs process involving quantum coherence and delocalized peridinin-Chl states and an incoherent, 2.5 ps process involving the distorted S2 state of peridinin. The torsional evolution on the S2

Ultrafast Excited-State Dynamics of Cytosine Aza-Derivative and Analogues.

PubMed

Zhou, Zhongneng; Zhou, Xueyao; Wang, Xueli; Jiang, Bin; Li, Yongle; Chen, Jinquan; Xu, Jianhua

2017-04-13

Excited state dynamics of 5-azacytosine (5-AC), 2,4-diamino-1,3,5-triazine (2,4-DT), and 2-amino-1,3,5-triazine (2-AT) were comprehensively investigated by steady state absorption, fluorescence, and femtosecond transient absorption measurements. Time-dependent density functional theory (TDDFT) calculations were performed to help assign the absorption bands and understand the excited state decay mechanisms. The experimental results of excited singlet state dynamics for 5-AC, 2,4-DT, and 2-AT with femtosecond time resolution were reported for the first time. Two distinct decay pathways, with ∼1 ps and tens of picosecond lifetimes, were observed in 5-AC. Only one decay pathway with 17 ps lifetime was observed in 2,4-DT while an emissive state was found in 2-AT. TDDFT calculations suggest that 5-AC has a dark nπ* (S 1 ) state below the first allowed ππ* (S 2 ) state, which leads to the ultrafast decay of the ππ* state. In 2,4-DT, there is no dark nπ* state below the bright ππ* (S 1 ) state and the 17 ps lifetime is assigned to the relaxation from the ππ* (S 1 ) state to ground state. Two dark nπ* states (S 1 and S 2 ) were found in 2-AT, which exhibits much more complex excited state dynamics compared with the other two. Photoluminescence in 2-AT has been confirmed to be fluorescence emission from its bright ππ* (S 3 ) state. Our results strongly suggest that electronic structures are very sensitive to the substitution on the triazine ring and that the photophysical properties of nucleic acid analogues depend highly on their molecular structures.

Formation of hemoglobin photoproduct is responsible for two-photon and single photon-excited fluorescence of red blood cells

NASA Astrophysics Data System (ADS)

Shirshin, Evgeny A.; Yakimov, Boris P.; Rodionov, Sergey A.; Omelyanenko, Nikolai P.; Priezzhev, Alexander V.; Fadeev, Victor V.; Lademann, Juergen; Darvin, Maxim E.

2018-07-01

Two-photon excited fluorescence of red blood cells (RBC) has been reported to be applicable for their assessment in vitro and in vivo. The corresponding fluorescence emission was ascribed to hemoglobin (Hb), however, as Hb is essentially non-fluorescent at single-photon excitation, the mechanism of two-photon excited fluorescence of RBC remains debatable. Here we show that a fluorescent photoproduct, characterized by an ultrafast decay of excitation, is formed after irradiation of Hb with femtosecond laser pulses with ca. 8 · 10‑5 quantum yield, and that it is also fluorescent at single-photon excitation. The formation of a similar photoproduct was also shown for Hb continuous wave irradiation with blue light with ca. 10‑5 formation quantum yield. The kinetics of the Hb photoproduct formation and its spectral properties were investigated. The obtained results clarify the processes responsible for RBC fluorescence observed in two-photon microscopy experiments.

Fluorescence Spectrum and Decay Measurement for Hsil VS Normal Cytology Differentiation in Liquid Pap Smear Supernatant

NASA Astrophysics Data System (ADS)

Vaitkuviene, A.; Gegzna, V.; Juodkazis, S.; Jursenas, S.; Miasojedovas, S.; Kurtinaitiene, R.; Rimiene, J.; Vaitkus, J.

2009-06-01

Cervical smear material contains endo and exocervical cells, mucus and inflammative, immune cells in cases of pathology. Just not destroyed keratinocytes lay on the glass for microscopy. Liquid cytology supernatant apart other diagnostics could be used for photodiagnostic. The spectroscopic parameters suitable for Normal and HSIL cytology groups supernatant differentiation are demonstrated. The dried liquid PAP supernatant fractions—sediment and liquid were investigated. Excitation and emission matrices (EEM), supernatant fluorescence decay measured under 280 nm diode short pulse excitation and fluorescence spectroscopy by excitation with 355 nm laser light were analyzed. The differences between Normal and HSIL groups were statistically proven in the certain spectral regions. Fluorescence decay peculiarities show spectral regions consisting of few fluorophores. Obtained results on fluorescence differences in Normal and HSIL groups' supernatant shows the potency of photodiagnosis application in cervical screening.

Hard-X-Ray-Induced Multistep Ultrafast Dissociation

NASA Astrophysics Data System (ADS)

Travnikova, Oksana; Marchenko, Tatiana; Goldsztejn, Gildas; Jänkälä, Kari; Sisourat, Nicolas; Carniato, Stéphane; Guillemin, Renaud; Journel, Loïc; Céolin, Denis; Püttner, Ralph; Iwayama, Hiroshi; Shigemasa, Eiji; Piancastelli, Maria Novella; Simon, Marc

2016-05-01

Creation of deep core holes with very short (τ ≤1 fs ) lifetimes triggers a chain of relaxation events leading to extensive nuclear dynamics on a few-femtosecond time scale. Here we demonstrate a general multistep ultrafast dissociation on an example of HCl following Cl 1 s →σ* excitation. Intermediate states with one or multiple holes in the shallower core electron shells are generated in the course of the decay cascades. The repulsive character and large gradients of the potential energy surfaces of these intermediates enable ultrafast fragmentation after the absorption of a hard x-ray photon.

Correlation of conformational heterogeneity of the tryptophyl side chain and time-resolved fluorescence intensity decay kinetics

NASA Astrophysics Data System (ADS)

Laws, William R.; Ross, J. B. Alexander

1992-04-01

The time-resolved fluorescence properties of a tryptophan residue should be useful for probing protein structure, function, and dynamics. To date, however, the non-single exponential fluorescence intensity decay kinetics for numerous peptides and proteins having a single tryptophan residue have not been adequately explained. Many possibilities have been considered and include: (1) contributions from the 1La and 1Lb states of indole; (2) excited-state hydrogen exchange; and (3) environmental heterogeneity from (chi) 1 and (chi) 2 rotamers. In addition, it has been suggested that generally many factors contribute to the decay and a distribution of probabilities may be more appropriate. Two recent results support multiple species due to conformational heterogeneity as the major contributor to complex kinetics. First, a rotationally constrained tryptophan analogue has fluorescence intensity decay kinetics that can be described by the sum of two exponentials with amplitudes comparable to the relative populations of the two rotational isomers. Second, the multiple exponentials observed for tyrosine-containing model compounds and peptides correlate with the (chi) 1 rotamer populations independently determined by 1H NMR. We now report similar correlations between rotamer populations and fluorescence intensity decay kinetics for a tryptophan analogue of oxytocin. It appears for this compound that either (chi) 2 rotations do not appreciably alter the indole environment, (chi) 2 rotations are rapid enough to average the observed dependence, or only one of two possible (chi) 2 populations is associated with each (chi) 1 rotamer.

Applications of time-resolved laser fluorescence spectroscopy to the environmental biogeochemistry of actinides.

PubMed

Collins, Richard N; Saito, Takumi; Aoyagi, Noboru; Payne, Timothy E; Kimura, Takaumi; Waite, T David

2011-01-01

Time-resolved laser fluorescence spectroscopy (TRLFS) is a useful means of identifying certain actinide species resulting from various biogeochemical processes. In general, TRLFS differentiates chemical species of a fluorescent metal ion through analysis of different excitation and emission spectra and decay lifetimes. Although this spectroscopic technique has largely been applied to the analysis of actinide and lanthanide ions having fluorescence decay lifetimes on the order of microseconds, such as UO , Cm, and Eu, continuing development of ultra-fast and cryogenic TRLFS systems offers the possibility to obtain speciation information on metal ions having room-temperature fluorescence decay lifetimes on the order of nanoseconds to picoseconds. The main advantage of TRLFS over other advanced spectroscopic techniques is the ability to determine in situ metal speciation at environmentally relevant micromolar to picomolar concentrations. In the context of environmental biogeochemistry, TRLFS has principally been applied to studies of (i) metal speciation in aqueous and solid phases and (ii) the coordination environment of metal ions sorbed to mineral and bacterial surfaces. In this review, the principles of TRLFS are described, and the literature reporting the application of this methodology to the speciation of actinides in systems of biogeochemical interest is assessed. Significant developments in TRLFS methodology and advanced data analysis are highlighted, and we outline how these developments have the potential to further our mechanistic understanding of actinide biogeochemistry. American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America.

Fluorescence decay kinetics and imaging of NAD(P)H and flavins as metabolic indicators

NASA Astrophysics Data System (ADS)

Schneckenburger, Herbert; Koenig, Karsten

1992-07-01

The intrinsic fluorescence of various cell cultures in the blue and green spectral range has been attributed mainly to hydrated nicotinamide adenine dinucleotide (NADH) and flavin molecules. Their fluorescence decay curves were measured with subnanosecond resolution. The reduced coenzymes NADH and hydrated nicotinamide adenine dinucleotide phosphate NADPH, both showed a biexponential decay pattern in solution with similar time constants, but different relative intensities of the two components. They could thus be distinguished from one another as well as from their oxidized forms. The NADPH fluorescence of Saccharomyces cerevisiae was located within the cytoplasm and its organelles and was by about a factor of 4 higher for respiratory-deficient than for intact yeast strains. Intracellular flavin fluorescence showed a triexponential behavior--probably due to a superposition of protein-bound and free flavin molecules. The lifetime of the shortest component varied within the range of 0.20 to 0.50 ns between respiratory-deficient and intact yeast strains, and the relative intensity of this component was most pronounced for the intact strain DL1. Time- resolved fluorescence seems therefore to be an appropriate method of probe the function of the respiratory chain and--in the further step--to differentiate between various types of cells and tissues in medical diagnosis or environmental research.

PsbS is required for systemic acquired acclimation and post-excess-light-stress optimization of chlorophyll fluorescence decay times in Arabidopsis

PubMed Central

Ciszak, Kamil; Kulasek, Milena; Barczak, Anna; Grzelak, Justyna; Maćkowski, Sebastian; Karpiński, Stanisław

2015-01-01

Systemic acquired acclimation (SAA) is an important light acclimatory mechanism that depends on the global adjustments of non-photochemical quenching and chloroplast retrograde signaling. As the exact regulation of these processes is not known, we measured time-resolved fluorescence of chlorophyll a in Arabidopsis thaliana leaves exposed to excess light, in leaves undergoing SAA, and in leaves after excess light episode. We compare the behavior induced in wild-type plants with null mutant of non-photochemical quenching (npq4–1). The wild type rosettes exhibit a small reduction of fluorescence decay times in leaves directly exposed to excess light and in leaves undergoing SAA in ambient low light. However in npq4–1 exposition to excess light results in much faster fluorescence decay, which is insensitive to excitation power. At the same time npq4–1 leaves undergoing SAA displayed intermediate fluorescence decay. The npq4–1 plants also lost the ability to optimize florescence decay, and thus chlorophyll a dynamics up to 2 h after excess light episode. The fluorescence decay dynamics in both WT and npq4–1 can be described by a set of 3 maximum decay times. Based on the results, we concluded that functional PsbS is required for optimization of absorbed photon fate and optimal light acclimatory responses such as SAA or after excess light stress. PMID:25654166

Fluorescence decay data analysis correcting for detector pulse pile-up at very high count rates

NASA Astrophysics Data System (ADS)

Patting, Matthias; Reisch, Paja; Sackrow, Marcus; Dowler, Rhys; Koenig, Marcelle; Wahl, Michael

2018-03-01

Using time-correlated single photon counting for the purpose of fluorescence lifetime measurements is usually limited in speed due to pile-up. With modern instrumentation, this limitation can be lifted significantly, but some artifacts due to frequent merging of closely spaced detector pulses (detector pulse pile-up) remain an issue to be addressed. We propose a data analysis method correcting for this type of artifact and the resulting systematic errors. It physically models the photon losses due to detector pulse pile-up and incorporates the loss in the decay fit model employed to obtain fluorescence lifetimes and relative amplitudes of the decay components. Comparison of results with and without this correction shows a significant reduction of systematic errors at count rates approaching the excitation rate. This allows quantitatively accurate fluorescence lifetime imaging at very high frame rates.

PyFDAP: automated analysis of fluorescence decay after photoconversion (FDAP) experiments.

PubMed

Bläßle, Alexander; Müller, Patrick

2015-03-15

We developed the graphical user interface PyFDAP for the fitting of linear and non-linear decay functions to data from fluorescence decay after photoconversion (FDAP) experiments. PyFDAP structures and analyses large FDAP datasets and features multiple fitting and plotting options. PyFDAP was written in Python and runs on Ubuntu Linux, Mac OS X and Microsoft Windows operating systems. The software, a user guide and a test FDAP dataset are freely available for download from http://people.tuebingen.mpg.de/mueller-lab. © The Author 2014. Published by Oxford University Press. All rights reserved. For Permissions, please e-mail: journals.permissions@oup.com.

Solvent-modified ultrafast decay dynamics in conjugated polymer/dye labeled single stranded DNA

NASA Astrophysics Data System (ADS)

Kim, Inhong; Kang, Mijeong; Woo, Han Young; Oh, Jin-Woo; Kyhm, Kwangseuk

2015-07-01

We have investigated that organic solvent (DMSO, dimethyl sulfoxide) modifies energy transfer efficiency between conjugated polymers (donors) and fluorescein-labeled single stranded DNAs (acceptors). In a mixture of buffer and organic solvent, fluorescence of the acceptors is significantly enhanced compared to that of pure water solution. This result can be attributed to change of the donor-acceptor environment such as decreased hydrophobicity of polymers, screening effect of organic solvent molecules, resulting in an enhanced energy transfer efficiency. Time-resolved fluorescence decay of the donors and the acceptors was modelled by considering the competition between the energy harvesting Foerster resonance energy transfer and the energy-wasting quenching. This enables to quantity that the Foerster distance (R0 = 43.3 Å) and resonance energy transfer efficiency (EFRET = 58.7 %) of pure buffer solution become R0 = 38.6 Å and EFRET = 48.0 % when 80% DMSO/buffer mixture is added.

Heterogenous fluorescence decay of (4→6)-and (4→8)-linked dimers of (+)-catechin and (-) epicatechin as a result of rotational isomerism.

Treesearch

Wolfgang R. Bergmann; Mary D. Barkley; Richard W. Hemingway; Wayne Mattice

1987-01-01

The time-resolved fluorescence of (+)-catechin and ( -)-epicatechin decays as a single exponential. In contrast dimers formed from (+)-catechin and (-)-epicatechin have more complex decays unless rotation about the interflavan bond is constrained by the introduction of a new ring. The fluorescence decay in unconstrained dimers is adequately described by the sum of two...

Ultrafast quantum control of ionization dynamics in krypton.

PubMed

Hütten, Konrad; Mittermair, Michael; Stock, Sebastian O; Beerwerth, Randolf; Shirvanyan, Vahe; Riemensberger, Johann; Duensing, Andreas; Heider, Rupert; Wagner, Martin S; Guggenmos, Alexander; Fritzsche, Stephan; Kabachnik, Nikolay M; Kienberger, Reinhard; Bernhardt, Birgitta

2018-02-19

Ultrafast spectroscopy with attosecond resolution has enabled the real time observation of ultrafast electron dynamics in atoms, molecules and solids. These experiments employ attosecond pulses or pulse trains and explore dynamical processes in a pump-probe scheme that is selectively sensitive to electronic state of matter via photoelectron or XUV absorption spectroscopy or that includes changes of the ionic state detected via photo-ion mass spectrometry. Here, we demonstrate how the implementation of combined photo-ion and absorption spectroscopy with attosecond resolution enables tracking the complex multidimensional excitation and decay cascade of an Auger auto-ionization process of a few femtoseconds in highly excited krypton. In tandem with theory, our study reveals the role of intermediate electronic states in the formation of multiply charged ions. Amplitude tuning of a dressing laser field addresses different groups of decay channels and allows exerting temporal and quantitative control over the ionization dynamics in rare gas atoms.

Excitation laser energy dependence of surface-enhanced fluorescence showing plasmon-induced ultrafast electronic dynamics in dye molecules

NASA Astrophysics Data System (ADS)

Itoh, Tamitake; Yamamoto, Yuko S.; Tamaru, Hiroharu; Biju, Vasudevanpillai; Murase, Norio; Ozaki, Yukihiro

2013-06-01

We find unique properties accompanying surface-enhanced fluorescence (SEF) from dye molecules adsorbed on Ag nanoparticle aggregates, which generate surface-enhanced Raman scattering. The properties are observed in excitation laser energy dependence of SEF after excluding plasmonic spectral modulation in SEF. The unique properties are large blue shifts of fluorescence spectra, deviation of ratios between anti-Stokes SEF intensity and Stokes from those of normal fluorescence, super-broadening of Stokes spectra, and returning to original fluorescence by lower energy excitation. We elucidate that these properties are induced by electromagnetic enhancement of radiative decay rates exceeding the vibrational relaxation rates within an electronic excited state, which suggests that molecular electronic dynamics in strong plasmonic fields can be largely deviated from that in free space.

Ultrafast Method for the Analysis of Fluorescence Lifetime Imaging Microscopy Data Based on the Laguerre Expansion Technique

PubMed Central

Jo, Javier A.; Fang, Qiyin; Marcu, Laura

2007-01-01

We report a new deconvolution method for fluorescence lifetime imaging microscopy (FLIM) based on the Laguerre expansion technique. The performance of this method was tested on synthetic and real FLIM images. The following interesting properties of this technique were demonstrated. 1) The fluorescence intensity decay can be estimated simultaneously for all pixels, without a priori assumption of the decay functional form. 2) The computation speed is extremely fast, performing at least two orders of magnitude faster than current algorithms. 3) The estimated maps of Laguerre expansion coefficients provide a new domain for representing FLIM information. 4) The number of images required for the analysis is relatively small, allowing reduction of the acquisition time. These findings indicate that the developed Laguerre expansion technique for FLIM analysis represents a robust and extremely fast deconvolution method that enables practical applications of FLIM in medicine, biology, biochemistry, and chemistry. PMID:19444338

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

NASA Astrophysics Data System (ADS)

Silva, Norberto De Jesus

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

Correlation of tryptophan fluorescence intensity decay parameters with sup 1 H NMR-determined rotamer conformations: (tryptophan sup 2 )oxytocin

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

Ross, J.B.A.; Schwartz, G.P.; Laws, W.R.

1992-02-18

While the fluorescence decay kinetics of tyrosine model compounds can be explained in terms of heterogeneity derived from the three ground-state {chi}{sup 1} rotamers, a similar correlation has yet to be directly observed for a tryptophan residue. In addition, the asymmetric indole ring might also lead to heterogeneity from {chi}{sup 2} rotations. In this paper, the time-resolved and steady-state fluorescence properties of (tryptophan{sup 2})oxytocin at pH 3 are presented and compared with {sup 1}H NMR results. According to the unrestricted analyses of individual fluorescence decay curves taken as a function of emission wavelength-independent decay constants, only three exponential terms aremore » required. In addition, the preexponential weighting factors (amplitudes) have the same relative relationship (weights) as the {sup 1}H NMR-determined {chi}{sup 1} rotamer populations of the indole side chain. {sup 15}N was used in heteronuclear coupling experiments to confirm the rotamer assignments. Inclusion of a linked function restricting the decay amplitudes to the {chi}{sup 1} rotamer populations in the individual decay curve analyses and in the global analysis confirms this correlation. According to qualitative nuclear Overhauser data, there are two {chi}{sup 2} populations.« less

Correction Approach for Delta Function Convolution Model Fitting of Fluorescence Decay Data in the Case of a Monoexponential Reference Fluorophore.

PubMed

Talbot, Clifford B; Lagarto, João; Warren, Sean; Neil, Mark A A; French, Paul M W; Dunsby, Chris

2015-09-01

A correction is proposed to the Delta function convolution method (DFCM) for fitting a multiexponential decay model to time-resolved fluorescence decay data using a monoexponential reference fluorophore. A theoretical analysis of the discretised DFCM multiexponential decay function shows the presence an extra exponential decay term with the same lifetime as the reference fluorophore that we denote as the residual reference component. This extra decay component arises as a result of the discretised convolution of one of the two terms in the modified model function required by the DFCM. The effect of the residual reference component becomes more pronounced when the fluorescence lifetime of the reference is longer than all of the individual components of the specimen under inspection and when the temporal sampling interval is not negligible compared to the quantity (τR (-1) - τ(-1))(-1), where τR and τ are the fluorescence lifetimes of the reference and the specimen respectively. It is shown that the unwanted residual reference component results in systematic errors when fitting simulated data and that these errors are not present when the proposed correction is applied. The correction is also verified using real data obtained from experiment.

Biomass conversion determined via fluorescent cellulose decay assay.

PubMed

Wischmann, Bente; Toft, Marianne; Malten, Marco; McFarland, K C

2012-01-01

An example of a rapid microtiter plate assay (fluorescence cellulose decay, FCD) that determines the conversion of cellulose in a washed biomass substrate is reported. The conversion, as verified by HPLC, is shown to correlate to the monitored FCD in the assay. The FCD assay activity correlates to the performance of multicomponent enzyme mixtures and is thus useful for the biomass industry. The development of an optimized setup of the 96-well microtiter plate is described, and is used to test a model that shortens the assay incubation time from 72 to 24h. A step-by-step procedure of the final assay is described. Copyright © 2012 Elsevier Inc. All rights reserved.

Ultrafast X-ray Auger probing of photoexcited molecular dynamics

DOE PAGES

McFarland, B. K.; Farrell, J. P.; Miyabe, S.; ...

2014-06-23

Here, molecules can efficiently and selectively convert light energy into other degrees of freedom. Disentangling the underlying ultrafast motion of electrons and nuclei of the photoexcited molecule presents a challenge to current spectroscopic approaches. Here we explore the photoexcited dynamics of molecules by an interaction with an ultrafast X-ray pulse creating a highly localized core hole that decays via Auger emission. We discover that the Auger spectrum as a function of photoexcitation—X-ray-probe delay contains valuable information about the nuclear and electronic degrees of freedom from an element-specific point of view. For the nucleobase thymine, the oxygen Auger spectrum shifts towardsmore » high kinetic energies, resulting from a particular C–O bond stretch in the ππ* photoexcited state. A subsequent shift of the Auger spectrum towards lower kinetic energies displays the electronic relaxation of the initial photoexcited state within 200 fs. Ab-initio simulations reinforce our interpretation and indicate an electronic decay to the nπ* state.« less

Oligomeric State of Lipocalin-1 (LCN1) by Multiangle Laser Light Scattering and Fluorescence Anisotropy Decay

PubMed Central

Gasymov, Oktay K.; Abduragimov, Adil R.; Merschak, Petra; Redl, Bernhard; Glasgow, Ben J.

2007-01-01

Multiangle laser light scattering and fluorescence anisotropy decay measurements clarified the oligomeric states of native and recombinant tear lipocalin (lipocalin-1, TL). Native TL is monomeric. Recombinant TL (5-68 μM) with or without the histidine tag shows less than 7% dimer formation that is not in equilibrium with the monomeric form. Fluorescence anisotropy decay showed a correlation time of 9-10 ns for TL (10 μM- 1mM). Hydrodynamic calculations based on the crystallographic structure of a monomeric TL mutant closely concur with the observed correlation time. The solution properties calculated with HYDROPRO and SOLPRO programs from the available crystallographic structure of a monomeric TL mutant concur closely with the observed fluorescence anisotropy decay. The resulting model shows that protein topology is the major determinant of rotational correlation time and accounts for deviation from the Stokes-Einstein relation. The data challenge previous gel filtration studies to show that native TL exists predominantly as a monomer in solution rather than as a dimer. Delipidation of TL results in a formation of a complex oligomeric state (up to 25%). These findings are important as the dynamic processes in the tear film are limited by diffusional, translational as well as rotational, properties of the protein. PMID:17869594

Ultrafast Decay of the Solvated Electron in a Neat Polar Solvent: The Unusual Case of Propylene Carbonate.

PubMed

Le Caër, Sophie; Ortiz, Daniel; Marignier, Jean-Louis; Schmidhammer, Uli; Belloni, Jacqueline; Mostafavi, Mehran

2016-01-07

The behavior of carbonates is critical for a detailed understanding of aging phenomena in Li-ion batteries. Here we study the first reaction stages of propylene carbonate (PC), a cyclical carbonate, by picosecond pulse radiolysis. An absorption band with a maximum around 1360 nm is observed at 20 ps after the electron pulse and is shifted to 1310 nm after 50 ps. This band presents the features of a solvated electron absorption band, the solvation lasting up to 50 ps. Surprisingly, in this polar solvent, the solvated electron follows an ultrafast decay and disappears with a half time of 360 ps. This is attributed to the formation of a radical anion PC(-•). The yield of the solvated electron is low, suggesting that the radical anions are mainly directly produced from presolvated electrons. These results demonstrate that the initial electron transfers mechanisms are strongly different in linear compared with cyclical carbonates.

An ultrafast X-ray scintillating detector made of ZnO(Ga)

NASA Astrophysics Data System (ADS)

Zhang, Qingmin; Yan, Jun; Deng, Bangjie; Zhang, Jingwen; Lv, Jinge; Wen, Xin; Gao, Keqing

2017-12-01

Owing to its ultrafast scintillation, quite high light yield, strong radiation resistance, and non-deliquescence, ZnO(Ga) is a highly promising choice for an ultrafast X-ray detector. Because of its high deposition rate, good production repeatability and strong adhesive force, reactive magnetron sputtering was used to produce a ZnO(Ga) crystal on a quartz glass substrate, after the production conditions were optimized. The fluorescence lifetime of the sample was 173 ps. An ultrafast X-ray scintillating detector, equipped with a fast microchannel plate (MCP) photomultiplier tube (PMT), was developed and the X-ray tests show a signal full width at half maximum (FWHM) of only 385.5 ps. Moreover, derivation from the previous measurement shows the ZnO(Ga) has an ultrafast time response (FWHM = 355.1 ps) and a high light yield (14740 photons/MeV).

Fluorescence Quenching of Alpha-Fetoprotein by Gold Nanoparticles: Effect of Dielectric Shell on Non-Radiative Decay

NASA Astrophysics Data System (ADS)

Zhu, Jian; Li, Jian-Jun; Wang, A.-Qing; Chen, Yu; Zhao, Jun-Wu

2010-09-01

Fluorescence quenching spectrometry was applied to study the interactions between gold colloidal nanoparticles and alpha-fetoprotein (AFP). Experimental results show that the gold nanoparticles can quench the fluorescence emission of adsorbed AFP effectively. Furthermore, the intensity of fluorescence emission peak decreases monotonously with the increasing gold nanoparticles content. A mechanism based on surface plasmon resonance-induced non-radiative decay was investigated to illuminate the effect of a dielectric shell on the fluorescence quenching ability of gold nanoparticles. The calculation results show that the increasing dielectric shell thickness may improve the monochromaticity of fluorescence quenching. However, high energy transfer efficiency can be obtained within a wide wavelength band by coating a thinner dielectric shell.

Non-adiabatic dynamics of isolated green fluorescent protein chromophore anion

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

Zhao, Li, E-mail: zhaoli282@dicp.ac.cn, E-mail: pwzhou@dicp.ac.cn, E-mail: libinsnet@dicp.ac.cn, E-mail: aihuagao@dicp.ac.cn; Gao, Ai-Hua, E-mail: zhaoli282@dicp.ac.cn, E-mail: pwzhou@dicp.ac.cn, E-mail: libinsnet@dicp.ac.cn, E-mail: aihuagao@dicp.ac.cn; University of the Chinese Academy of Sciences, Beijing 100049

2014-12-21

On-the-fly ab initio molecular dynamics calculations have been performed to investigate the relaxation mechanism of green fluorescent protein chromophore anion under vacuum. The CASSCF surface hopping simulation method based on Zhu-Nakamura theory is applied to present the real-time conformational changes of the target molecule. The static calculations and dynamics simulation results suggest that not only the twisting motion around bridging bonds between imidazolinone and phenoxy groups but the strength mode of C=O and pyramidalization character of bridging atom are major factors on the ultrafast fluorescence quenching process of the isolated chromophore anion. The abovementioned factors bring the molecule to themore » vicinity of conical intersections on its potential energy surface and to finish the internal conversion process. A Hula-like twisting pattern is displayed during the relaxation process and the entire decay process disfavors a photoswitching pattern which corresponds to cis-trans photoisomerization.« less

Variations in the heterogeneity of the decay of the fluorescence in six procyanidin dimers

Treesearch

Donghwan Cho; Rujiang Tian; Lawrence J. Porter; Richard W. Hemingway; Wayne L. Mattice

1990-01-01

The decay of the fluorescence has been measured in 1,4-dioxane for six dimers of (2R,3R)-(-)-epicatechin and (2R,3S)-(+)-catechin, hereafter denoted simply epicatechin and catechin. The dimers are epicatechin-(4β→8)-catechin, epicatechin-(4β→8)-epicatechin...

Excited-State Proton-Transfer-Induced Trapping Enhances the Fluorescence Emission of a Locked GFP Chromophore

PubMed Central

2016-01-01

The chemical locking of the central single bond in core chromophores of green fluorescent proteins (GFPs) influences their excited-state behavior in a distinct manner. Experimentally, it significantly enhances the fluorescence quantum yield of GFP chromophores with an ortho-hydroxyl group, while it has almost no effect on the photophysics of GFP chromophores with a para-hydroxyl group. To unravel the underlying physical reasons for this different behavior, we report static electronic structure calculations and nonadiabatic dynamics simulations on excited-state intramolecular proton transfer, cis–trans isomerization, and excited-state deactivation in a locked ortho-substituted GFP model chromophore (o-LHBI). On the basis of our previous and present results, we find that the S1 keto species is responsible for the fluorescence emission of the unlocked o-HBI and the locked o-LHBI species. Chemical locking does not change the parts of the S1 and S0 potential energy surfaces relevant to enol–keto tautomerization; hence, in both chromophores, there is an ultrafast excited-state intramolecular proton transfer that takes only 35 fs on average. However, the locking effectively hinders the S1 keto species from approaching the keto S1/S0 conical intersections so that most of trajectories are trapped in the S1 keto region for the entire 2 ps simulation time. Therefore, the fluorescence quantum yield of o-LHBI is enhanced compared with that of unlocked o-HBI, in which the S1 excited-state decay is efficient and ultrafast. In the case of the para-substituted GFP model chromophores p-HBI and p-LHBI, chemical locking hardly affects their efficient excited-state deactivation via cis–trans isomerization; thus, the fluorescence quantum yields in these chromophores remain very low. The insights gained from the present work may help to guide the design of new GFP chromophores with improved fluorescence emission and brightness. PMID:26744782

Ultrafast electronic and vibrational dynamics of stabilized A state mutants of the green fluorescent protein (GFP): Snipping the proton wire

NASA Astrophysics Data System (ADS)

Stoner-Ma, Deborah; Jaye, Andrew A.; Ronayne, Kate L.; Nappa, Jérôme; Tonge, Peter J.; Meech, Stephen R.

2008-06-01

Two blue absorbing and emitting mutants (S65G/T203V/E222Q and S65T at pH 5.5) of the green fluorescent protein (GFP) have been investigated through ultrafast time resolved infra-red (TRIR) and fluorescence spectroscopy. In these mutants, in which the excited state proton transfer reaction observed in wild-type GFP has been blocked, the photophysics are dominated by the neutral A state. It was found that the A∗ excited state lifetime is short, indicating that it is relatively less stabilised in the protein matrix than the anionic form. However, the lifetime of the A state can be increased through modifications to the protein structure. The TRIR spectra show that a large shifts in protein vibrational modes on excitation of the A state occurs in both these GFP mutants. This is ascribed to a change in H-bonding interactions between the protein matrix and the excited state.

Ultrafast Dephasing and Incoherent Light Photon Echoes in Organic Amorphous Systems

NASA Astrophysics Data System (ADS)

Yano, Ryuzi; Matsumoto, Yoshinori; Tani, Toshiro; Nakatsuka, Hiroki

1989-10-01

Incoherent light photon echoes were observed in organic amorphous systems (cresyl violet in polyvinyl alcohol and 1,4-dihydroxyanthraquinone in polymethacrylic acid) by using temporally-incoherent nanosecond laser pulses. It was found that an echo decay curve of an organic amorphous system is composed of a sharp peak which decays very rapidly and a slowly decaying wing at the tail. We show that the persistent hole burning (PHB) spectra were reproduced by the Fourier-cosine transforms of the echo decay curves. We claim that in general, we must take into account the multi-level feature of the system in order to explain ultrafast dephasing at very low temperatures.

Characterization of Geiger mode avalanche photodiodes for fluorescence decay measurements

NASA Astrophysics Data System (ADS)

Jackson, John C.; Phelan, Don; Morrison, Alan P.; Redfern, R. Michael; Mathewson, Alan

2002-05-01

Geiger mode avalanche photodiodes (APD) can be biased above the breakdown voltage to allow detection of single photons. Because of the increase in quantum efficiency, magnetic field immunity, robustness, longer operating lifetime and reduction in costs, solid-state detectors capable of operating at non-cryogenic temperatures and providing single photon detection capabilities provide attractive alternatives to the photomultiplier tube (PMT). Shallow junction Geiger mode APD detectors provide the ability to manufacture photon detectors and detector arrays with CMOS compatible processing steps and allows the use of novel Silicon-on-Insulator(SoI) technology to provide future integrated sensing solutions. Previous work on Geiger mode APD detectors has focused on increasing the active area of the detector to make it more PMT like, easing the integration of discrete reaction, detection and signal processing into laboratory experimental systems. This discrete model for single photon detection works well for laboratory sized test and measurement equipment, however the move towards microfluidics and systems on a chip requires integrated sensing solutions. As we move towards providing integrated functionality of increasingly nanoscopic sized emissions, small area detectors and detector arrays that can be easily integrated into marketable systems, with sensitive small area single photon counting detectors will be needed. This paper will demonstrate the 2-dimensional and 3-dimensional simulation of optical coupling that occurs in Geiger mode APDs. Fabricated Geiger mode APD detectors optimized for fluorescence decay measurements were characterized and preliminary results show excellent results for their integration into fluorescence decay measurement systems.

The photoluminescence of a fluorescent lamp: didactic experiments on the exponential decay

NASA Astrophysics Data System (ADS)

Onorato, Pasquale; Gratton, Luigi; Malgieri, Massimiliano; Oss, Stefano

2017-01-01

The lifetimes of the photoluminescent compounds contained in the coating of fluorescent compact lamps are usually measured using specialised instruments, including pulsed lasers and/or spectrofluorometers. Here we discuss how some low cost apparatuses, based on the use of either sensors for the educational lab or commercial digital photo cameras, can be employed to the same aim. The experiments do not require that luminescent phosphors are hazardously extracted from the compact fluorescent lamp, that also contains mercury. We obtain lifetime measurements for specific fluorescent elements of the bulb coating, in good agreement with the known values. We also address the physical mechanisms on which fluorescence lamps are based in a simplified way, suitable for undergraduate students; and we discuss in detail the physics of the lamp switch-off by analysing the time dependent spectrum, measured through a commercial fiber-optic spectrometer. Since the experiment is not hazardous in any way, requires a simple setup up with instruments which are commonly found in educational labs, and focuses on the typical features of the exponential decay, it is suitable for being performed in the undergraduate laboratory.

Ultrafast chemical interface scattering as an additional decay channel for nascent nonthermal electrons in small metal nanoparticles.

PubMed

Bauer, Christophe; Abid, Jean-Pierre; Fermin, David; Girault, Hubert H

2004-05-15

The use of 4.2 nm gold nanoparticles wrapped in an adsorbates shell and embedded in a TiO2 metal oxide matrix gives the opportunity to investigate ultrafast electron-electron scattering dynamics in combination with electronic surface phenomena via the surface plasmon lifetimes. These gold nanoparticles (NPs) exhibit a large nonclassical broadening of the surface plasmon band, which is attributed to a chemical interface damping. The acceleration of the loss of surface plasmon phase coherence indicates that the energy and the momentum of the collective electrons can be dissipated into electronic affinity levels of adsorbates. As a result of the preparation process, gold NPs are wrapped in a shell of sulfate compounds that gives rise to a large density of interfacial molecules confined between Au and TiO2, as revealed by Fourier-transform-infrared spectroscopy. A detailed analysis of the transient absorption spectra obtained by broadband femtosecond transient absorption spectroscopy allows separating electron-electron and electron-phonon interaction. Internal thermalization times (electron-electron scattering) are determined by probing the decay of nascent nonthermal electrons (NNEs) and the build-up of the Fermi-Dirac electron distribution, giving time constants of 540 to 760 fs at 0.42 and 0.34 eV from the Fermi level, respectively. Comparison with literature data reveals that lifetimes of NNEs measured for these small gold NPs are more than four times longer than for silver NPs with similar sizes. The surprisingly long internal thermalization time is attributed to an additional decay mechanism (besides the classical e-e scattering) for the energy loss of NNEs, identified as the ultrafast chemical interface scattering process. NNEs experience an inelastic resonant scattering process into unoccupied electronic states of adsorbates, that directly act as an efficient heat bath, via the excitation of molecular vibrational modes. The two-temperature model is no longer

Ultrafast All-Optical Switching of Germanium-Based Flexible Metaphotonic Devices.

PubMed

Lim, Wen Xiang; Manjappa, Manukumara; Srivastava, Yogesh Kumar; Cong, Longqing; Kumar, Abhishek; MacDonald, Kevin F; Singh, Ranjan

2018-03-01

Incorporating semiconductors as active media into metamaterials offers opportunities for a wide range of dynamically switchable/tunable, technologically relevant optical functionalities enabled by strong, resonant light-matter interactions within the semiconductor. Here, a germanium-thin-film-based flexible metaphotonic device for ultrafast optical switching of terahertz radiation is experimentally demonstrated. A resonant transmission modulation depth of 90% is achieved, with an ultrafast full recovery time of 17 ps. An observed sub-picosecond decay constant of 670 fs is attributed to the presence of trap-assisted recombination sites in the thermally evaporated germanium film. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Single molecule fluorescence imaging as a technique for barium tagging in neutrinoless double beta decay

NASA Astrophysics Data System (ADS)

Jones, B. J. P.; McDonald, A. D.; Nygren, D. R.

2016-12-01

Background rejection is key to success for future neutrinoless double beta decay experiments. To achieve sensitivity to effective Majorana lifetimes of ~ 1028 years, backgrounds must be controlled to better than 0.1 count per ton per year, beyond the reach of any present technology. In this paper we propose a new method to identify the birth of the barium daughter ion in the neutrinoless double beta decay of 136Xe. The method adapts Single Molecule Fluorescent Imaging, a technique from biochemistry research with demonstrated single ion sensitivity. We explore possible SMFI dyes suitable for the problem of barium ion detection in high pressure xenon gas, and develop a fiber-coupled sensing system with which we can detect the presence of bulk Ba++ ions remotely. We show that our sensor produces signal-to-background ratios as high as 85 in response to Ba++ ions when operated in aqueous solution. We then describe the next stage of this R&D program, which will be to demonstrate chelation and fluorescence in xenon gas. If a successful barium ion tag can be developed using SMFI adapted for high pressure xenon gas detectors, the first essentially zero background, ton-scale neutrinoless double beta decay technology could be realized.

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

PubMed

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. © 2014 by The American Society for Biochemistry and Molecular Biology, Inc.

Sizing protein-templated gold nanoclusters by time resolved fluorescence anisotropy decay measurements

NASA Astrophysics Data System (ADS)

Soleilhac, Antonin; Bertorelle, Franck; Antoine, Rodolphe

2018-03-01

Protein-templated gold nanoclusters (AuNCs) are very attractive due to their unique fluorescence properties. A major problem however may arise due to protein structure changes upon the nucleation of an AuNC within the protein for any future use as in vivo probes, for instance. In this work, we propose a simple and reliable fluorescence based technique measuring the hydrodynamic size of protein-templated gold nanoclusters. This technique uses the relation between the time resolved fluorescence anisotropy decay and the hydrodynamic volume, through the rotational correlation time. We determine the molecular size of protein-directed AuNCs, with protein templates of increasing sizes, e.g. insulin, lysozyme, and bovine serum albumin (BSA). The comparison of sizes obtained by other techniques (e.g. dynamic light scattering and small-angle X-ray scattering) between bare and gold clusters containing proteins allows us to address the volume changes induced either by conformational changes (for BSA) or the formation of protein dimers (for insulin and lysozyme) during cluster formation and incorporation.

Sizing protein-templated gold nanoclusters by time resolved fluorescence anisotropy decay measurements.

PubMed

Soleilhac, Antonin; Bertorelle, Franck; Antoine, Rodolphe

2018-03-15

Protein-templated gold nanoclusters (AuNCs) are very attractive due to their unique fluorescence properties. A major problem however may arise due to protein structure changes upon the nucleation of an AuNC within the protein for any future use as in vivo probes, for instance. In this work, we propose a simple and reliable fluorescence based technique measuring the hydrodynamic size of protein-templated gold nanoclusters. This technique uses the relation between the time resolved fluorescence anisotropy decay and the hydrodynamic volume, through the rotational correlation time. We determine the molecular size of protein-directed AuNCs, with protein templates of increasing sizes, e.g. insulin, lysozyme, and bovine serum albumin (BSA). The comparison of sizes obtained by other techniques (e.g. dynamic light scattering and small-angle X-ray scattering) between bare and gold clusters containing proteins allows us to address the volume changes induced either by conformational changes (for BSA) or the formation of protein dimers (for insulin and lysozyme) during cluster formation and incorporation. Copyright © 2017 Elsevier B.V. All rights reserved.

Existence of a new emitting singlet state of proflavine: femtosecond dynamics of the excited state processes and quantum chemical studies in different solvents.

PubMed

Kumar, Karuppannan Senthil; Selvaraju, Chellappan; Malar, Ezekiel Joy Padma; Natarajan, Paramasivam

2012-01-12

Proflavine (3,6-diaminoacridine) shows fluorescence emission with lifetime, 4.6 ± 0.2 ns, in all the solvents irrespective of the solvent polarity. To understand this unusual photophysical property, investigations were carried out using steady state and time-resolved fluorescence spectroscopy in the pico- and femtosecond time domain. Molecular geometries in the ground and low-lying excited states of proflavine were examined by complete structural optimization using ab initio quantum chemical computations at HF/6-311++G** and CIS/6-311++G** levels. Time dependent density functional theory (TDDFT) calculations were performed to study the excitation energies in the low-lying excited states. The steady state absorption and emission spectral details of proflavine are found to be influenced by solvents. The femtosecond fluorescence decay of the proflavine in all the solvents follows triexponential function with two ultrafast decay components (τ(1) and τ(2)) in addition to the nanosecond component. The ultrafast decay component, τ(1), is attributed to the solvation dynamics of the particular solvent used. The second ultrafast decay component, τ(2), is found to vary from 50 to 215 ps depending upon the solvent. The amplitudes of the ultrafast decay components vary with the wavelength and show time dependent spectral shift in the emission maximum. The observation is interpreted that the time dependent spectral shift is not only due to solvation dynamics but also due to the existence of more than one emitting state of proflavine in the solvent used. Time resolved area normalized emission spectral (TRANES) analysis shows an isoemissive point, indicating the presence of two emitting states in homogeneous solution. Detailed femtosecond fluorescence decay analysis allows us to isolate the two independent emitting components of the close lying singlet states. The CIS and TDDFT calculations also support the existence of the close lying emitting states. The near constant

Ultrafast Phenomena XIV

NASA Astrophysics Data System (ADS)

Kobayashi, Takayoshi; Okada, Tadashi; Kobayashi, Tetsuro; Nelson, Keith A.; de Silvestri, Sandro

Ultrafast Phenomena XIV presents the latest advances in ultrafast science, including ultrafast laser and measurement technology as well as studies of ultrafast phenomena. Pico-, femto-, and atosecond processes relevant in physics, chemistry, biology, and engineering are presented. Ultrafast technology is now having a profound impact within a wide range of applications, among them imaging, material diagnostics, and transformation and high-speed optoelectronics . This book summarizes results presented at the 14th Ultrafast Phenomena Conference and reviews the state of the art in this important and rapidly advancing field.

Development of ZnO:Ga as an Ultrafast Scintillator

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

Bourret-Courchesne, E.D.; Derenzo, S.E.; Weber, M.J.

We report on several methods for synthesizing the ultra-fast scintillator ZnO(Ga), and measurements of the resulting products. This material has characteristics that make it an excellent alpha detector for tagging the time and direction of individual neutrons produced by t-d and d-d neutron generators (associated particle imaging). The intensity and decay time are strongly dependent on the method used for dopant incorporation. We compare samples made by diffusion of Ga metal to samples made by solid state reaction between ZnO and Ga2O3 followed by reduction in hydrogen. The latter is much more successful and has a pure, strong near-band-edge fluorescencemore » and an ultra-fast decay time of the x-ray-excited luminescence. The luminescence increases dramatically as the temperature is reduced to 10K. We also present results of an alternate low-temperature synthesis that produces luminescent particles with a more uniform size distribution. We examine possible mechanisms for the bright near-band-edge scintillation and favor the explanation that it is due to the recombination of Ga3+ donor electrons with ionization holes trapped on H+ ion acceptors.« less

Fluorescence decay time imaging using an imaging photon detector with a radio frequency photon correlation system

NASA Astrophysics Data System (ADS)

Morgan, Christopher G.; Mitchell, A. C.; Murray, J. G.

1990-05-01

An imaging photon detector has been modified to incorporate fast timing electronics coupled to a custom built photon correlator interfaced to a RISC computer. Using excitation with intensity- muodulated light, fluorescence images can be readily obtained where contrast is determined by the decay time of emission, rather than by intensity. This technology is readily extended to multifrequency phase/demodulation fluorescence imaging or to differential polarised phase fluorometry. The potential use of the correlator for confocal imaging with a laser scanner is also briefly discussed.

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

PubMed Central

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

2016-01-01

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

A new front-face optical cell for measuring weak fluorescent emissions with time resolution in the picosecond time scale.

PubMed

Gryczynski, Z; Bucci, E

1993-11-01

Recent developments of ultrafast fluorimeters allow measuring time-resolved fluorescence on the picosecond time scale. This implies one is able to monitor lifetimes and anisotropy decays of highly quenched systems and of systems that contain fluorophores having lifetimes in the subnanosecond range; both systems that emit weak signals. The combination of weak signals and very short lifetimes makes the measurements prone to distortions which are negligible in standard fluorescence experiments. To cope with these difficulties, we have designed a new optical cell for front-face optics which offers to the excitation beam a horizontal free liquid surface in the absence of interactions with optical windows. The new cell has been tested with probes of known lifetimes and anisotropies. It proved very useful in detecting tryptophan fluorescence in hemoglobin. If only diluted samples are available, which cannot be used in front-face optics, regular square geometry can still be utilized by inserting light absorbers into a cuvette of 1 cm path length.

Ultrafast hydrogen bond dynamics and partial electron transfer after photoexcitation of diethyl ester of 7-(diethylamino)-coumarin-3-phosphonic acid and its benzoxaphosphorin analog.

PubMed

Wagner, M S; Ilieva, E D; Petkov, P St; Nikolova, R D; Kienberger, R; Iglev, H

2015-04-21

The solvation dynamics after optical excitation of two phosphono-substituted coumarin derivatives dissolved in various solutions are studied by fluorescence up-conversion spectroscopy and quantum chemical simulations. The Kamlet-Taft analysis of the conventional absorption and emission spectra suggests weakening of the solvent-solute H-bonds upon optical excitation, which is in contrast to the results gained by the quantum simulations and earlier studies reported for coumarin derivatives without phosphono groups. The simulations give evidence that the solvent reorganisation around the excited fluorophore leads to partial electron transfer to the first solvation shell. The process occurs on a timescale between 1 and 10 ps depending on the solvent polarity and leads to a fast decay of the time-resolved emission signal. Using the ultrafast spectral shift of the time-dependent fluorescence we estimated the relaxation time of the H-bonds in the electronically excited state to be about 0.6 ps in water, 1.5 ps in ethanol and 2.8 ps in formamide.

Monitoring solute interactions with poly(ethylene oxide)-modified colloidal silica nanoparticles via fluorescence anisotropy decay.

PubMed

Tleugabulova, Dina; Duft, Andy M; Brook, Michael A; Brennan, John D

2004-01-06

The fluorescence-based nanosize metrology approach, proposed recently by Geddes and Birch (Geddes, C. D.; Birch, D. J. S. J. Non-Cryst. Solids 2000, 270, 191), was used to characterize the extent of binding of a fluorescent cationic solute, rhodamine 6G (R6G), to the surface of silica particles after modification of the surface with the hydrophilic polymer poly(ethylene oxide) (PEO) of various molecular weights. The measurement of the rotational dynamics of R6G in PEO solutions showed the absence of strong interactions between R6G and PEO chains in water and the ability of the dye to sense the presence of polymer clusters in 30 wt % solutions. Time-resolved anisotropy decays of polymer-modified Ludox provided direct evidence for distribution of the dye between bound and free states, with the bound dye showing two decay components: a nanosecond decay component that is consistent with local motions of bound probes and a residual anisotropy component due to slow rotation of large silica particles. The data showed that the dye was strongly adsorbed to unmodified silica nanoparticles, to the extent that less than 1% of the dye was present in the surrounding aqueous solution. Addition of PEO blocked the adsorption of the dye to a significant degree, with up to 50% of the probe being present in the aqueous solution for Ludox samples containing 30 wt % of low molecular weight PEO. The addition of such agents also decreased the value and increased the fractional contribution of the nanosecond rotational correlation time, suggesting that polymer adsorption altered the degree of local motion of the bound probe. Atomic force microscopy imaging studies provided no evidence for a change in the particle size upon surface modification but did suggest interparticle aggregation after polymer adsorption. Thus, this redistribution of the probe is interpreted as being due to coverage of particles with the polymer, resulting in lower adsorption of R6G to the silica. The data clearly

Robust Bayesian Fluorescence Lifetime Estimation, Decay Model Selection and Instrument Response Determination for Low-Intensity FLIM Imaging

PubMed Central

Rowley, Mark I.; Coolen, Anthonius C. C.; Vojnovic, Borivoj; Barber, Paul R.

2016-01-01

We present novel Bayesian methods for the analysis of exponential decay data that exploit the evidence carried by every detected decay event and enables robust extension to advanced processing. Our algorithms are presented in the context of fluorescence lifetime imaging microscopy (FLIM) and particular attention has been paid to model the time-domain system (based on time-correlated single photon counting) with unprecedented accuracy. We present estimates of decay parameters for mono- and bi-exponential systems, offering up to a factor of two improvement in accuracy compared to previous popular techniques. Results of the analysis of synthetic and experimental data are presented, and areas where the superior precision of our techniques can be exploited in Förster Resonance Energy Transfer (FRET) experiments are described. Furthermore, we demonstrate two advanced processing methods: decay model selection to choose between differing models such as mono- and bi-exponential, and the simultaneous estimation of instrument and decay parameters. PMID:27355322

Demonstration of Single-Barium-Ion Sensitivity for Neutrinoless Double-Beta Decay Using Single-Molecule Fluorescence Imaging.

PubMed

McDonald, A D; Jones, B J P; Nygren, D R; Adams, C; Álvarez, V; Azevedo, C D R; Benlloch-Rodríguez, J M; Borges, F I G M; Botas, A; Cárcel, S; Carrión, J V; Cebrián, S; Conde, C A N; Díaz, J; Diesburg, M; Escada, J; Esteve, R; Felkai, R; Fernandes, L M P; Ferrario, P; Ferreira, A L; Freitas, E D C; Goldschmidt, A; Gómez-Cadenas, J J; González-Díaz, D; Gutiérrez, R M; Guenette, R; Hafidi, K; Hauptman, J; Henriques, C A O; Hernandez, A I; Hernando Morata, J A; Herrero, V; Johnston, S; Labarga, L; Laing, A; Lebrun, P; Liubarsky, I; López-March, N; Losada, M; Martín-Albo, J; Martínez-Lema, G; Martínez, A; Monrabal, F; Monteiro, C M B; Mora, F J; Moutinho, L M; Muñoz Vidal, J; Musti, M; Nebot-Guinot, M; Novella, P; Palmeiro, B; Para, A; Pérez, J; Querol, M; Repond, J; Renner, J; Riordan, S; Ripoll, L; Rodríguez, J; Rogers, L; Santos, F P; Dos Santos, J M F; Simón, A; Sofka, C; Sorel, M; Stiegler, T; Toledo, J F; Torrent, J; Tsamalaidze, Z; Veloso, J F C A; Webb, R; White, J T; Yahlali, N

2018-03-30

A new method to tag the barium daughter in the double-beta decay of ^{136}Xe is reported. Using the technique of single molecule fluorescent imaging (SMFI), individual barium dication (Ba^{++}) resolution at a transparent scanning surface is demonstrated. A single-step photobleach confirms the single ion interpretation. Individual ions are localized with superresolution (∼2  nm), and detected with a statistical significance of 12.9σ over backgrounds. This lays the foundation for a new and potentially background-free neutrinoless double-beta decay technology, based on SMFI coupled to high pressure xenon gas time projection chambers.

Demonstration of Single-Barium-Ion Sensitivity for Neutrinoless Double-Beta Decay Using Single-Molecule Fluorescence Imaging

NASA Astrophysics Data System (ADS)

McDonald, A. D.; Jones, B. J. P.; Nygren, D. R.; Adams, C.; Álvarez, V.; Azevedo, C. D. R.; Benlloch-Rodríguez, J. M.; Borges, F. I. G. M.; Botas, A.; Cárcel, S.; Carrión, J. V.; Cebrián, S.; Conde, C. A. N.; Díaz, J.; Diesburg, M.; Escada, J.; Esteve, R.; Felkai, R.; Fernandes, L. M. P.; Ferrario, P.; Ferreira, A. L.; Freitas, E. D. C.; Goldschmidt, A.; Gómez-Cadenas, J. J.; González-Díaz, D.; Gutiérrez, R. M.; Guenette, R.; Hafidi, K.; Hauptman, J.; Henriques, C. A. O.; Hernandez, A. I.; Hernando Morata, J. A.; Herrero, V.; Johnston, S.; Labarga, L.; Laing, A.; Lebrun, P.; Liubarsky, I.; López-March, N.; Losada, M.; Martín-Albo, J.; Martínez-Lema, G.; Martínez, A.; Monrabal, F.; Monteiro, C. M. B.; Mora, F. J.; Moutinho, L. M.; Muñoz Vidal, J.; Musti, M.; Nebot-Guinot, M.; Novella, P.; Palmeiro, B.; Para, A.; Pérez, J.; Querol, M.; Repond, J.; Renner, J.; Riordan, S.; Ripoll, L.; Rodríguez, J.; Rogers, L.; Santos, F. P.; dos Santos, J. M. F.; Simón, A.; Sofka, C.; Sorel, M.; Stiegler, T.; Toledo, J. F.; Torrent, J.; Tsamalaidze, Z.; Veloso, J. F. C. A.; Webb, R.; White, J. T.; Yahlali, N.; NEXT Collaboration

2018-03-01

A new method to tag the barium daughter in the double-beta decay of Xe 136 is reported. Using the technique of single molecule fluorescent imaging (SMFI), individual barium dication (Ba++ ) resolution at a transparent scanning surface is demonstrated. A single-step photobleach confirms the single ion interpretation. Individual ions are localized with superresolution (˜2 nm ), and detected with a statistical significance of 12.9 σ over backgrounds. This lays the foundation for a new and potentially background-free neutrinoless double-beta decay technology, based on SMFI coupled to high pressure xenon gas time projection chambers.

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

PubMed

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

2016-04-20

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

Ultrafast photophysics of pi-conjugated polymers for organic light emitting diode applications

NASA Astrophysics Data System (ADS)

Olejnik, Ella

In this work we used the pump-probe photomodulation (PM) spectroscopy technique to measure the transient PM spectrum and decay kinetics in various pi -- conjugated polymers (PCPs) films and blends. Using two ultrafast laser systems, we covered a broad spectral range from 0.25 -- 2.5 eV in the time domain from 200 fs to 1 ns with 150 fs time resolution. We also used continuous wave (CW) photomodulation spectroscopy, photoluminescence (PL), electro-absorption and doping-induced absorption to study the photoexcitations and other optical properties of PCPs and guest/ host blends. In particular we studied two different types of Poly(thienylenevinylene) polymer derivatives. One polymer type is the ordered regio-regular (RR) and regio-random (RRa) -- PTV in which the dark exciton, 2Ag is the lowest excited state. In these polymers the photoexcited exciton shows very fast decay kinetics due to the internal conversion to the dark exciton, which results in weak PL emission; thus these two polymers are non-luminescent. The other PTV derivative is the imide -- PTV which is more luminescent due to the proximity of 1Bu and 2Ag states, that results in longer decay kinetics and a difference between the calculated value of the QEPL (9%) and the measured one (1%). We also demonstrate transient strain spectroscopy in RR -- PTV thin films, where the ultrafast energy release associated with the exciton decay gives rise to substantial static and dynamic strains in the film that dramatically influences the film's transient PM response. We also study the photophysics of poly(dioctyloxy) phenylenevinylene polymer with different isotopes, where we substituted hydrogen (H-polymer) by deuterium (D-polymer), and 12C by 13C isotopes. From the transient decay kinetics measurements we found that the exciton recombination in DOO -- PPV consists of two processes. These are: intrinsic monomolecular, and exciton-exciton annihilation (bimolecular). In the D -- polymer, different probe frequencies of

Protonation-induced ultrafast torsional dynamics in 9-anthrylbenzimidazole: a pH activated molecular rotor.

PubMed

Nandi, Amitabha; Kushwaha, Archana; Das, Dipanwita; Ghosh, Rajib

2018-03-07

We report the photophysical properties and excited state dynamics of 9-anthrylbenzimidazole (ANBI) which exhibits protonation-induced molecular rotor properties. In contrast to the highly emissive behavior of neutral ANBI, protonation of the benzimidazole group of ANBI induces efficient nonradiative deactivation by ultrafast torsional motion around the bond connecting the anthracene and benzimidazole units, as revealed by ultrafast transient absorption and fluorescence spectroscopy. Contrary to viscosity-independent fluorescence of neutral dyes, protonated ANBI is shown to display linear variation of emission yield and lifetime with solvent viscosity. The protonation-induced molecular rotor properties in the studied system are shown to be driven by enhanced charge transfer and are corroborated by quantum chemical calculations. Potential application as a microviscosity sensor of acidic regions in a heterogeneous environment by these proton-activated molecular rotor properties of ANBI is discussed.

Ultrafast decay of hot phonons in an AlGaN/AlN/AlGaN/GaN camelback channel

NASA Astrophysics Data System (ADS)

Leach, J. H.; Wu, M.; Morkoç, H.; Liberis, J.; Šermukšnis, E.; Ramonas, M.; Matulionis, A.

2011-11-01

A bottleneck for heat dissipation from the channel of a GaN-based heterostructure field-effect transistor is treated in terms of the lifetime of nonequilibrium (hot) longitudinal optical phonons, which are responsible for additional scattering of electrons in the voltage-biased quasi-two-dimensional channel. The hot-phonon lifetime is measured for an Al0.33Ga0.67N/AlN/Al0.1Ga0.9N/GaN heterostructure where the mobile electrons are spread in a composite Al0.1Ga0.9N/GaN channel and form a camelback electron density profile at high electric fields. In accordance with plasmon-assisted hot-phonon decay, the parameter of importance for the lifetime is not the total charge in the channel (the electron sheet density) but rather the electron density profile. This is demonstrated by comparing two structures with equal sheet densities (1 × 1013 cm-2), but with different density profiles. The camelback channel profile exhibits a shorter hot-phonon lifetime of ˜270 fs as compared with ˜500 fs reported for a standard Al0.33Ga0.67N/AlN/GaN channel at low supplied power levels. When supplied power is sufficient to heat the electrons > 600 K, ultrafast decay of hot phonons is observed in the case of the composite channel structure. In this case, the electron density profile spreads to form a camelback profile, and hot-phonon lifetime reduces to ˜50 fs.

Real-time method and apparatus for measuring the decay-time constant of a fluorescing phosphor

DOEpatents

Britton, Jr., Charles L.; Beshears, David L.; Simpson, Marc L.; Cates, Michael R.; Allison, Steve W.

1999-01-01

A method for determining the decay-time constant of a fluorescing phosphor is provided, together with an apparatus for performing the method. The apparatus includes a photodetector for detecting light emitted by a phosphor irradiated with an excitation pulse and for converting the detected light into an electrical signal. The apparatus further includes a differentiator for differentiating the electrical signal and a zero-crossing discrimination circuit that outputs a pulse signal having a pulse width corresponding to the time period between the start of the excitation pulse and the time when the differentiated electrical signal reaches zero. The width of the output pulse signal is proportional to the decay-time constant of the phosphor.

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

NASA Astrophysics Data System (ADS)

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.

Enhanced fluorescence of epicocconone in surfactant assemblies as a consequence of depth-dependent microviscosity.

PubMed

Panda, Debashis; Khatua, Saumyakanti; Datta, Anindya

2007-02-22

The extents of fluorescence enhancement of epicocconone are found to be different in the micelles of the surfactants sodium dodecyl sulfate (SDS) and Triton X100 (TX 100). A decrease in fluorescence, observed in the cationic cetyltrimethylammonium bromide (CTAB) micelles, is rationalized by the formation of anions of the fluorophore at the Stern layer. To understand the difference in the effects of SDS and TX 100, the nature of the excited-state process in the fluorophore has been investigated by fluorescence spectroscopy, supported by complementary quantum chemical calculations. The excited-state dynamics of epicocconone is found to depend on polarity and viscosity of the medium, with a more pronounced dependence on viscosity. An inspection of the molecular orbitals involved in the electronic absorption of the molecule reveals the possibility of photoisomerization, which conforms to the observed solvent dependence of the fluorescence spectral properties. An apparent mismatch between trends observed in steady-state spectra and those in temporal decays indicates a significant contribution of an ultrafast component, which cannot be detected in the time resolution of our instrument. The viscosity dependence of the fluorescence quantum yields provides an explanation for the difference in the extents of fluorescence enhancement in the two micelles, in the light of location of the fluorophore at different depths of the micelle. The enhancement of fluorescence, with an unchanged fluorescence maximum, opens up the possibility that the fluorophore could be a useful dual emitting marker for fluorescence microscopy of heterogeneous systems, as the fluorescence of protein-bound epicocconone has been previously reported to be significantly red-shifted.

Ultrafast Photoinduced Electron Transfer in a π-Conjugated Oligomer/Porphyrin Complex.

PubMed

Aly, Shawkat M; Goswami, Subhadip; Alsulami, Qana A; Schanze, Kirk S; Mohammed, Omar F

2014-10-02

Controlling charge transfer (CT), charge separation (CS), and charge recombination (CR) at the donor-acceptor interface is extremely important to optimize the conversion efficiency in solar cell devices. In general, ultrafast CT and slow CR are desirable for optimal device performance. In this Letter, the ultrafast excited-state CT between platinum oligomer (DPP-Pt(acac)) as a new electron donor and porphyrin as an electron acceptor is monitored for the first time using femtosecond (fs) transient absorption (TA) spectroscopy with broad-band capability and 120 fs temporal resolution. Turning the CT on/off has been shown to be possible either by switching from an organometallic oligomer to a metal-free oligomer or by controlling the charge density on the nitrogen atom of the porphyrin meso unit. Our time-resolved data show that the CT and CS between DPP-Pt(acac) and cationic porphyrin are ultrafast (approximately 1.5 ps), and the CR is slow (ns time scale), as inferred from the formation and the decay of the cationic and anionic species. We also found that the metallic center in the DPP-Pt(acac) oligomer and the positive charge on the porphyrin are the keys to switching on/off the ultrafast CT process.

Research on the ultrafast fluorescence property of thylakoid membranes of the wild-type and mutant rice

NASA Astrophysics Data System (ADS)

Ren, Zhao-Yu; Xu, Xiao-Ming; Wang, Shui-Cai; Xin, Yue-Yong; He, Jun-Fang; Hou, Xun

2003-10-01

A high yielding rice variety mutant (Oryza sativa L., Zhenhui 249) with low chlorophyll b (Chl b) has been discovered in natural fields. It has a quality character controlled by a pair of recessive genes (nuclear gene). The partial loss of Chl b in content affects the efficiency of light harvest in a light harvest complex (LHC), thus producing the difference of the exciting energy transfer and the efficiency of photochemistry conversion between the mutant and wild-type rice in photosynthetic unit. The efficiency of utilizing light energy is higher in the mutant than that in the wild-type rice relatively. For further discussion of the above-mentioned difference and learning about the mechanism of the increase in the photochemical efficiency of the mutant, the pico-second resolution fluorescence spectrum measurement with delay-frame-scanning single photon counting technique is adopted. Thylakoid membranes of the mutant and the wild-type rice are excited by an Ar+ laser with a pulse width of 120 ps, repetition rate of 4 MHz and wavelength of 514 nm. Compared with the time and spectrum property of exciting fluorescence, conclusions of those ultrafast dynamic experiments are: 1) The speeds of the exciting energy transferred in photo-system I are faster than that in photo-system II in both samples. 2) The speeds of the exciting energy transfer of mutant sample are faster than those of the wild-type. This might be one of the major reasons why the efficiency of photosynthesis is higher in mutant than that in the wild-type rice.

Demonstration of Single-Barium-Ion Sensitivity for Neutrinoless Double-Beta Decay Using Single-Molecule Fluorescence Imaging

DOE PAGES

McDonald, A. D.; Jones, B. J. P.; Nygren, D. R.; ...

2018-03-26

A new method to tag the barium daughter in the double beta decay ofmore » $$^{136}$$Xe is reported. Using the technique of single molecule fluorescent imaging (SMFI), individual barium dication (Ba$$^{++}$$) resolution at a transparent scanning surface has been demonstrated. A single-step photo-bleach confirms the single ion interpretation. Individual ions are localized with super-resolution ($$\\sim$$2~nm), and detected with a statistical significance of 12.9~$$\\sigma$$ over backgrounds. This lays the foundation for a new and potentially background-free neutrinoless double beta decay technology, based on SMFI coupled to high pressure xenon gas time projection chambers.« less

Progress towards barium daughter tagging in Xe136 decay using single molecule fluorescence imaging

NASA Astrophysics Data System (ADS)

McDonald, Austin; NEXT Collaboration

2017-09-01

The existence of Majorana fermions is of great interest as it may be related to the asymmetry between matter and anti-matter particles in the universe. However, the search for them has proven to be a difficult one. Neutrino-less Double Beta decay (NLDB) offers a possible opportunity for direct observation of a Majorana Fermion. The rate for NLDB decay may be as low as 1 count /ton /year if the mass ordering is inverted. Current detector technologies have background rates between 4 to 300 count /ton /year /ROI at the 100kg scale which is much larger than the universal goal of 0.1 count /ton /year /ROI desired for ton-scale detectors. The premise of my research is to develop new detector technologies that will allow for a background-free experiment. My current work is to develop a sensor that will tag the daughter ion Ba++ from the Xe136 decay. The development of a sensor that is sensitive to single barium ion detection based on the single molecule fluorescence imaging technique is the major focus of this work. If successful, this could provide a path to a background-free experiment.

Progress towards barium daughter tagging in Xe136 decay using single molecule fluorescence imaging

NASA Astrophysics Data System (ADS)

McDonald, Austin; Jones, Ben; Benson, Jordan; Nygren, David; NEXT Collaboration

2017-01-01

The existence of Majorana Fermions has been predicted, and is of great interest as it may be related to the asymmetry between matter and anti-matter particles in the universe. However, the search for them has proven to be a difficult one. Neutrino-less Double Beta decay (NLDB) offers a possible opportunity for direct observation of a Majorana Fermion. The rate for NLDB decay may be as low as 1 count / ton / year . Current detector technologies have background rates between 4 to 300 count / ton / year / ROI which is much larger than the universal goal of 0 . 1 count / ton / year / ROI desired for ton-scale detectors. The premise of my research is to develop new detector technologies that will allow for a background-free experiment. My current work is to develop a sensor that will tag the daughter ion Ba++ from the Xe136 decay. The development of a sensor that is sensitive to single barium ion detection based on the single molecule fluorescence imaging technique is the major focus of this work. If successful, this could provide a path to a background-free experiment.

Ultra-fast relaxation, decoherence, and localization of photoexcited states in π-conjugated polymers

NASA Astrophysics Data System (ADS)

Mannouch, Jonathan R.; Barford, William; Al-Assam, Sarah

2018-01-01

The exciton relaxation dynamics of photoexcited electronic states in poly(p-phenylenevinylene) are theoretically investigated within a coarse-grained model, in which both the exciton and nuclear degrees of freedom are treated quantum mechanically. The Frenkel-Holstein Hamiltonian is used to describe the strong exciton-phonon coupling present in the system, while external damping of the internal nuclear degrees of freedom is accounted for by a Lindblad master equation. Numerically, the dynamics are computed using the time evolving block decimation and quantum jump trajectory techniques. The values of the model parameters physically relevant to polymer systems naturally lead to a separation of time scales, with the ultra-fast dynamics corresponding to energy transfer from the exciton to the internal phonon modes (i.e., the C-C bond oscillations), while the longer time dynamics correspond to damping of these phonon modes by the external dissipation. Associated with these time scales, we investigate the following processes that are indicative of the system relaxing onto the emissive chromophores of the polymer: (1) Exciton-polaron formation occurs on an ultra-fast time scale, with the associated exciton-phonon correlations present within half a vibrational time period of the C-C bond oscillations. (2) Exciton decoherence is driven by the decay in the vibrational overlaps associated with exciton-polaron formation, occurring on the same time scale. (3) Exciton density localization is driven by the external dissipation, arising from "wavefunction collapse" occurring as a result of the system-environment interactions. Finally, we show how fluorescence anisotropy measurements can be used to investigate the exciton decoherence process during the relaxation dynamics.

Ultrafast Hydration Dynamics and Coupled Water-Protein Fluctuations in Apomyoglobin

NASA Astrophysics Data System (ADS)

Yang, Yi; Zhang, Luyuan; Wang, Lijuan; Zhong, Dongping

2009-06-01

Protein hydration dynamics are of fundamental importance to its structure and function. Here, we characterize the global solvation dynamics and anisotropy dynamics around the apomyoglobin surface in different conformational states (native and molten globule) by measuring the Stokes shift and anisotropy decay of tryptophan with femtosecond-resolved fluorescence upconversion. With site-directed mutagenesis, we designed sixteen mutants with one tryptophan in each, and placed the probe at a desirable position ranging from buried in the protein core to fully solvent-exposed on the protein surface. In all protein sites studied, two distinct solvation relaxations (1-8 ps and 20-200 ps) were observed, reflecting the initial collective water relaxation and subsequent hydrogen-bond network restructuring, respectively, and both are strongly correlated with protein's local structures and chemical properties. The hydration dynamics of the mutants in molten globule state are faster than those observed in native state, indicating that the protein becomes more flexible and less structured when its conformation is converted from fully-folded native state to partially-folded molten globule state. Complementary, fluorescence anisotropy dynamics of all mutants in native state show an increasing trend of wobbling times (40-260 ps) when the location of the probe is changed from a loop, to a lateral helix, and then, to the compact protein core. Such an increase in wobbling times is related to the local protein structural rigidity, which relates the interaction of water with side chains. The ultrafast hydration dynamics and related side-chain motion around the protein surface unravel the coupled water-protein fluctuations on the picosecond time scales and indicate that the local protein motions are slaved by hydrating water fluctuations.

Optimizing ultrafast illumination for multiphoton-excited fluorescence imaging

PubMed Central

Stoltzfus, Caleb R.; Rebane, Aleksander

2016-01-01

We study the optimal conditions for high throughput two-photon excited fluorescence (2PEF) and three-photon excited fluorescence (3PEF) imaging using femtosecond lasers. We derive relations that allow maximization of the rate of imaging depending on the average power, pulse repetition rate, and noise characteristics of the laser, as well as on the size and structure of the sample. We perform our analysis using ~100 MHz, ~1 MHz and 1 kHz pulse rates and using both a tightly-focused illumination beam with diffraction-limited image resolution, as well loosely focused illumination with a relatively low image resolution, where the latter utilizes separate illumination and fluorescence detection beam paths. Our theoretical estimates agree with the experiments, which makes our approach especially useful for optimizing high throughput imaging of large samples with a field-of-view up to 10x10 cm2. PMID:27231620

Ultrafast electronic dynamics driven by nuclear motion

NASA Astrophysics Data System (ADS)

Vendrell, Oriol

2016-05-01

The transfer of electrical charge on a microscopic scale plays a fundamental role in chemistry, in biology, and in technological applications. In this contribution, we will discuss situations in which nuclear motion plays a central role in driving the electronic dynamics of photo-excited or photo-ionized molecular systems. In particular, we will explore theoretically the ultrafast transfer of a double electron hole between the functional groups of glycine after K-shell ionization and subsequent Auger decay. Although a large energy gap of about 15 eV initially exists between the two electronic states involved and coherent electronic dynamics play no role in the hole transfer, we will illustrate how the double hole can be transferred within 3 to 4 fs between both functional ends of the glycine molecule driven solely by specific nuclear displacements and non-Born-Oppenheimer effects. This finding challenges the common wisdom that nuclear dynamics of the molecular skeleton are unimportant for charge transfer processes at the few-femtosecond time scale and shows that they can even play a prominent role. We thank the Hamburg Centre for Ultrafast Imaging and the Volkswagen Foundation for financial support.

Nonequilibrium dynamics of the phonon gas in ultrafast-excited antimony

NASA Astrophysics Data System (ADS)

Krylow, Sergej; Zijlstra, Eeuwe S.; Kabeer, Fairoja Cheenicode; Zier, Tobias; Bauerhenne, Bernd; Garcia, Martin E.

2017-12-01

The ultrafast relaxation dynamics of a nonequilibrium phonon gas towards thermal equilibrium involves many-body collisions that cannot be properly described by perturbative approaches. Here, we develop a nonperturbative method to elucidate the microscopic mechanisms underlying the decay of laser-excited coherent phonons in the presence of electron-hole pairs, which so far are not fully understood. Our theory relies on ab initio molecular dynamics simulations on laser-excited potential-energy surfaces. Those simulations are compared with runs in which the laser-excited coherent phonon is artificially deoccupied. We apply this method to antimony and show that the decay of the A1 g phonon mode at low laser fluences can be accounted mainly to three-body down-conversion processes of an A1 g phonon into acoustic phonons. For higher excitation strengths, however, we see a crossover to a four-phonon process, in which two A1 g phonons decay into two optical phonons.

Room-temperature ultrafast nonlinear spectroscopy of a single molecule

NASA Astrophysics Data System (ADS)

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

2018-01-01

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

Ultrafast photophysics of transition metal complexes.

PubMed

Chergui, Majed

2015-03-17

The properties of transition metal complexes are interesting not only for their potential applications in solar energy conversion, OLEDs, molecular electronics, biology, photochemistry, etc. but also for their fascinating photophysical properties that call for a rethinking of fundamental concepts. With the advent of ultrafast spectroscopy over 25 years ago and, more particularly, with improvements in the past 10-15 years, a new area of study was opened that has led to insightful observations of the intramolecular relaxation processes such as internal conversion (IC), intersystem crossing (ISC), and intramolecular vibrational redistribution (IVR). Indeed, ultrafast optical spectroscopic tools, such as fluorescence up-conversion, show that in many cases, intramolecular relaxation processes can be extremely fast and even shorter than time scales of vibrations. In addition, more and more examples are appearing showing that ultrafast ISC rates do not scale with the magnitude of the metal spin-orbit coupling constant, that is, that there is no heavy-atom effect on ultrafast time scales. It appears that the structural dynamics of the system and the density of states play a crucial role therein. While optical spectroscopy delivers an insightful picture of electronic relaxation processes involving valence orbitals, the photophysics of metal complexes involves excitations that may be centered on the metal (called metal-centered or MC) or the ligand (called ligand-centered or LC) or involve a transition from one to the other or vice versa (called MLCT or LMCT). These excitations call for an element-specific probe of the photophysics, which is achieved by X-ray absorption spectroscopy. In this case, transitions from core orbitals to valence orbitals or higher allow probing the electronic structure changes induced by the optical excitation of the valence orbitals, while also delivering information about the geometrical rearrangement of the neighbor atoms around the atom of

Interpreting Quasi-Thermal Effects in Ultrafast Spectroscopy of Hydrogen-Bonded Systems.

PubMed

Stingel, Ashley M; Petersen, Poul B

2018-03-15

Vibrational excitation of molecules in the condensed phase relaxes through vibrational modes of decreasing energy to ultimately generate an equilibrium state in which the energy is distributed among low-frequency modes. In ultrafast vibrational spectroscopy, changes in the vibrational features of hydrogen-bonded NH and OH stretch modes are typically observed to persist long after these high-frequency vibrations have relaxed. Due to the resemblance to the spectral changes caused by heating the sample, these features are typically described as arising from a hot ground state. However, these spectral features appear on ultrafast time scales that are much too fast to result from a true thermal state, and significant differences between the thermal difference spectrum and the induced quasi-thermal changes in ultrafast spectroscopy are often observed. Here, we examine and directly compare the thermal and quasi-thermal responses of the hydrogen-bonded homodimer of 7-azaindole with temperature-dependent FTIR spectroscopy and ultrafast mid-IR continuum spectroscopy. We find that the thermal difference spectra contain contributions from both dissociation of the hydrogen bonds and from frequency shifts due to changes in the thermal population of low-frequency modes. The transient spectra in ultrafast vibrational spectroscopy are also found to contain two contributions: initial frequency shifts over 2.3 ± 0.11 ps associated with equilibration of the initial excitation, and frequency shifts associated with the excitation of several fingerprint modes, which decay over 21.8 ± 0.11 ps, giving rise to a quasi-thermal response caused by a distribution of fingerprint modes being excited within the sample ensemble. This resembles the thermal frequency shifts due to population changes of low-frequency modes, but not the overall thermal spectrum, which is dominated by features caused by dimer dissociation. These findings provide insight into the changes in the vibrational spectrum

Picosecond phase-velocity dispersion of hypersonic phonons imaged with ultrafast electron microscopy

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

Cremons, Daniel R.; Du, Daniel X.; Flannigan, David J.

We describe the direct imaging—with four-dimensional ultrafast electron microscopy—of the emergence, evolution, dispersion, and decay of photoexcited, hypersonic coherent acoustic phonons in nanoscale germanium wedges. Coherent strain waves generated via ultrafast in situ photoexcitation were imaged propagating with initial phase velocities of up to 35 km/s across discrete micrometer-scale crystal regions. We then observe that, while each wave front travels at a constant velocity, the entire wave train evolves with a time-varying phase-velocity dispersion, displaying a single-exponential decay to the longitudinal speed of sound (5 km/s) and with a mean lifetime of 280 ps. We also find that the wavemore » trains propagate along a single in-plane direction oriented parallel to striations introduced during specimen preparation, independent of crystallographic direction. Elastic-plate modeling indicates the dynamics arise from excitation of a single, symmetric (dilatational) guided acoustic mode. Further, by precisely determining the experiment time-zero position with a plasma-lensing method, we find that wave-front emergence occurs approximately 100 ps after femtosecond photoexcitation, which matches well with Auger recombination times in germanium. We conclude by discussing the similarities between the imaged hypersonic strain-wave dynamics and electron/hole plasma-wave dynamics in strongly photoexcited semiconductors.« less

Picosecond phase-velocity dispersion of hypersonic phonons imaged with ultrafast electron microscopy

DOE PAGES

Cremons, Daniel R.; Du, Daniel X.; Flannigan, David J.

2017-12-05

We describe the direct imaging—with four-dimensional ultrafast electron microscopy—of the emergence, evolution, dispersion, and decay of photoexcited, hypersonic coherent acoustic phonons in nanoscale germanium wedges. Coherent strain waves generated via ultrafast in situ photoexcitation were imaged propagating with initial phase velocities of up to 35 km/s across discrete micrometer-scale crystal regions. We then observe that, while each wave front travels at a constant velocity, the entire wave train evolves with a time-varying phase-velocity dispersion, displaying a single-exponential decay to the longitudinal speed of sound (5 km/s) and with a mean lifetime of 280 ps. We also find that the wavemore » trains propagate along a single in-plane direction oriented parallel to striations introduced during specimen preparation, independent of crystallographic direction. Elastic-plate modeling indicates the dynamics arise from excitation of a single, symmetric (dilatational) guided acoustic mode. Further, by precisely determining the experiment time-zero position with a plasma-lensing method, we find that wave-front emergence occurs approximately 100 ps after femtosecond photoexcitation, which matches well with Auger recombination times in germanium. We conclude by discussing the similarities between the imaged hypersonic strain-wave dynamics and electron/hole plasma-wave dynamics in strongly photoexcited semiconductors.« less

Ultrafast hole carrier relaxation dynamics in p-type CuO nanowires

PubMed Central

2011-01-01

Ultrafast hole carrier relaxation dynamics in CuO nanowires have been investigated using transient absorption spectroscopy. Following femtosecond pulse excitation in a non-collinear pump-probe configuration, a combination of non-degenerate transmission and reflection measurements reveal initial ultrafast state filling dynamics independent of the probing photon energy. This behavior is attributed to the occupation of states by photo-generated carriers in the intrinsic hole region of the p-type CuO nanowires located near the top of the valence band. Intensity measurements indicate an upper fluence threshold of 40 μJ/cm2 where carrier relaxation is mainly governed by the hole dynamics. The fast relaxation of the photo-generated carriers was determined to follow a double exponential decay with time constants of 0.4 ps and 2.1 ps. Furthermore, time-correlated single photon counting measurements provide evidence of three exponential relaxation channels on the nanosecond timescale. PMID:22151927

White light for the fast lane: supercontinuum generation in all-normal dispersion fibers for ultrafast photonics

NASA Astrophysics Data System (ADS)

Heidt, Alexander M.

2014-03-01

This talk will give an overview of the unique properties of supercontinuum generation (SCG) in all-normal dispersion (ANDi) fibers pumped by ultrashort pulses and the possibilities they offer for ultrafast photonics applications. In contrast to their anomalously pumped counterparts, the SCG process in ANDi fibers conserves a single ultrashort pulse in the time domain, completely suppresses soliton formation and decay, and avoids noise-amplifying nonlinear dynamics. The resulting spectra combine the best of both worlds - the broad, more than octave-spanning bandwidths usually associated with anomalous dispersion pumping with the high temporal coherence, pulse-to-pulse stability and well-defined temporal pulse characteristics known from the normal dispersion regime. These characteristics are ideally suited for ultrafast photonics, and I will present application examples including the generation of high quality single-cycle pulses and their amplification, as well as ultrafast spectroscopy. This talk will also explore the exciting new possibilities enabled by extending this approach into the mid-IR spectral region using novel soft glass fiber designs.

Dynamics of Functionalized Surface Molecular Monolayers Studied with Ultrafast Infrared Vibrational Spectroscopy

PubMed Central

Rosenfeld, Daniel E.; Nishida, Jun; Yan, Chang; Gengeliczki, Zsolt; Smith, Brian J.; Fayer, Michael D.

2012-01-01

The structural dynamics of thin films consisting of tricarbonyl (1,10-phenanthroline)rhenium chloride (RePhen(CO)3Cl) linked to an alkyl silane monolayer through a triazole linker synthesized on silica-on-calcium-fluoride substrates are investigated using ultrafast infrared (IR) techniques. Ultrafast 2D IR vibrational echo experiments and polarization selective heterodyne detected transient grating (HDTG) measurements, as well as polarization dependent FT-IR and AFM experiments are employed to study the samples. The vibrational echo experiments measure spectral diffusion, while the HDTG experiments measure the vibrational excited state population relaxation and investigate the vibrational transition dipole orientational anisotropy decay. To investigate the anticipated impact of vibrational excitation transfer, which can be caused by the high concentration of RePhen(CO)3Cl in the monolayer, a concentration dependence of the spectral diffusion is measured. To generate a range of concentrations, mixed monolayers consisting of both hydrogen terminated and triazole/RePhen(CO)3Cl terminated alkyl silanes are synthesized. It is found that the measured rate of spectral diffusion is independent of concentration, with all samples showing spectral diffusion of 37 ± 6 ps. To definitively test for vibrational excitation transfer, polarization selective HDTG experiments are conducted. Excitation transfer will cause anisotropy decay. Polarization resolved heterodyne detected transient grating spectroscopy is sensitive to anisotropy decay (depolarization) caused by excitation transfer and molecular reorientation. The HDTG experiments show no evidence of anisotropy decay on the appropriate time scale, demonstrating the absence of excitation transfer the RePhen(CO)3Cl. Therefore the influence of excitation transfer on spectral diffusion is inconsequential in these samples, and the vibrational echo measurements of spectral diffusion report solely on structural dynamics. A small

Ultrafast spectroscopic investigation of a fullerene poly(3-hexylthiophene) dyad

NASA Astrophysics Data System (ADS)

Banerji, Natalie; Seifter, Jason; Wang, Mingfeng; Vauthey, Eric; Wudl, Fred; Heeger, Alan J.

2011-08-01

We present the femtosecond spectroscopic investigation of a covalently linked dyad, PCB-P3HT, formed by a segment of the conjugated polymer P3HT (regioregular poly(3-hexylthiophene)) that is end capped with the fullerene derivative PCB ([6,6]-phenyl-C61-butyric acid ester), adapted from PCBM. The fluorescence of the P3HT segment in tetrahydrofuran (THF) solution is reduced by 64% in the dyad compared to a control compound without attached fullerene (P3HT-OH). Fluorescence upconversion measurements reveal that the partial fluorescence quenching of PCB-P3HT in THF is multiphasic and occurs on an average time scale of 100 ps, in parallel to excited-state relaxation processes. Judging from ultrafast transient absorption experiments, the origin of the quenching is excitation energy transfer from the P3HT donor to the PCB acceptor. Due to the much higher solubility of P3HT compared to PCB in THF, the PCB-P3HT dyad molecules self-assemble into micelles. When pure C60 is added to the solution, it is incorporated into the fullerene-rich center of the micelles. This dramatically increases the solubility of C60 but does not lead to significant additional quenching of the P3HT fluorescence by the C60 contained in the micelles. In PCB-P3HT thin films drop-cast from THF, the micelle structure is conserved. In contrast to solution, quantitative and ultrafast (<150 fs) charge separation occurs in the solid-state films and leads to the formation of long-lived mobile charge carriers with characteristic transient absorption signatures similar to those that have been observed in P3HT:PCBM bulk heterojunction blends. While π-stacking interactions between neighboring P3HT chains are weak in the micelles, they are strong in thin films drop-cast from ortho-dichlorobenzene. Here, PCB-P3HT self-assembles into a network of long fibers, clearly seen in atomic force microscopy images. Ultrafast charge separation occurs also for the fibrous morphology, but the transient absorption experiments

Ultrafast photo-initiated molecular quantum dynamics in the DNA dinucleotide d(ApG) revealed by broadband transient absorption spectroscopy.

PubMed

Stuhldreier, Mayra C; Temps, Friedrich

2013-01-01

The ultrafast photo-initiated quantum dynamics of the adenine-guanine dinucleotide d(ApG) in aqueous solution (pH 7) has been studied by femtosecond time-resolved spectroscopy after excitation at lambda = 260 nm. The results reveal a hierarchy of processes on time scales from tau < 100 fs to tau > 100 ps. Characteristic spectro-temporal signatures are observed indicating the transformation of the molecules in the electronic relaxation from the photo-excited state to a long-lived exciplex. In particular, broadband UV/VIS excited-state absorption (ESA) measurements detected a distinctive absorption by the excited dinucleotide around lambda = 335 nm, approximately 0.5 eV to the blue compared to the maximum of the broad and unstructured ESA spectrum after excitation of an equimolar mixture of the mononucleotides dAMP and dGMP. A similar feature has been identified as signature of the excimer in the dynamics of the adenine dinucleotide d(ApA). The lifetime of the d(ApG) exciplex was found to be tau = 124 +/- 4 ps both from the ESA decay time and from the ground-state recovery time, far longer than the sub-picosecond lifetimes of excited dAMP or dGMP. Fluorescence-time profiles measured by the up-conversion technique indicate that the exciplex state is reached around approximately 6 ps after excitation. Very weak residual fluorescence at longer times red-shifted to the emission from the photo-excited state shows that the exciplex is almost optically dark, but still has enough oscillator strength to give rise to the dual fluorescence of the dinucleotide in the static fluorescence spectrum.

Structure of {sup 81}Ga populated from the {beta}{sup -} decay of {sup 81}Zn

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

Paziy, V.; Mach, H.; Fraile, L. M.

2013-06-10

We report on the results of the {beta}-decay of {sup 81}Zn. The experiment was performed at the CERN ISOLDE facility in the framework of a systematic ultra-fast timing investigation of neutron-rich nuclei populated in the decay of Zn. The present analysis included {beta}-gated {gamma}-ray singles and {gamma}-{gamma} coincidences from the decay of {sup 81}Zn to {sup 81}Ga and leads to a new and much more extensive level scheme of {sup 81}Ga. A new half-life of {sup 81}Zn is provided.

Ultrafast photoconductivity of undoped cuprates

NASA Astrophysics Data System (ADS)

Dodge, J. Steven; Farahani, Amir; Petersen, Jesse; Liang, Ruixing; Bozovic, Ivan

2010-03-01

Using a visible pump-THz probe technique, we studied the ultrafast transient photoconductivity of the insulating cuprate La2CuO4, and compared it with earlier measurements of Sr2CuO2Cl2 and YBa2Cu3O6. In all these compounds, we observe a rapid onset of photoconductivity that is followed by a non-exponential relaxation on a picosecond time scales, the dynamics of which are independent of photocarrier concentration ranging from 0.2 to 1.5 percent. The photoconductivity decay is qualitatively similar to the decay of the photoinduced gap absorption in Sr2CuO2Cl2,footnotetextJ. S. Dodge, arXiv:0910.5048 indicating a common origin for the two effects. Assuming a quantum efficiency of unity, the estimated peak mobility for all three compounds is within 0.1-0.4 cm^2/V.s; this is lower than the Hall mobility in chemically doped systems with similar carrier concentrations,footnotetext Ando et al, Phys. Rev. Lett. 87, 017001 (2001) but orders of magnitude larger than earlier DC photoconductivity results.footnotetextThio et al, Phys. Rev. B 42, 10800 (1990) The similarity of the peak photoconductivity across three different compounds indicates that it is an intrinsic feature of the copper oxide plane.

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

NASA Astrophysics Data System (ADS)

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

2006-10-01

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

Direct and simultaneous observation of ultrafast electron and hole dynamics in germanium.

PubMed

Zürch, Michael; Chang, Hung-Tzu; Borja, Lauren J; Kraus, Peter M; Cushing, Scott K; Gandman, Andrey; Kaplan, Christopher J; Oh, Myoung Hwan; Prell, James S; Prendergast, David; Pemmaraju, Chaitanya D; Neumark, Daniel M; Leone, Stephen R

2017-06-01

Understanding excited carrier dynamics in semiconductors is crucial for the development of photovoltaics and efficient photonic devices. However, overlapping spectral features in optical pump-probe spectroscopy often render assignments of separate electron and hole carrier dynamics ambiguous. Here, ultrafast electron and hole dynamics in germanium nanocrystalline thin films are directly and simultaneously observed by ultrafast transient absorption spectroscopy in the extreme ultraviolet at the germanium M 4,5 edge. We decompose the spectra into contributions of electronic state blocking and photo-induced band shifts at a carrier density of 8 × 10 20  cm -3 . Separate electron and hole relaxation times are observed as a function of hot carrier energies. A first-order electron and hole decay of ∼1 ps suggests a Shockley-Read-Hall recombination mechanism. The simultaneous observation of electrons and holes with extreme ultraviolet transient absorption spectroscopy paves the way for investigating few- to sub-femtosecond dynamics of both holes and electrons in complex semiconductor materials and across junctions.

Direct and simultaneous observation of ultrafast electron and hole dynamics in germanium

PubMed Central

Zürch, Michael; Chang, Hung-Tzu; Borja, Lauren J.; Kraus, Peter M.; Cushing, Scott K.; Gandman, Andrey; Kaplan, Christopher J.; Oh, Myoung Hwan; Prell, James S.; Prendergast, David; Pemmaraju, Chaitanya D.; Neumark, Daniel M.; Leone, Stephen R.

2017-01-01

Understanding excited carrier dynamics in semiconductors is crucial for the development of photovoltaics and efficient photonic devices. However, overlapping spectral features in optical pump-probe spectroscopy often render assignments of separate electron and hole carrier dynamics ambiguous. Here, ultrafast electron and hole dynamics in germanium nanocrystalline thin films are directly and simultaneously observed by ultrafast transient absorption spectroscopy in the extreme ultraviolet at the germanium M4,5 edge. We decompose the spectra into contributions of electronic state blocking and photo-induced band shifts at a carrier density of 8 × 1020 cm−3. Separate electron and hole relaxation times are observed as a function of hot carrier energies. A first-order electron and hole decay of ∼1 ps suggests a Shockley–Read–Hall recombination mechanism. The simultaneous observation of electrons and holes with extreme ultraviolet transient absorption spectroscopy paves the way for investigating few- to sub-femtosecond dynamics of both holes and electrons in complex semiconductor materials and across junctions. PMID:28569752

Ultrafast Microfluidic Cellular Imaging by Optical Time-Stretch.

PubMed

Lau, Andy K S; Wong, Terence T W; Shum, Ho Cheung; Wong, Kenneth K Y; Tsia, Kevin K

2016-01-01

There is an unmet need in biomedicine for measuring a multitude of parameters of individual cells (i.e., high content) in a large population efficiently (i.e., high throughput). This is particularly driven by the emerging interest in bringing Big-Data analysis into this arena, encompassing pathology, drug discovery, rare cancer cell detection, emulsion microdroplet assays, to name a few. This momentum is particularly evident in recent advancements in flow cytometry. They include scaling of the number of measurable colors from the labeled cells and incorporation of imaging capability to access the morphological information of the cells. However, an unspoken predicament appears in the current technologies: higher content comes at the expense of lower throughput, and vice versa. For example, accessing additional spatial information of individual cells, imaging flow cytometers only achieve an imaging throughput ~1000 cells/s, orders of magnitude slower than the non-imaging flow cytometers. In this chapter, we introduce an entirely new imaging platform, namely optical time-stretch microscopy, for ultrahigh speed and high contrast label-free single-cell (in a ultrafast microfluidic flow up to 10 m/s) imaging and analysis with an ultra-fast imaging line-scan rate as high as tens of MHz. Based on this technique, not only morphological information of the individual cells can be obtained in an ultrafast manner, quantitative evaluation of cellular information (e.g., cell volume, mass, refractive index, stiffness, membrane tension) at nanometer scale based on the optical phase is also possible. The technology can also be integrated with conventional fluorescence measurements widely adopted in the non-imaging flow cytometers. Therefore, these two combinatorial and complementary measurement capabilities in long run is an attractive platform for addressing the pressing need for expanding the "parameter space" in high-throughput single-cell analysis. This chapter provides the

Measurement of elastic precursor decay in pre-heated aluminum films under ultra-fast laser generated shocks

DOE PAGES

Zuanetti, Bryan; McGrane, Shawn David; Bolme, Cynthia Anne; ...

2018-05-18

Here, this article presents results from laser-driven shock compression experiments performed on pre-heated pure aluminum films at temperatures ranging from 23 to 400 °C. The samples were vapor deposited on the surface of a 500 μm thick sapphire substrate and mounted onto a custom holder with an integrated ring-heater to enable variable initial temperature conditions. A chirped pulse amplified laser was used to generate a pulse for both shocking the films and for probing the free surface velocity using Ultrafast Dynamic Ellipsometry. The particle velocity traces measured at the free surface clearly show elastic and plastic wave separation, which wasmore » used to estimate the decay of the elastic precursor amplitude over propagation distances ranging from 0.278 to 4.595 μm. Elastic precursors (which also correspond to dynamic material strength under uniaxial strain) of increasing amplitudes were observed with increasing initial sample temperatures for all propagation distances, which is consistent with expectations for aluminum in a deformation regime where phonon drag limits the mobility of dislocations. The experimental results show peak elastic amplitudes corresponding to axial stresses of over 7.5 GPa; estimates for plastic strain-rates in the samples are of the order 10 9/s. The measured elastic amplitudes at the micron length scales are compared with those at the millimeter length-scales using a two-parameter model and used to correlate the rate sensitivity of the dynamic strength at strain-rates ranging from 10 3 to 10 9/s and elevated temperature conditions. The overall trend, as inferred from the experimental data, indicates that the temperature-strengthening effect decreases with increasing plastic strain-rates.« less

Measurement of elastic precursor decay in pre-heated aluminum films under ultra-fast laser generated shocks

NASA Astrophysics Data System (ADS)

Zuanetti, Bryan; McGrane, Shawn D.; Bolme, Cynthia A.; Prakash, Vikas

2018-05-01

This article presents results from laser-driven shock compression experiments performed on pre-heated pure aluminum films at temperatures ranging from 23 to 400 °C. The samples were vapor deposited on the surface of a 500 μm thick sapphire substrate and mounted onto a custom holder with an integrated ring-heater to enable variable initial temperature conditions. A chirped pulse amplified laser was used to generate a pulse for both shocking the films and for probing the free surface velocity using Ultrafast Dynamic Ellipsometry. The particle velocity traces measured at the free surface clearly show elastic and plastic wave separation, which was used to estimate the decay of the elastic precursor amplitude over propagation distances ranging from 0.278 to 4.595 μm. Elastic precursors (which also correspond to dynamic material strength under uniaxial strain) of increasing amplitudes were observed with increasing initial sample temperatures for all propagation distances, which is consistent with expectations for aluminum in a deformation regime where phonon drag limits the mobility of dislocations. The experimental results show peak elastic amplitudes corresponding to axial stresses of over 7.5 GPa; estimates for plastic strain-rates in the samples are of the order 109/s. The measured elastic amplitudes at the micron length scales are compared with those at the millimeter length-scales using a two-parameter model and used to correlate the rate sensitivity of the dynamic strength at strain-rates ranging from 103 to 109/s and elevated temperature conditions. The overall trend, as inferred from the experimental data, indicates that the temperature-strengthening effect decreases with increasing plastic strain-rates.

Measurement of elastic precursor decay in pre-heated aluminum films under ultra-fast laser generated shocks

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

Zuanetti, Bryan; McGrane, Shawn David; Bolme, Cynthia Anne

Here, this article presents results from laser-driven shock compression experiments performed on pre-heated pure aluminum films at temperatures ranging from 23 to 400 °C. The samples were vapor deposited on the surface of a 500 μm thick sapphire substrate and mounted onto a custom holder with an integrated ring-heater to enable variable initial temperature conditions. A chirped pulse amplified laser was used to generate a pulse for both shocking the films and for probing the free surface velocity using Ultrafast Dynamic Ellipsometry. The particle velocity traces measured at the free surface clearly show elastic and plastic wave separation, which wasmore » used to estimate the decay of the elastic precursor amplitude over propagation distances ranging from 0.278 to 4.595 μm. Elastic precursors (which also correspond to dynamic material strength under uniaxial strain) of increasing amplitudes were observed with increasing initial sample temperatures for all propagation distances, which is consistent with expectations for aluminum in a deformation regime where phonon drag limits the mobility of dislocations. The experimental results show peak elastic amplitudes corresponding to axial stresses of over 7.5 GPa; estimates for plastic strain-rates in the samples are of the order 10 9/s. The measured elastic amplitudes at the micron length scales are compared with those at the millimeter length-scales using a two-parameter model and used to correlate the rate sensitivity of the dynamic strength at strain-rates ranging from 10 3 to 10 9/s and elevated temperature conditions. The overall trend, as inferred from the experimental data, indicates that the temperature-strengthening effect decreases with increasing plastic strain-rates.« less

The X-ray Fluorescence Microscopy Beamline at the Australian Synchrotron

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

Paterson, D.; Jonge, M. D. de; Howard, D. L.

2011-09-09

A hard x-ray micro-nanoprobe has commenced operation at the Australian Synchrotron providing versatile x-ray fluorescence microscopy across an incident energy range from 4 to 25 keV. Two x-ray probes are used to collect {mu}-XRF and {mu}-XANES for elemental and chemical microanalysis: a Kirkpatrick-Baez mirror microprobe for micron resolution studies and a Fresnel zone plate nanoprobe capable of 60-nm resolution. Some unique aspects of the beamline design and operation are discussed. An advanced energy dispersive x-ray fluorescence detection scheme named Maia has been developed for the beamline, which enables ultrafast x-ray fluorescence microscopy.

Safranine fluorescent staining of wood cell walls.

PubMed

Bond, J; Donaldson, L; Hill, S; Hitchcock, K

2008-06-01

Safranine is an azo dye commonly used for plant microscopy, especially as a stain for lignified tissues such as xylem. Safranine fluorescently labels the wood cell wall, producing green/yellow fluorescence in the secondary cell wall and red/orange fluorescence in the middle lamella (ML) region. We examined the fluorescence behavior of safranine under blue light excitation using a variety of wood- and fiber-based samples of known composition to interpret the observed color differentiation of different cell wall types. We also examined the basis for the differences in fluorescence emission using spectral confocal microscopy to examine lignin-rich and cellulose-rich cell walls including reaction wood and decayed wood compared to normal wood. Our results indicate that lignin-rich cell walls, such as the ML of tracheids, the secondary wall of compression wood tracheids, and wood decayed by brown rot, tend to fluoresce red or orange, while cellulose-rich cell walls such as resin canals, wood decayed by white rot, cotton fibers and the G-layer of tension wood fibers, tend to fluoresce green/yellow. This variation in fluorescence emission seems to be due to factors including an emission shift toward red wavelengths combined with dye quenching at shorter wavelengths in regions with high lignin content. Safranine fluorescence provides a useful way to differentiate lignin-rich and cellulose-rich cell walls without counterstaining as required for bright field microscopy.

Ultrafast optical excitations in supramolecular metallacycles with charge transfer properties.

PubMed

Flynn, Daniel C; Ramakrishna, Guda; Yang, Hai-Bo; Northrop, Brian H; Stang, Peter J; Goodson, Theodore

2010-02-03

New organometallic materials such as two-dimensional metallacycles and three-dimensional metallacages are important for the development of novel optical, electronic, and energy related applications. In this article, the ultrafast dynamics of two different platinum-containing metallacycles have been investigated by femtosecond fluorescence upconversion and transient absorption. These measurements were carried out in an effort to probe the charge transfer dynamics and the rate of intersystem crossing in metallacycles of different geometries and dimensions. The processes of ultrafast intersystem crossing and charge transfer vary between the two different classes of metallacyclic systems studied. For rectangular anthracene-containing metallacycles, the electronic coupling between adjacent ligands was relatively weak, whereas for the triangular phenanthrene-containing structures, there was a clear interaction between the conjugated ligand and the metal complex center. The transient lifetimes increased with increasing conjugation in that case. The results show that differences in the dimensionality and structure of metallacycles result in different optical properties, which may be utilized in the design of nonlinear optical materials and potential new, longer-lived excited state materials for further electronic applications.

Ultrafast Graphene Light Emitters.

PubMed

Kim, Young Duck; Gao, Yuanda; Shiue, Ren-Jye; Wang, Lei; Aslan, Ozgur Burak; Bae, Myung-Ho; Kim, Hyungsik; Seo, Dongjea; Choi, Heon-Jin; Kim, Suk Hyun; Nemilentsau, Andrei; Low, Tony; Tan, Cheng; Efetov, Dmitri K; Taniguchi, Takashi; Watanabe, Kenji; Shepard, Kenneth L; Heinz, Tony F; Englund, Dirk; Hone, James

2018-02-14

Ultrafast electrically driven nanoscale light sources are critical components in nanophotonics. Compound semiconductor-based light sources for the nanophotonic platforms have been extensively investigated over the past decades. However, monolithic ultrafast light sources with a small footprint remain a challenge. Here, we demonstrate electrically driven ultrafast graphene light emitters that achieve light pulse generation with up to 10 GHz bandwidth across a broad spectral range from the visible to the near-infrared. The fast response results from ultrafast charge-carrier dynamics in graphene and weak electron-acoustic phonon-mediated coupling between the electronic and lattice degrees of freedom. We also find that encapsulating graphene with hexagonal boron nitride (hBN) layers strongly modifies the emission spectrum by changing the local optical density of states, thus providing up to 460% enhancement compared to the gray-body thermal radiation for a broad peak centered at 720 nm. Furthermore, the hBN encapsulation layers permit stable and bright visible thermal radiation with electronic temperatures up to 2000 K under ambient conditions as well as efficient ultrafast electronic cooling via near-field coupling to hybrid polaritonic modes under electrical excitation. These high-speed graphene light emitters provide a promising path for on-chip light sources for optical communications and other optoelectronic applications.

Anomalous ultrafast dynamics of hot plasmonic electrons in nanostructures with hot spots

DOE PAGES

Harutyunyan, Hayk; Martinson, Alex B. F.; Rosenmann, Daniel; ...

2015-08-03

The interaction of light and matter in metallic nanosystems is mediated by the collective oscillation of surface electrons, called plasmons. After excitation, plasmons are absorbed by the metal electrons through inter- and intraband transitions, creating a highly non-thermal distribution of electrons. The electron population then decays through electron-electron interactions, creating a hot electron distribution within a few hundred femtoseconds, followed by a further relaxation via electron-phonon scattering on the timescale of a few pico-seconds. In the spectral domain, hot plasmonic electrons induce changes to the plasmonic resonance of the nanostructure by modifying the dielectric constant of the metal. Here, wemore » report on the observation of anomalously strong changes to the ultrafast temporal and spectral responses of these excited hot plasmonic electrons in hybrid metal/oxide nanostructures as a result of varying the geometry and composition of the nanostructure and the excitation wavelength. In particular, we show a large ultrafast, pulsewidth-limited contribution to the excited electron decay signal in hybrid nanostructures containing hot spots. The intensity of this contribution correlates with the efficiency of the generation of highly excited surface electrons. Using theoretical models, we attribute this effect to the generation of hot plasmonic electrons from hot spots. Finally, we then develop general principles to enhance the generation of energetic electrons through specifically designed plasmonic nanostructures that could be used in applications where hot electron generation is beneficial, such as in solar photocatalysis, photodetectors and nonlinear devices.« less

Anomalous ultrafast dynamics of hot plasmonic electrons in nanostructures with hot spots.

PubMed

Harutyunyan, Hayk; Martinson, Alex B F; Rosenmann, Daniel; Khorashad, Larousse Khosravi; Besteiro, Lucas V; Govorov, Alexander O; Wiederrecht, Gary P

2015-09-01

The interaction of light and matter in metallic nanosystems is mediated by the collective oscillation of surface electrons, called plasmons. After excitation, plasmons are absorbed by the metal electrons through inter- and intraband transitions, creating a highly non-thermal distribution of electrons. The electron population then decays through electron-electron interactions, creating a hot electron distribution within a few hundred femtoseconds, followed by a further relaxation via electron-phonon scattering on the timescale of a few picoseconds. In the spectral domain, hot plasmonic electrons induce changes to the plasmonic resonance of the nanostructure by modifying the dielectric constant of the metal. Here, we report on the observation of anomalously strong changes to the ultrafast temporal and spectral responses of these excited hot plasmonic electrons in hybrid metal/oxide nanostructures as a result of varying the geometry and composition of the nanostructure and the excitation wavelength. In particular, we show a large ultrafast, pulsewidth-limited contribution to the excited electron decay signal in hybrid nanostructures containing hot spots. The intensity of this contribution correlates with the efficiency of the generation of highly excited surface electrons. Using theoretical models, we attribute this effect to the generation of hot plasmonic electrons from hot spots. We then develop general principles to enhance the generation of energetic electrons through specifically designed plasmonic nanostructures that could be used in applications where hot electron generation is beneficial, such as in solar photocatalysis, photodetectors and nonlinear devices.

Porphyrin involvement in redshift fluorescence in dentin decay

NASA Astrophysics Data System (ADS)

Slimani, A.; Panayotov, I.; Levallois, B.; Cloitre, T.; Gergely, C.; Bec, N.; Larroque, C.; Tassery, H.; Cuisinier, F.

2014-05-01

The aim of this study was to evaluate the porphyrin involvement in the red fluorescence observed in dental caries with Soprolife® light-induced fluorescence camera in treatments mode (SOPRO, ACTEON Group, La Ciotat, France) and Vistacam® camera (DÜRR DENTAL AG, Bietigheim-Bissingen, Germany). The International Caries Detection and Assessment System (ICDAS) was used to rand the samples. Human teeth cross-sections, ranked from ICDAS score 0 to 6, were examined by epi-fluorescence microscopy and Confocal Raman microscopy. Comparable studies were done with Protoporphyrin IX, Porphyrin I and Pentosidine solutions. An RGB analysis of Soprolife® images was performed using ImageJ Software (1.46r, National Institutes of Health, USA). Fluorescence spectroscopy and MicroRaman spectroscopy revealed the presence of Protoporphyrin IX, in carious enamel, dentin and dental plaque. However, the presence of porphyrin I and pentosidine cannot be excluded. The results indicated that not only porphyrin were implicated in the red fluorescence, Advanced Glygation Endproducts (AGEs) of the Maillard reaction also contributed to this phenomenon.

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

NASA Astrophysics Data System (ADS)

Pu, Yang; Alfano, Robert R.

2015-03-01

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

Distributed ultrafast fibre laser

PubMed Central

Liu, Xueming; Cui, Yudong; Han, Dongdong; Yao, Xiankun; Sun, Zhipei

2015-01-01

A traditional ultrafast fibre laser has a constant cavity length that is independent of the pulse wavelength. The investigation of distributed ultrafast (DUF) lasers is conceptually and technically challenging and of great interest because the laser cavity length and fundamental cavity frequency are changeable based on the wavelength. Here, we propose and demonstrate a DUF fibre laser based on a linearly chirped fibre Bragg grating, where the total cavity length is linearly changeable as a function of the pulse wavelength. The spectral sidebands in DUF lasers are enhanced greatly, including the continuous-wave (CW) and pulse components. We observe that all sidebands of the pulse experience the same round-trip time although they have different round-trip distances and refractive indices. The pulse-shaping of the DUF laser is dominated by the dissipative processes in addition to the phase modulations, which makes our ultrafast laser simple and stable. This laser provides a simple, stable, low-cost, ultrafast-pulsed source with controllable and changeable cavity frequency. PMID:25765454

Ultrafast intramolecular charge transfer with N-(4-cyanophenyl)carbazole. Evidence for a LE precursor and dual LE + ICT fluorescence.

PubMed

Galievsky, Victor A; Druzhinin, Sergey I; Demeter, Attila; Mayer, Peter; Kovalenko, Sergey A; Senyushkina, Tamara A; Zachariasse, Klaas A

2010-12-09

The photophysics of N-(4-cyanophenyl)carbazole (NP4CN) was investigated by using absorption and fluorescence spectra, picosecond fluorescence decays, and femtosecond transient absorption. In the nonpolar n-hexane as well as in the polar solvent acetonitrile (MeCN), a locally excited (LE) state is detected, as a precursor for the intramolecular charge transfer (ICT) state. A LE → ICT reaction time τ(2) at 22 °C of 0.95 ps in ethyl cyanide (EtCN) and 0.32 ps in MeCN is determined from the decay of the LE excited state absorption (ESA) maximum around 620 nm. In the ESA spectrum of NP4CN in n-hexane at a pump-probe delay time of 100 ps, an important contribution of the LE band remains alongside the ICT band, in contrast to what is observed in EtCN and MeCN. This shows that a LE ⇄ ICT equilibrium is established in this solvent and the ICT reaction time of 0.5 ps is equal to the reciprocal of the sum of the forward and backward ICT rate constants 1/(k(a) + k(d)). In the photostationary S(0) → S(n) absorption spectrum of NP4CN in n-hexane and MeCN, an additional CT absorption band appears, absent in the sum of the spectra of its electron donor (D) and acceptor (A) subgroups carbazole and benzonitrile. This CT band is located at an energy of ∼4000 cm(-1) lower than for N-phenylcarbazole (NPC), due to the larger electron affinity of the benzonitrile moiety of NP4CN than the phenyl subunit of NPC. The fluorescence spectrum of NP4CN in n-hexane at 25 °C mainly consists of a structured LE emission, with a small ICT admixture, indicating that a LE → ICT reaction just starts to occur under these conditions. In di-n-pentyl ether (DPeE) and di-n-butyl ether (DBE), a LE emission is found upon cooling at the high-energy edge of the ICT fluorescence band, caused by the onset of dielectric solvent relaxation. This is not the case in more polar solvents, such as diethyl ether (DEE) and MeCN, in which a structureless ICT emission band fully overlaps the strongly quenched LE

Ultrafast Plasmon-Enhanced Hot Electron Generation at Ag Nanocluster/Graphite Heterojunctions.

PubMed

Tan, Shijing; Liu, Liming; Dai, Yanan; Ren, Jindong; Zhao, Jin; Petek, Hrvoje

2017-05-03

Hot electron processes at metallic heterojunctions are central to optical-to-chemical or electrical energy transduction. Ultrafast nonlinear photoexcitation of graphite (Gr) has been shown to create hot thermalized electrons at temperatures corresponding to the solar photosphere in less than 25 fs. Plasmonic resonances in metallic nanoparticles are also known to efficiently generate hot electrons. Here we deposit Ag nanoclusters (NC) on Gr to study the ultrafast hot electron generation and dynamics in their plasmonic heterojunctions by means of time-resolved two-photon photoemission (2PP) spectroscopy. By tuning the wavelength of p-polarized femtosecond excitation pulses, we find an enhancement of 2PP yields by 2 orders of magnitude, which we attribute to excitation of a surface-normal Mie plasmon mode of Ag/Gr heterojunctions at 3.6 eV. The 2PP spectra include contributions from (i) coherent two-photon absorption of an occupied interface state (IFS) 0.2 eV below the Fermi level, which electronic structure calculations assign to chemisorption-induced charge transfer, and (ii) hot electrons in the π*-band of Gr, which are excited through the coherent screening response of the substrate. Ultrafast pump-probe measurements show that the IFS photoemission occurs via virtual intermediate states, whereas the characteristic lifetimes attribute the hot electrons to population of the π*-band of Gr via the plasmon dephasing. Our study directly probes the mechanisms for enhanced hot electron generation and decay in a model plasmonic heterojunction.

Roadmap on ultrafast optics

NASA Astrophysics Data System (ADS)

Reid, Derryck T.; Heyl, Christoph M.; Thomson, Robert R.; Trebino, Rick; Steinmeyer, Günter; Fielding, Helen H.; Holzwarth, Ronald; Zhang, Zhigang; Del'Haye, Pascal; Südmeyer, Thomas; Mourou, Gérard; Tajima, Toshiki; Faccio, Daniele; Harren, Frans J. M.; Cerullo, Giulio

2016-09-01

The year 2015 marked the 25th anniversary of modern ultrafast optics, since the demonstration of the first Kerr lens modelocked Ti:sapphire laser in 1990 (Spence et al 1990 Conf. on Lasers and Electro-Optics, CLEO, pp 619-20) heralded an explosion of scientific and engineering innovation. The impact of this disruptive technology extended well beyond the previous discipline boundaries of lasers, reaching into biology labs, manufacturing facilities, and even consumer healthcare and electronics. In recognition of such a milestone, this roadmap on Ultrafast Optics draws together articles from some of the key opinion leaders in the field to provide a freeze-frame of the state-of-the-art, while also attempting to forecast the technical and scientific paradigms which will define the field over the next 25 years. While no roadmap can be fully comprehensive, the thirteen articles here reflect the most exciting technical opportunities presented at the current time in Ultrafast Optics. Several articles examine the future landscape for ultrafast light sources, from practical solid-state/fiber lasers and Raman microresonators to exotic attosecond extreme ultraviolet and possibly even zeptosecond x-ray pulses. Others address the control and measurement challenges, requiring radical approaches to harness nonlinear effects such as filamentation and parametric generation, coupled with the question of how to most accurately characterise the field of ultrafast pulses simultaneously in space and time. Applications of ultrafast sources in materials processing, spectroscopy and time-resolved chemistry are also discussed, highlighting the improvements in performance possible by using lasers of higher peak power and repetition rate, or by exploiting the phase stability of emerging new frequency comb sources.

Chromophore twisting in the excited state of a photoswitchable fluorescent protein captured by time-resolved serial femtosecond crystallography

NASA Astrophysics Data System (ADS)

Coquelle, Nicolas; Sliwa, Michel; Woodhouse, Joyce; Schirò, Giorgio; Adam, Virgile; Aquila, Andrew; Barends, Thomas R. M.; Boutet, Sébastien; Byrdin, Martin; Carbajo, Sergio; de La Mora, Eugenio; Doak, R. Bruce; Feliks, Mikolaj; Fieschi, Franck; Foucar, Lutz; Guillon, Virginia; Hilpert, Mario; Hunter, Mark S.; Jakobs, Stefan; Koglin, Jason E.; Kovacsova, Gabriela; Lane, Thomas J.; Lévy, Bernard; Liang, Mengning; Nass, Karol; Ridard, Jacqueline; Robinson, Joseph S.; Roome, Christopher M.; Ruckebusch, Cyril; Seaberg, Matthew; Thepaut, Michel; Cammarata, Marco; Demachy, Isabelle; Field, Martin; Shoeman, Robert L.; Bourgeois, Dominique; Colletier, Jacques-Philippe; Schlichting, Ilme; Weik, Martin

2018-01-01

Chromophores absorb light in photosensitive proteins and thereby initiate fundamental biological processes such as photosynthesis, vision and biofluorescence. An important goal in their understanding is the provision of detailed structural descriptions of the ultrafast photochemical events that they undergo, in particular of the excited states that connect chemistry to biological function. Here we report on the structures of two excited states in the reversibly photoswitchable fluorescent protein rsEGFP2. We populated the states through femtosecond illumination of rsEGFP2 in its non-fluorescent off state and observed their build-up (within less than one picosecond) and decay (on the several picosecond timescale). Using an X-ray free-electron laser, we performed picosecond time-resolved crystallography and show that the hydroxybenzylidene imidazolinone chromophore in one of the excited states assumes a near-canonical twisted configuration halfway between the trans and cis isomers. This is in line with excited-state quantum mechanics/molecular mechanics and classical molecular dynamics simulations. Our new understanding of the structure around the twisted chromophore enabled the design of a mutant that displays a twofold increase in its off-to-on photoswitching quantum yield.

Chromophore twisting in the excited state of a photoswitchable fluorescent protein captured by time-resolved serial femtosecond crystallography

DOE PAGES

Coquelle, Nicolas; Sliwa, Michel; Woodhouse, Joyce; ...

2017-09-11

Chromophores absorb light in photosensitive proteins and thereby initiate fundamental biological processes such as photosynthesis, vision and biofluorescence. An important goal in their understanding is the provision of detailed structural descriptions of the ultrafast photochemical events that they undergo, in particular of the excited states that connect chemistry to biological function. Here in this paper we report on the structures of two excited states in the reversibly photoswitchable fluorescent protein rsEGFP2. We populated the states through femtosecond illumination of rsEGFP2 in its non-fluorescent off state and observed their build-up (within less than one picosecond) and decay (on the several picosecondmore » timescale). Using an X-ray free-electron laser, we performed picosecond time-resolved crystallography and show that the hydroxybenzylidene imidazolinone chromophore in one of the excited states assumes a near-canonical twisted configuration halfway between the trans and cis isomers. This is in line with excited-state quantum mechanics/molecular mechanics and classical molecular dynamics simulations. Our new understanding of the structure around the twisted chromophore enabled the design of a mutant that displays a twofold increase in its off-to-on photoswitching quantum yield.« less

Chromophore twisting in the excited state of a photoswitchable fluorescent protein captured by time-resolved serial femtosecond crystallography

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

Coquelle, Nicolas; Sliwa, Michel; Woodhouse, Joyce

Chromophores absorb light in photosensitive proteins and thereby initiate fundamental biological processes such as photosynthesis, vision and biofluorescence. An important goal in their understanding is the provision of detailed structural descriptions of the ultrafast photochemical events that they undergo, in particular of the excited states that connect chemistry to biological function. Here in this paper we report on the structures of two excited states in the reversibly photoswitchable fluorescent protein rsEGFP2. We populated the states through femtosecond illumination of rsEGFP2 in its non-fluorescent off state and observed their build-up (within less than one picosecond) and decay (on the several picosecondmore » timescale). Using an X-ray free-electron laser, we performed picosecond time-resolved crystallography and show that the hydroxybenzylidene imidazolinone chromophore in one of the excited states assumes a near-canonical twisted configuration halfway between the trans and cis isomers. This is in line with excited-state quantum mechanics/molecular mechanics and classical molecular dynamics simulations. Our new understanding of the structure around the twisted chromophore enabled the design of a mutant that displays a twofold increase in its off-to-on photoswitching quantum yield.« less

Ultrafast photodissociation dynamics of 1,4-diiodobenzene

NASA Astrophysics Data System (ADS)

Stankus, Brian; Zotev, Nikola; Rogers, David M.; Gao, Yan; Odate, Asami; Kirrander, Adam; Weber, Peter M.

2018-05-01

The photodissociation dynamics of 1,4-diiodobenzene is investigated using ultrafast time-resolved photoelectron spectroscopy. Following excitation by laser pulses at 271 nm, the excited-state dynamics is probed by resonance-enhanced multiphoton ionization with 405 nm probe pulses. A progression of Rydberg states, which come into resonance sequentially, provide a fingerprint of the dissociation dynamics of the molecule. The initial excitation decays with a lifetime of 33 ± 4 fs, in good agreement with a previous study. The spectrum is interpreted by reference to ab initio calculations at the CASPT2(18,14) level, including spin-orbit coupling. We propose that both the 5B1 and 6B1 states are excited initially, and based on the calculations, we identify diabatic spin-orbit coupled states corresponding to the main dissociation pathways.

Ultrafast excited-state dynamics of 2,5-dimethylpyrrole.

PubMed

Yang, Dongyuan; Min, Yanjun; Chen, Zhichao; He, Zhigang; Yuan, Kaijun; Dai, Dongxu; Yang, Xueming; Wu, Guorong

2018-04-17

The ultrafast excited-state dynamics of 2,5-dimethylpyrrole following excitation at wavelengths in the range of 265.7-216.7 nm is studied using the time-resolved photoelectron imaging method. It is found that excitation at longer wavelengths (265.7-250.2 nm) results in the population of the S1(1πσ*) state, which decays out of the photoionization window in about 90 fs. At shorter pump wavelengths (242.1-216.7 nm), the assignments are less clear-cut. We tentatively assign the initially photoexcited state(s) to the 1π3p Rydberg state(s) which has lifetimes of 159 ± 20, 125 ± 15, 102 ± 10 and 88 ± 10 fs for the pump wavelengths of 242.1, 238.1, 232.6 and 216.7 nm, respectively. Internal conversion to the S1(1πσ*) state represents at most a minor decay channel. The methyl substitution effects on the decay dynamics of the excited states of pyrrole are also discussed. Methyl substitution on the pyrrole ring seems to enhance the direct internal conversion from the 1π3p Rydberg state to the ground state, while methyl substitution on the N atom has less influence and the internal conversion to the S1(πσ*) state represents a main channel.

Hydrogen Bond Switching among Flavin and Amino Acid Side Chains in the BLUF Photoreceptor Observed by Ultrafast Infrared Spectroscopy

PubMed Central

Bonetti, Cosimo; Mathes, Tilo; van Stokkum, Ivo H. M.; Mullen, Katharine M.; Groot, Marie-Louise; van Grondelle, Rienk; Hegemann, Peter; Kennis, John T. M.

2008-01-01

BLUF domains constitute a recently discovered class of photoreceptor proteins found in bacteria and eukaryotic algae. BLUF domains are blue-light sensitive through a FAD cofactor that is involved in an extensive hydrogen-bond network with nearby amino acid side chains, including a highly conserved tyrosine and glutamine. The participation of particular amino acid side chains in the ultrafast hydrogen-bond switching reaction with FAD that underlies photoactivation of BLUF domains is assessed by means of ultrafast infrared spectroscopy. Blue-light absorption by FAD results in formation of FAD•− and a bleach of the tyrosine ring vibrational mode on a picosecond timescale, showing that electron transfer from tyrosine to FAD constitutes the primary photochemistry. This interpretation is supported by the absence of a kinetic isotope effect on the fluorescence decay on H/D exchange. Subsequent protonation of FAD•− to result in FADH• on a picosecond timescale is evidenced by the appearance of a N-H bending mode at the FAD N5 protonation site and of a FADH• C=N stretch marker mode, with tyrosine as the likely proton donor. FADH• is reoxidized in 67 ps (180 ps in D2O) to result in a long-lived hydrogen-bond switched network around FAD. This hydrogen-bond switch shows infrared signatures from the C-OH stretch of tyrosine and the FAD C4=O and C=N stretches, which indicate increased hydrogen-bond strength at all these sites. The results support a previously hypothesized rotation of glutamine by ∼180° through a light-driven radical-pair mechanism as the determinant of the hydrogen-bond switch. PMID:18708458

Ultrafast and nonlinear surface-enhanced Raman spectroscopy.

PubMed

Gruenke, Natalie L; Cardinal, M Fernanda; McAnally, Michael O; Frontiera, Renee R; Schatz, George C; Van Duyne, Richard P

2016-04-21

Ultrafast surface-enhanced Raman spectroscopy (SERS) has the potential to study molecular dynamics near plasmonic surfaces to better understand plasmon-mediated chemical reactions such as plasmonically-enhanced photocatalytic or photovoltaic processes. This review discusses the combination of ultrafast Raman spectroscopic techniques with plasmonic substrates for high temporal resolution, high sensitivity, and high spatial resolution vibrational spectroscopy. First, we introduce background information relevant to ultrafast SERS: the mechanisms of surface enhancement in Raman scattering, the characterization of plasmonic materials with ultrafast techniques, and early complementary techniques to study molecule-plasmon interactions. We then discuss recent advances in surface-enhanced Raman spectroscopies with ultrafast pulses with a focus on the study of molecule-plasmon coupling and molecular dynamics with high sensitivity. We also highlight the challenges faced by this field by the potential damage caused by concentrated, highly energetic pulsed fields in plasmonic hotspots, and finally the potential for future ultrafast SERS studies.

Ultrafast Science Opportunities with Electron Microscopy

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

Durr, Hermann

X-rays and electrons are two of the most fundamental probes of matter. When the Linac Coherent Light Source (LCLS), the world’s first x-ray free electron laser, began operation in 2009, it transformed ultrafast science with the ability to generate laser-like x-ray pulses from the manipulation of relativistic electron beams. This document describes a similar future transformation. In Transmission Electron Microscopy, ultrafast relativistic (MeV energy) electron pulses can achieve unsurpassed spatial and temporal resolution. Ultrafast temporal resolution will be the next frontier in electron microscopy and can ideally complement ultrafast x-ray science done with free electron lasers. This document describes themore » Grand Challenge science opportunities in chemistry, material science, physics and biology that arise from an MeV ultrafast electron diffraction & microscopy facility, especially when coupled with linac-based intense THz and X-ray pump capabilities.« less

Direct and simultaneous observation of ultrafast electron and hole dynamics in germanium

DOE PAGES

Zurch, Michael; Chang, Hung -Tzu; Borja, Lauren J.; ...

2017-06-01

Understanding excited carrier dynamics in semiconductors is crucial for the development of photovoltaics and efficient photonic devices. However, overlapping spectral features in optical pump-probe spectroscopy often render assignments of separate electron and hole carrier dynamics ambiguous. Here, ultrafast electron and hole dynamics in germanium nanocrystalline thin films are directly and simultaneously observed by ultrafast transient absorption spectroscopy in the extreme ultraviolet at the germanium M 4,5 edge. We decompose the spectra into contributions of electronic state blocking and photo-induced band shifts at a carrier density of 8 × 10 20 cm –3. Separate electron and hole relaxation times are observedmore » as a function of hot carrier energies. A first-order electron and hole decay of ~1 ps suggests a Shockley–Read–Hall recombination mechanism. Furthermore, the simultaneous observation of electrons and holes with extreme ultraviolet transient absorption spectroscopy paves the way for investigating few- to sub-femtosecond dynamics of both holes and electrons in complex semiconductor materials and across junctions.« less

Direct and simultaneous observation of ultrafast electron and hole dynamics in germanium

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

Zurch, Michael; Chang, Hung -Tzu; Borja, Lauren J.

Understanding excited carrier dynamics in semiconductors is crucial for the development of photovoltaics and efficient photonic devices. However, overlapping spectral features in optical pump-probe spectroscopy often render assignments of separate electron and hole carrier dynamics ambiguous. Here, ultrafast electron and hole dynamics in germanium nanocrystalline thin films are directly and simultaneously observed by ultrafast transient absorption spectroscopy in the extreme ultraviolet at the germanium M 4,5 edge. We decompose the spectra into contributions of electronic state blocking and photo-induced band shifts at a carrier density of 8 × 10 20 cm –3. Separate electron and hole relaxation times are observedmore » as a function of hot carrier energies. A first-order electron and hole decay of ~1 ps suggests a Shockley–Read–Hall recombination mechanism. Furthermore, the simultaneous observation of electrons and holes with extreme ultraviolet transient absorption spectroscopy paves the way for investigating few- to sub-femtosecond dynamics of both holes and electrons in complex semiconductor materials and across junctions.« less

Ultrafast switching of valence and generation of coherent acoustic phonons in semiconducting rare-earth monosulfides

NASA Astrophysics Data System (ADS)

Punpongjareorn, Napat; He, Xing; Tang, Zhongjia; Guloy, Arnold M.; Yang, Ding-Shyue

2017-08-01

We report on the ultrafast carrier dynamics and generation of coherent acoustic phonons in YbS, a semiconducting rare-earth monochalcogenide, using two-color pump-probe reflectivity. Compared to the carrier relaxation processes and lifetimes of conventional semiconductors, recombination of photoexcited electrons with holes in localized f orbitals is found to take place rapidly with a density-independent time constant of <500 fs in YbS. Such carrier annihilation signifies the unique and ultrafast nature of valence restoration of ytterbium ions after femtosecond photoexcitation switching. Following transfer of the absorbed energy to the lattice, coherent acoustic phonons emerge on the picosecond timescale as a result of the thermal strain in the photoexcited region. By analyzing the electronic and structural dynamics, we obtain the physical properties of YbS including its two-photon absorption and thermooptic coefficients, the period and decay time of the coherent oscillation, and the sound velocity.

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

PubMed Central

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

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

PubMed

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.

Tracking of the nuclear wavepacket motion in cyanine photoisomerization by ultrafast pump-dump-probe spectroscopy.

PubMed

Wei, Zhengrong; Nakamura, Takumi; Takeuchi, Satoshi; Tahara, Tahei

2011-06-01

Understanding ultrafast reactions, which proceed on a time scale of nuclear motions, requires a quantitative characterization of the structural dynamics. To track such structural changes with time, we studied a nuclear wavepacket motion in photoisomerization of a prototype cyanine dye, 1,1'-diethyl-4,4'-cyanine, by ultrafast pump-dump-probe measurements in solution. The temporal evolution of wavepacket motion was examined by monitoring the efficiency of stimulated emission dumping, which was obtained from the recovery of a ground-state bleaching signal. The dump efficiency versus pump-dump delay exhibited a finite rise time, and it became longer (97 fs → 330 fs → 390 fs) as the dump pulse was tuned to longer wavelengths (690 nm → 950 nm → 1200 nm). This result demonstrates a continuous migration of the leading edge of the wavepacket on the excited-state potential from the Franck-Condon region toward the potential minimum. A slowly decaying feature of the dump efficiency indicated a considerable broadening of the wavepacket over a wide range of the potential, which results in the spread of a population distribution on the flat S(1) potential energy surface. The rapid migration as well as broadening of the wavepacket manifests a continuous nature of the structural dynamics and provides an intuitive visualization of this ultrafast reaction. We also discussed experimental strategies to evaluate reliable dump efficiencies separately from other ultrafast processes and showed a high capability and possibility of the pump-dump-probe method for spectroscopic investigation of unexplored potential regions such as conical intersections. © 2011 American Chemical Society

Ultrafast ultrasound localization microscopy for deep super-resolution vascular imaging

NASA Astrophysics Data System (ADS)

Errico, Claudia; Pierre, Juliette; Pezet, Sophie; Desailly, Yann; Lenkei, Zsolt; Couture, Olivier; Tanter, Mickael

2015-11-01

Non-invasive imaging deep into organs at microscopic scales remains an open quest in biomedical imaging. Although optical microscopy is still limited to surface imaging owing to optical wave diffusion and fast decorrelation in tissue, revolutionary approaches such as fluorescence photo-activated localization microscopy led to a striking increase in resolution by more than an order of magnitude in the last decade. In contrast with optics, ultrasonic waves propagate deep into organs without losing their coherence and are much less affected by in vivo decorrelation processes. However, their resolution is impeded by the fundamental limits of diffraction, which impose a long-standing trade-off between resolution and penetration. This limits clinical and preclinical ultrasound imaging to a sub-millimetre scale. Here we demonstrate in vivo that ultrasound imaging at ultrafast frame rates (more than 500 frames per second) provides an analogue to optical localization microscopy by capturing the transient signal decorrelation of contrast agents—inert gas microbubbles. Ultrafast ultrasound localization microscopy allowed both non-invasive sub-wavelength structural imaging and haemodynamic quantification of rodent cerebral microvessels (less than ten micrometres in diameter) more than ten millimetres below the tissue surface, leading to transcranial whole-brain imaging within short acquisition times (tens of seconds). After intravenous injection, single echoes from individual microbubbles were detected through ultrafast imaging. Their localization, not limited by diffraction, was accumulated over 75,000 images, yielding 1,000,000 events per coronal plane and statistically independent pixels of ten micrometres in size. Precise temporal tracking of microbubble positions allowed us to extract accurately in-plane velocities of the blood flow with a large dynamic range (from one millimetre per second to several centimetres per second). These results pave the way for deep non

Ultrafast ultrasound localization microscopy for deep super-resolution vascular imaging.

PubMed

Errico, Claudia; Pierre, Juliette; Pezet, Sophie; Desailly, Yann; Lenkei, Zsolt; Couture, Olivier; Tanter, Mickael

2015-11-26

Non-invasive imaging deep into organs at microscopic scales remains an open quest in biomedical imaging. Although optical microscopy is still limited to surface imaging owing to optical wave diffusion and fast decorrelation in tissue, revolutionary approaches such as fluorescence photo-activated localization microscopy led to a striking increase in resolution by more than an order of magnitude in the last decade. In contrast with optics, ultrasonic waves propagate deep into organs without losing their coherence and are much less affected by in vivo decorrelation processes. However, their resolution is impeded by the fundamental limits of diffraction, which impose a long-standing trade-off between resolution and penetration. This limits clinical and preclinical ultrasound imaging to a sub-millimetre scale. Here we demonstrate in vivo that ultrasound imaging at ultrafast frame rates (more than 500 frames per second) provides an analogue to optical localization microscopy by capturing the transient signal decorrelation of contrast agents--inert gas microbubbles. Ultrafast ultrasound localization microscopy allowed both non-invasive sub-wavelength structural imaging and haemodynamic quantification of rodent cerebral microvessels (less than ten micrometres in diameter) more than ten millimetres below the tissue surface, leading to transcranial whole-brain imaging within short acquisition times (tens of seconds). After intravenous injection, single echoes from individual microbubbles were detected through ultrafast imaging. Their localization, not limited by diffraction, was accumulated over 75,000 images, yielding 1,000,000 events per coronal plane and statistically independent pixels of ten micrometres in size. Precise temporal tracking of microbubble positions allowed us to extract accurately in-plane velocities of the blood flow with a large dynamic range (from one millimetre per second to several centimetres per second). These results pave the way for deep non

Fluorescence spectroscopy and confocal microscopy of the mycotoxin citrinin in condensed phase and hydrogel films.

PubMed

Lauer, Milena H; Gehlen, Marcelo H; de Jesus, Karen; Berlinck, Roberto G S

2014-05-01

The emission spectra, quantum yields and fluorescence lifetimes of citrinin in organic solvents and hydrogel films have been determined. Citrinin shows complex fluorescence decays due to the presence of two tautomers in solution and interconversion from excited-state double proton transfer (ESDPT) process. The fluorescence decay times associated with the two tautomers have values near 1 and 5 ns depending on the medium. In hydrogel films of agarose and alginate, fluorescence imaging showed that citrinin is not homogeneously dispersed and highly emissive micrometer spots may be formed. Fluorescence spectrum and decay analysis are used to recognize the presence of citrinin in hydrogel films using confocal fluorescence microscopy and spectroscopy.

Simultaneous determination of 11 designated hallucinogenic phenethylamines by ultra-fast liquid chromatography with fluorescence detection.

PubMed

Min, Jun Zhe; Shimizu, Yoshiha; Toyo'oka, Toshimasa; Inagaki, Shinsuke; Kikura-Hanajiri, Ruri; Goda, Yukihiro

2008-10-01

To avoid the spreading of illegal drugs, a designated drug regulation system was introduced along with revision of the Pharmaceutical Affairs Law in Japan in 2006, and 32 substances including phenethylamine-type drugs were listed in April 2007. In this study, a new simultaneous determination method, based on ultra-fast liquid chromatography coupled with fluorescence detection (UFLC-FL), was developed for the 11 designated phenethylamine drugs. The phenethylamines were labeled with 4-(N,N-dimethylaminosulfonyl)-7-fluoro-2,1,3-benzoxadiazole (DBD-F) at 60 degrees C for 2h in 0.1M borax (pH 9.3). The resulting 11 fluorophores were completely separated by reversed-phase chromatography using an ACQUITY UPLC BEH C(18) column (2.1 mm x 100 mm 1.7 microm) and fluorometrically detected at 550 nm (excitation at 450 nm). The calibration curves obtained from the peak areas versus the injection amounts of the phenethylamines showed a good linearity. The limits of detection (signal-to-noise ratio of 3: S/N=3) on the chromatogram were in the range from 10 fmol (PMMA) to 2.5pmol (MMDA-2). Good accuracy (%) and precision (CV) by intra-day assay and inter-day assay were also obtained using the present procedure. The method was applied to the qualitative and quantitative analyses of phenethylamine in real products obtained from the Japanese market. As the results, BDB (0.24 mg/mg), MMDA-2 (0.98 mg/mL) and 2C-I (0.016 mg/mg) were identified from the different products (powder, liquid and mushroom like). Because the procedure is simple, selective and sensitive, the present method seems to be useful for the qualitative and quantitative analyses of the designated phenethylamines in various samples including biological specimens.

Study on ultra-fast single photon counting spectrometer based on PCI

NASA Astrophysics Data System (ADS)

Zhang, Xi-feng

2010-10-01

The time-correlated single photon counting spectrometer developed uses PCI bus technology. We developed the ultrafast data acquisition card based on PCI, replace multi-channel analyzer primary. The system theory and design of the spectrometer are presented in detail, and the process of operation is introduced with the integration of the system. Many standard samples have been measured and the data have been analyzed and contrasted. Experimental results show that the spectrometer, s sensitive is single photon counting, and fluorescence life-span and time resolution is picosecond level. And the instrument could measure time-resolved spectroscopy.

Ultrafast energy relaxation in single light-harvesting complexes.

PubMed

Malý, Pavel; Gruber, J Michael; Cogdell, Richard J; Mančal, Tomáš; van Grondelle, Rienk

2016-03-15

Energy relaxation in light-harvesting complexes has been extensively studied by various ultrafast spectroscopic techniques, the fastest processes being in the sub-100-fs range. At the same time, much slower dynamics have been observed in individual complexes by single-molecule fluorescence spectroscopy (SMS). In this work, we use a pump-probe-type SMS technique to observe the ultrafast energy relaxation in single light-harvesting complexes LH2 of purple bacteria. After excitation at 800 nm, the measured relaxation time distribution of multiple complexes has a peak at 95 fs and is asymmetric, with a tail at slower relaxation times. When tuning the excitation wavelength, the distribution changes in both its shape and position. The observed behavior agrees with what is to be expected from the LH2 excited states structure. As we show by a Redfield theory calculation of the relaxation times, the distribution shape corresponds to the expected effect of Gaussian disorder of the pigment transition energies. By repeatedly measuring few individual complexes for minutes, we find that complexes sample the relaxation time distribution on a timescale of seconds. Furthermore, by comparing the distribution from a single long-lived complex with the whole ensemble, we demonstrate that, regarding the relaxation times, the ensemble can be considered ergodic. Our findings thus agree with the commonly used notion of an ensemble of identical LH2 complexes experiencing slow random fluctuations.

EDITORIAL: Ultrafast magnetization processes

NASA Astrophysics Data System (ADS)

Hillebrands, Burkard

2008-09-01

anisotropic magnetoresistance and pulsed inductive microwave magnetometry to measure the time-resolved precessional magnetization dynamics. The intrinsic and non-local Gilbert damping in polycrystalline Ni films is also addressed by J Walowski et al [164016] using femtosecond laser pulses. Several spin-wave modes are observed and their dissipation is studied. Non-local damping by spin currents emitted into a non-magnetic metallic layer of either vanadium, palladium or dysprosium is studied. Dissipation in small magnetic Ni81Fe19 rings is studied using Brillouin light scattering microscopy by H Schultheiss et al [164017]. They investigate the spatial profiles and the decay constants of spin-wave quasi-eigenmodes. We hope that this cluster of papers will help to stimulate and advance a better understanding of this very interesting field of ultrafast magnetization processes.

Ultrafast intersystem-crossing in platinum containing π-conjugated polymers with tunable spin-orbit coupling.

PubMed

Sheng, C-X; Singh, S; Gambetta, A; Drori, T; Tong, M; Tretiak, S; Vardeny, Z V

2013-01-01

The development of efficient organic light-emitting diodes (OLED) and organic photovoltaic cells requires control over the dynamics of spin sensitive excitations. Embedding heavy metal atoms in π-conjugated polymer chains enhances the spin-orbit coupling (SOC), and thus facilitates intersystem crossing (ISC) from the singlet to triplet manifolds. Here we use various nonlinear optical spectroscopies such as two-photon absorption and electroabsorption in conjunction with electronic structure calculations, for studying the energies, emission bands and ultrafast dynamics of spin photoexcitations in two newly synthesized π-conjugated polymers that contain intrachain platinum (Pt) atoms separated by one (Pt-1) or three (Pt-3) organic spacer units. The controllable SOC in these polymers leads to a record ISC time of <~1 ps in Pt-1 and ~6 ps in Pt-3. The tunable ultrafast ISC rate modulates the intensity ratio of the phosphorescence and fluorescence emission bands, with potential applications for white OLEDs.

Ultrashort fluorescence lifetimes of hydrogen-bonded base pairs of guanosine and cytidine in solution.

PubMed

Schwalb, Nina K; Michalak, Thomas; Temps, Friedrich

2009-12-24

The optically excited electronic states of hydrogen-bonded homo- and heterodimers of guanosine (G) and deoxycytidine (C) were investigated by femtosecond fluorescence up-conversion spectroscopy. The base pairs were prepared in CHCl(3) solution by employing tert-butyldimethylsilyl (TBDMS) groups at the OH positions of the ribose (G) or deoxyribose (C) moieties to enhance the solubilities of the nucleosides in organic solvents. The H-bonded complexes that were obtained were characterized by FTIR spectroscopy. Fluorescence lifetime measurements were performed following electronic excitation at a series of UV wavelengths from lambda(pump) = 294 nm, close to the electronic origins of the bases, to lambda(pump) = 262 nm, where significant excess vibronic energy is deposited in the molecules, at nucleoside concentrations of c(0) = 0.1 and 1.0 mM. The experimental results revealed the existence of an ultrafast deactivation pathway for the optically prepared electronically excited state(s) of the G.C Watson-Crick base pair, which was found to have a lifetime of tau(GC) = 0.30(3) ps (with 2sigma error limits) irrespective of the pump wavelength. A similar short decay time, tau(GG) = 0.32(2) ps, was observed for the respective excited G.G homodimer. In contrast, the excited G monomer displayed a significantly longer-lived and wavelength-dependent deactivation, requiring three time constants, between 0.43(6) ps < or = tau(G,1) < or = 1.2(1) ps, 4.2(8) ps < or = tau(G,2) < or = 8(1) ps, and tau(G,3) = 195(32) ps. Self-complexation of C, on the other hand, led to a longer-lived excited state with a lifetime estimated between 1 ps < or = tau(CC) < or = 10 ps, compared to the dominant initial subpicosecond decay time of the C monomer of tau(C,1) = 0.80(4) ps.

Polarization-dependent force driving the Eg mode in bismuth under optical excitation: comparison of first-principles theory with ultra-fast x-ray experiments

NASA Astrophysics Data System (ADS)

Fahy, Stephen; Murray, Eamonn

2015-03-01

Using first principles electronic structure methods, we calculate the induced force on the Eg (zone centre transverse optical) phonon mode in bismuth immediately after absorption of a ultrafast pulse of polarized light. To compare the results with recent ultra-fast, time-resolved x-ray diffraction experiments, we include the decay of the force due to carrier scattering, as measured in optical Raman scattering experiments, and simulate the optical absorption process, depth-dependent atomic driving forces, and x-ray diffraction in the experimental geometry. We find excellent agreement between the theoretical predictions and the observed oscillations of the x-ray diffraction signal, indicating that first-principles theory of optical absorption is well suited to the calculation of initial atomic driving forces in photo-excited materials following ultrafast excitation. This work is supported by Science Foundation Ireland (Grant No. 12/IA/1601) and EU Commission under the Marie Curie Incoming International Fellowships (Grant No. PIIF-GA-2012-329695).

Spatial Temperature Mapping within Polymer Nanocomposites Undergoing Ultrafast Photothermal Heating via Gold Nanorods

PubMed Central

Maity, Somsubhra; Wu, Wei-Chen; Xu, Chao; Tracy, Joseph B.; Gundogdu, Kenan; Bochinski, Jason R.; Clarke, Laura I.

2015-01-01

Heat emanates from gold nanorods (GNRs) under ultrafast optical excitation of the localized surface plasmon resonance. The steady state nanoscale temperature distribution formed within a polymer matrix embedded with GNRs undergoing pulsed femtosecond photothermal heating is determined experimentally using two independent ensemble optical techniques. Physical rotation of the nanorods reveals the average local temperature of the polymer melt in the immediate spatial volume surrounding them while fluorescence of homogeneously-distributed perylene molecules monitors temperature over sample regions at larger distances from the GNRs. Polarization-sensitive fluorescence measurements of the perylene probes provide an estimate of the average size of the quasi-molten region surrounding each nanorod (that is, the boundary between softened polymer and solid material as the temperature decreases radially away from each particle) and distinguishes the steady state temperature in the solid and melt regions. Combining these separate methods enables nanoscale spatial mapping of the average steady state temperature distribution caused by ultrafast excitation of the GNRs. These observations definitively demonstrate the presence of a steady-state temperature gradient and indicate that localized heating via the photothermal effect within materials enables nanoscale thermal manipulations without significantly altering the bulk sample temperature in these systems. These quantitative results are further verified by reorienting nanorods within a solid polymer nanofiber without inducing any morphological changes to the highly temperature-sensitive nanofiber surface. Temperature differences of 70 – 90 °C were observed over a distances of ~100 nm. PMID:25379775

Electric Switching of Fluorescence Decay in Gold-Silica-Dye Nematic Nanocolloids Mediated by Surface Plasmons.

PubMed

Jiang, Li; Mundoor, Haridas; Liu, Qingkun; Smalyukh, Ivan I

2016-07-26

Tunable composite materials with interesting physical behavior can be designed through integrating unique optical properties of solid nanostructures with facile responses of soft matter to weak external stimuli, but this approach remains challenged by their poorly controlled coassembly at the mesoscale. Using scalable wet chemical synthesis procedures, we fabricated anisotropic gold-silica-dye colloidal nanostructures and then organized them into the device-scale (demonstrated for square-inch cells) electrically tunable composites by simultaneously invoking molecular and colloidal self-assembly. We show that the ensuing ordered colloidal dispersions of shape-anisotropic nanostructures exhibit tunable fluorescence decay rates and intensity. We characterize how these properties depend on low-voltage fields and polarization of both the excitation and emission light, demonstrating a great potential for the practical realization of an interesting breed of nanostructured composite materials.

Interactions between natural organic ligands and trace metals studied by fluorescence lifetime and fluorescence quenching

NASA Astrophysics Data System (ADS)

Nouhi, Ayoub; Hajjoul, Houssam; Redon, Roland; Gagné, Jean-Pierre; Mounier, Stéphane

2017-04-01

Improved insight on the interactions between natural organic ligands and trace metals is of paramount importance for better understanding transport and toxicity pathways of metal ions in the environment. Fluorescence spectroscopy allows introspecting ligands-metals interactions. Time-resolved laser fluorescence spectroscopy (TRLFS) measures fluorophore lifetime probing the local molecular environment. Excitation Emission Fluorescence Matrices (EEFMs) and their statistical treatment : parallel factor analysis (PARAFAC) using PROGMEEF Matlab homemade program, can give insight on the number or nature of organic fluorophores involved in the interactions. Quenching of fluorescence by metals can occur following two processes: dynamic and static quenching (Lakowicz, 2013). In the first case, quenching is caused by physical collisions among molecules and in the second case fluorophores can form nonfluorescent complexes with quenchers. It is possible to identify the different mechanisms because each type of quenching corresponds to a different mathematical model (Lakowicz, 2013; Valeur and Berberan-Santos, 2012). In TRLFS, the study of fluorescence decay's laws induced by nanosecond pulsed laser will allow to exactly qualify the type of interaction. The crucial point of the temporal deconvolution will be the evaluation of the best fitting between the different physical models and the decays measured. From the most suitable time decay model, it will be possible to deduce the quenching which modifies the fluorescence. The aim of this study was to characterize interactions between natural organic ligands and trace metals using fluorescence tools to evaluate the fluorescence lifetime of the fluorophore, the occurrence of quenching in presence of metal, discuss its mechanism and estimate conditional stability constants if a complex organic ligand-metal is formed. This study has been done in two steps. First, we have examined the interactions between salicylic acid and copper in

Simultaneous Fluorescence and Phosphorescence Lifetime Imaging Microscopy in Living Cells

NASA Astrophysics Data System (ADS)

Jahn, Karolina; Buschmann, Volker; Hille, Carsten

2015-09-01

In living cells, there are always a plethora of processes taking place at the same time. Their precise regulation is the basis of cellular functions, since small failures can lead to severe dysfunctions. For a comprehensive understanding of intracellular homeostasis, simultaneous multiparameter detection is a versatile tool for revealing the spatial and temporal interactions of intracellular parameters. Here, a recently developed time-correlated single-photon counting (TCSPC) board was evaluated for simultaneous fluorescence and phosphorescence lifetime imaging microscopy (FLIM/PLIM). Therefore, the metabolic activity in insect salivary glands was investigated by recording ns-decaying intrinsic cellular fluorescence, mainly related to oxidized flavin adenine dinucleotide (FAD) and the μs-decaying phosphorescence of the oxygen-sensitive ruthenium-complex Kr341. Due to dopamine stimulation, the metabolic activity of salivary glands increased, causing a higher pericellular oxygen consumption and a resulting increase in Kr341 phosphorescence decay time. Furthermore, FAD fluorescence decay time decreased, presumably due to protein binding, thus inducing a quenching of FAD fluorescence decay time. Through application of the metabolic drugs antimycin and FCCP, the recorded signals could be assigned to a mitochondrial origin. The dopamine-induced changes could be observed in sequential FLIM and PLIM recordings, as well as in simultaneous FLIM/PLIM recordings using an intermediate TCSPC timing resolution.

Transient and stationary spectroscopy of cytochrome c: ultrafast internal conversion controls photoreduction.

PubMed

Löwenich, Dennis; Kleinermanns, Karl; Karunakaran, Venugopal; Kovalenko, Sergey Alexander

2008-01-01

Photoreduction of cytochrome c (Cyt c) has been reinvestigated using femtosecond-to-nanosecond transient absorption and stationary spectroscopy. Femtosecond spectra of oxidized Cyt c, recorded in the probe range 270-1000 nm, demonstrate similar evolution upon 266 or 403 nm excitation: an ultrafast 0.3 ps internal conversion followed by a 4 ps vibrational cooling. Late transient spectra after 20 ps, from the cold ground-state chromophore, reveal a small but measurable signal from reduced Cyt c. The yield phi for Fe3+-->Fe2+ photoreduction is measured to be phi(403) = 0.016 and phi(266) = 0.08 for 403 and 266 nm excitation. These yields lead to a guess of the barrier E(f)(A) = 55 kJ mol(-1) for thermal ground-state electron transfer (ET). Nanosecond spectra initially show the typical absorption from reduced Cyt c and then exhibit temperature-dependent sub-microsecond decays (0.5 micros at 297 K), corresponding to a barrier E(A)(b) = 33 kJ mol(-1) for the back ET reaction and a reaction energy DeltaE = 22 kJ mol(-1). The nanosecond transients do not decay to zero on a second time scale, demonstrating the stability of some of the reduced Cyt c. The yields calculated from this stable reduced form agree with quasistationary reduction yields. Modest heating of Cyt c leads to its efficient thermal reduction as demonstrated by differential stationary absorption spectroscopy. In summary, our results point to ultrafast internal conversion of oxidized Cyt c upon UV or visible excitation, followed by Fe-porphyrin reduction due to thermal ground-state ET as the prevailing mechanism.

Resolving environmental microheterogeneity and dielectric relaxation in fluorescence kinetics of protein

NASA Astrophysics Data System (ADS)

Rolinski, Olaf J.; McLaughlin, Damien; Birch, David J. S.; Vyshemirsky, Vladislav

2016-09-01

The fluorescence intensity decay of protein is easily measurable and reports on the intrinsic fluorophore-local environment interactions on the sub-nm spatial and sub-ns temporal scales, which are consistent with protein activity in numerous biomedical and industrial processes. This makes time-resolved fluorescence a perfect tool for understanding, monitoring and controlling these processes at the molecular level, but the complexity of the decay, which has been traditionally fitted to multi-exponential functions, has hampered the development of this technique over the last few decades. Using the example of tryptophan in HSA we present the alternative to the conventional approach to modelling intrinsic florescence intensity decay in protein where the key factors determining fluorescence decay, i.e. the excited-state depopulation and the dielectric relaxation (Toptygin and Brand 2000 Chem. Phys. Lett. 322 496-502), are represented by the individual relaxation functions. This allows quantification of both effects separately by determining their parameters from the global analysis of a series of fluorescence intensity decays measured at different detection wavelengths. Moreover, certain pairs of the recovered parameters of tryptophan were found to be correlated, indicating the influence of the dielectric relaxation on the transient rate of the electronic transitions. In this context the potential for the dual excited state depopulation /dielectric relaxation fluorescence lifetime sensing is discussed.

Ultrafast dynamics during the photoinduced phase transition in VO2

NASA Astrophysics Data System (ADS)

Wegkamp, Daniel; Stähler, Julia

2015-12-01

The phase transition of VO2 from a monoclinic insulator to a rutile metal, which occurs thermally at TC = 340 K, can also be driven by strong photoexcitation. The ultrafast dynamics during this photoinduced phase transition (PIPT) have attracted great scientific attention for decades, as this approach promises to answer the question of whether the insulator-to-metal (IMT) transition is caused by electronic or crystallographic processes through disentanglement of the different contributions in the time domain. We review our recent results achieved by femtosecond time-resolved photoelectron, optical, and coherent phonon spectroscopy and discuss them within the framework of a selection of latest, complementary studies of the ultrafast PIPT in VO2. We show that the population change of electrons and holes caused by photoexcitation launches a highly non-equilibrium plasma phase characterized by enhanced screening due to quasi-free carriers and followed by two branches of non-equilibrium dynamics: (i) an instantaneous (within the time resolution) collapse of the insulating gap that precedes charge carrier relaxation and significant ionic motion and (ii) an instantaneous lattice potential symmetry change that represents the onset of the crystallographic phase transition through ionic motion on longer timescales. We discuss the interconnection between these two non-thermal pathways with particular focus on the meaning of the critical fluence of the PIPT in different types of experiments. Based on this, we conclude that the PIPT threshold identified in optical experiments is most probably determined by the excitation density required to drive the lattice potential change rather than the IMT. These considerations suggest that the IMT can be driven by weaker excitation, predicting a transiently metallic, monoclinic state of VO2 that is not stabilized by the non-thermal structural transition and, thus, decays on ultrafast timescales.

Characterizing non-photochemical quenching in leaves through fluorescence lifetime snapshots

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

Sylak-Glassman, Emily J.; Zaks, Julia; Amarnath, Kapil

2015-03-12

A technique is described to measure the fluorescence decay profiles of intact leaves during adaptation to high light and subsequent relaxation to dark conditions. We illustrate how to ensure that photosystem II reaction centers are closed and compare data for wild type Arabidopsis thaliana with conventional pulse-amplitude modulated (PAM) fluorescence measurements. Unlike PAM measurements, the lifetime measurements are not sensitive to photobleaching or chloroplast shielding, and the form of the fluorescence decay provides additional information to test quantitative models of excitation dynamics in intact leaves.

Harmonium: An Ultrafast Vacuum Ultraviolet Facility.

PubMed

Arrell, Christopher A; Ojeda, José; Longetti, Luca; Crepaldi, Alberto; Roth, Silvan; Gatti, Gianmarco; Clark, Andrew; van Mourik, Frank; Drabbels, Marcel; Grioni, Marco; Chergui, Majed

2017-05-31

Harmonium is a vacuum ultraviolet (VUV) photon source built within the Lausanne Centre for Ultrafast Science (LACUS). Utilising high harmonic generation, photons from 20-110 eV are available to conduct steady-state or ultrafast photoelectron and photoion spectroscopies (PES and PIS). A pulse preserving monochromator provides either high energy resolution (70 meV) or high temporal resolution (40 fs). Three endstations have been commissioned for: a) PES of liquids; b) angular resolved PES (ARPES) of solids and; c) coincidence PES and PIS of gas phase molecules or clusters. The source has several key advantages: high repetition rate (up to 15 kHz) and high photon flux (1011 photons per second at 38 eV). The capabilities of the facility complement the Swiss ultrafast and X-ray community (SwissFEL, SLS, NCCR MUST, etc.) helping to maintain Switzerland's leading role in ultrafast science in the world.

Ultrafast spatiotemporal relaxation dynamics of excited electrons in a metal nanostructure detected by femtosecond-SNOM.

PubMed

Li, Zhi; Yue, Song; Chen, Jianjun; Gong, Qihuang

2010-06-21

Ultrahigh spatiotemporal resolved pump-probe signal near a gold nano-slit is detected by femtosecond-SNOM. By employing two-color pump-probe configuration and probing at the interband transition wavelength of the gold, signal contributed by surface plasmon polariton is avoided and spatiotemporal evolvement of excited electrons is successfully observed. From the contrast decaying of the periodical distribution of the pump-probe signal, ultrafast diffusion of excited electrons with a time scale of a few hundred femtoseconds is clearly identified. For comparison, such phenomenon cannot be observed by the one-color pump-probe configuration.

Scanning ultrafast electron microscopy.

PubMed

Yang, Ding-Shyue; Mohammed, Omar F; Zewail, Ahmed H

2010-08-24

Progress has been made in the development of four-dimensional ultrafast electron microscopy, which enables space-time imaging of structural dynamics in the condensed phase. In ultrafast electron microscopy, the electrons are accelerated, typically to 200 keV, and the microscope operates in the transmission mode. Here, we report the development of scanning ultrafast electron microscopy using a field-emission-source configuration. Scanning of pulses is made in the single-electron mode, for which the pulse contains at most one or a few electrons, thus achieving imaging without the space-charge effect between electrons, and still in ten(s) of seconds. For imaging, the secondary electrons from surface structures are detected, as demonstrated here for material surfaces and biological specimens. By recording backscattered electrons, diffraction patterns from single crystals were also obtained. Scanning pulsed-electron microscopy with the acquired spatiotemporal resolutions, and its efficient heat-dissipation feature, is now poised to provide in situ 4D imaging and with environmental capability.

Scanning ultrafast electron microscopy

PubMed Central

Yang, Ding-Shyue; Mohammed, Omar F.; Zewail, Ahmed H.

2010-01-01

Progress has been made in the development of four-dimensional ultrafast electron microscopy, which enables space-time imaging of structural dynamics in the condensed phase. In ultrafast electron microscopy, the electrons are accelerated, typically to 200 keV, and the microscope operates in the transmission mode. Here, we report the development of scanning ultrafast electron microscopy using a field-emission-source configuration. Scanning of pulses is made in the single-electron mode, for which the pulse contains at most one or a few electrons, thus achieving imaging without the space-charge effect between electrons, and still in ten(s) of seconds. For imaging, the secondary electrons from surface structures are detected, as demonstrated here for material surfaces and biological specimens. By recording backscattered electrons, diffraction patterns from single crystals were also obtained. Scanning pulsed-electron microscopy with the acquired spatiotemporal resolutions, and its efficient heat-dissipation feature, is now poised to provide in situ 4D imaging and with environmental capability. PMID:20696933

Ultrafast energy relaxation in single light-harvesting complexes

DOE PAGES

Maly, Pavel; Gruber, J. Michael; Cogdell, Richard J.; ...

2016-02-22

Energy relaxation in light-harvesting complexes has been extensively studied by various ultrafast spectroscopic techniques, the fastest processes being in the sub–100-fs range. At the same time, much slower dynamics have been observed in individual complexes by single-molecule fluorescence spectroscopy (SMS). In this work, we use a pump–probe-type SMS technique to observe the ultrafast energy relaxation in single light-harvesting complexes LH2 of purple bacteria. After excitation at 800 nm, the measured relaxation time distribution of multiple complexes has a peak at 95 fs and is asymmetric, with a tail at slower relaxation times. When tuning the excitation wavelength, the distribution changesmore » in both its shape and position. The observed behavior agrees with what is to be expected from the LH2 excited states structure. As we show by a Redfield theory calculation of the relaxation times, the distribution shape corresponds to the expected effect of Gaussian disorder of the pigment transition energies. By repeatedly measuring few individual complexes for minutes, we find that complexes sample the relaxation time distribution on a timescale of seconds. Furthermore, by comparing the distribution from a single long-lived complex with the whole ensemble, we demonstrate that, regarding the relaxation times, the ensemble can be considered ergodic. Lastly, our findings thus agree with the commonly used notion of an ensemble of identical LH2 complexes experiencing slow random fluctuations.« less

Ultrafast energy relaxation in single light-harvesting complexes

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

Maly, Pavel; Gruber, J. Michael; Cogdell, Richard J.

Energy relaxation in light-harvesting complexes has been extensively studied by various ultrafast spectroscopic techniques, the fastest processes being in the sub–100-fs range. At the same time, much slower dynamics have been observed in individual complexes by single-molecule fluorescence spectroscopy (SMS). In this work, we use a pump–probe-type SMS technique to observe the ultrafast energy relaxation in single light-harvesting complexes LH2 of purple bacteria. After excitation at 800 nm, the measured relaxation time distribution of multiple complexes has a peak at 95 fs and is asymmetric, with a tail at slower relaxation times. When tuning the excitation wavelength, the distribution changesmore » in both its shape and position. The observed behavior agrees with what is to be expected from the LH2 excited states structure. As we show by a Redfield theory calculation of the relaxation times, the distribution shape corresponds to the expected effect of Gaussian disorder of the pigment transition energies. By repeatedly measuring few individual complexes for minutes, we find that complexes sample the relaxation time distribution on a timescale of seconds. Furthermore, by comparing the distribution from a single long-lived complex with the whole ensemble, we demonstrate that, regarding the relaxation times, the ensemble can be considered ergodic. Lastly, our findings thus agree with the commonly used notion of an ensemble of identical LH2 complexes experiencing slow random fluctuations.« less

Protochlorophyll complexes with similar steady-state fluorescence characteristics can differ in fluorescence lifetimes. A model study in Triton X-100.

PubMed

Myśliwa-Kurdziel, Beata; Solymosi, Katalin; Kruk, Jerzy; Böddi, Béla; Strzałka, Kazimierz

2007-03-01

The steady-state and time-resolved fluorescence characteristics of protochlorophyll (Pchl) dissolved in neat Triton X-100 and in Triton X-100 micelles were investigated, and the fluorescence lifetimes of different Pchl spectral forms were studied. Varying the concentration of Pchl or diluting the micellar solutions either with a buffer or with a micellar solution, 631-634, 645-655, 680-692 and above 700 nm emitting Pchl complexes were prepared, the ratios of which varied from one another. The fluorescence decay of the 631-634 nm emitting (monomeric) form had a mono-exponential character with a 5.4-ns fluorescence lifetime. The long-wavelength Pchl complexes (aggregates) had two fluorescence lifetime values within a range of 1.4-3.9 ns and 0.15-0.84 ns, which showed high variability in different environments. Depending on the conditions, either mono- or double-exponential fluorescence decay was found for a fluorescence band at 680-685 nm. These data show that despite their very similar steady-state fluorescence properties, Pchl complexes can differ in fluorescence lifetimes, which may reflect different molecular structures, intrinsic geometries or different molecular interactions. This underlines the importance of complex spectroscopic analysis for a precise description of native and artificial chlorophyllous pigment forms.

Ultrafast and nanoscale diodes

NASA Astrophysics Data System (ADS)

Zhang, Peng; Lau, Y. Y.

2016-10-01

Charge carrier transport across interfaces of dissimilar materials (including vacuum) is the essence of all electronic devices. Ultrafast charge transport across a nanometre length scale is of fundamental importance in the miniaturization of vacuum and plasma electronics. With the combination of recent advances in electronics, photonics and nanotechnology, these miniature devices may integrate with solid-state platforms, achieving superior performance. This paper reviews recent modelling efforts on quantum tunnelling, ultrafast electron emission and transport, and electrical contact resistance. Unsolved problems and challenges in these areas are addressed.

Pump-probe micro-spectroscopy by means of an ultra-fast acousto-optics delay line.

PubMed

Audier, Xavier; Balla, Naveen; Rigneault, Hervé

2017-01-15

We demonstrate femtosecond pump-probe transient absorption spectroscopy using a programmable dispersive filter as an ultra-fast delay line. Combined with fast synchronous detection, this delay line allows for recording of 6 ps decay traces at 34 kHz. With such acquisition speed, we perform single point pump-probe spectroscopy on bulk samples in 80 μs and hyperspectral pump-probe imaging over a field of view of 100 μm in less than a second. The usability of the method is illustrated in a showcase experiment to image and discriminate between two pigments in a mixture.

Ultrafast, large-field multiphoton microscopy based on an acousto-optic deflector and a spatial light modulator.

PubMed

Shao, Yonghong; Qin, Wan; Liu, Honghai; Qu, Junle; Peng, Xiang; Niu, Hanben; Gao, Bruce Z

2012-07-01

We present an ultrafast, large-field multiphoton excitation fluorescence microscope with high lateral and axial resolutions based on a two-dimensional (2-D) acousto-optical deflector (AOD) scanner and spatial light modulator (SLM). When a phase-only SLM is used to shape the near-infrared light from a mode-locked titanium:sapphire laser into a multifocus array including the 0-order beam, a 136 μm × 136 μm field of view is achieved with a 60× objective using a 2-D AOD scanner without any mechanical scan element. The two-photon fluorescence image of a neuronal network that was obtained using this system demonstrates that our microscopy permits observation of dynamic biological events in a large field with high-temporal and -spatial resolution.

Serum albumin binding sites properties in donors and in schizophrenia patients: the study of fluorescence decay of the probe K-35 using S-60 synchrotron pulse excitation

NASA Astrophysics Data System (ADS)

Gryzunov, Yu. A.; Syrejshchikova, T. I.; Komarova, M. N.; Misionzhnik, E. Yu; Uzbekov, M. G.; Molodetskich, A. V.; Dobretsov, G. E.; Yakimenko, M. N.

2000-06-01

The properties of serum albumin obtained from donors and from paranoid schizophrenia patients were studied with the fluorescent probe K-35 (N-carboxyphenylimide of dimethylaminonaphthalic acid) and time-resolved fluorescence spectroscopy on the SR beam station of the S-60 synchrotron of the Lebedev Physical Institute. The mean fluorescence quantum yield of K-35 in patients serum was decreased significantly by 25-60% comparing with donors. The analysis of pre-exponential factors of fluorescence decay using "amplitude standard" method has shown that in patient sera the fraction of K-35 molecules bound with albumin and inaccessible to fluorescence quenchers ("bright" K-35 molecules with τ1=8.0±0.4 ns) is 1.2-3 times less than in the donor sera. The fraction of K-35 molecules with partly quenched fluorescence ( τ2=1.44±0.22 ns) was significantly increased in schizophrenia patients. The results obtained suggest that the properties of binding region in serum albumin molecules of acute paranoid schizophrenia patients change significantly.

Uncovering Highly-Excited State Mixing in Acetone Using Ultrafast VUV Pulses and Coincidence Imaging Techniques

DOE PAGES

Couch, David E.; Kapteyn, Henry C.; Murnane, Margaret M.; ...

2017-03-17

Here, understanding the ultrafast dynamics of highly-excited electronic states of small molecules is critical for a better understanding of atmospheric and astrophysical processes, as well as for designing coherent control strategies for manipulating chemical dynamics. In highly excited states, nonadiabatic coupling, electron-electron interactions, and the high density of states govern dynamics. However, these states are computationally and experimentally challenging to access. Fortunately, new sources of ultrafast vacuum ultraviolet pulses, in combination with electron-ion coincidence spectroscopies, provide new tools to unravel the complex electronic landscape. Here we report time-resolved photoelectron-photoion coincidence experiments using 8 eV pump photons to study the highlymore » excited states of acetone. We uncover for the first time direct evidence that the resulting excited state consists of a mixture of both n y → 3p and π → π* character, which decays with a time constant of 330 fs. In the future, this approach can inform models of VUV photochemistry and aid in designing coherent control strategies for manipulating chemical reactions.« less

Uncovering Highly-Excited State Mixing in Acetone Using Ultrafast VUV Pulses and Coincidence Imaging Techniques

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

Couch, David E.; Kapteyn, Henry C.; Murnane, Margaret M.

Here, understanding the ultrafast dynamics of highly-excited electronic states of small molecules is critical for a better understanding of atmospheric and astrophysical processes, as well as for designing coherent control strategies for manipulating chemical dynamics. In highly excited states, nonadiabatic coupling, electron-electron interactions, and the high density of states govern dynamics. However, these states are computationally and experimentally challenging to access. Fortunately, new sources of ultrafast vacuum ultraviolet pulses, in combination with electron-ion coincidence spectroscopies, provide new tools to unravel the complex electronic landscape. Here we report time-resolved photoelectron-photoion coincidence experiments using 8 eV pump photons to study the highlymore » excited states of acetone. We uncover for the first time direct evidence that the resulting excited state consists of a mixture of both n y → 3p and π → π* character, which decays with a time constant of 330 fs. In the future, this approach can inform models of VUV photochemistry and aid in designing coherent control strategies for manipulating chemical reactions.« less

Fluorescent optical position sensor

DOEpatents

Weiss, Jonathan D.

2005-11-15

A fluorescent optical position sensor and method of operation. A small excitation source side-pumps a localized region of fluorescence at an unknown position along a fluorescent waveguide. As the fluorescent light travels down the waveguide, the intensity of fluorescent light decreases due to absorption. By measuring with one (or two) photodetectors the attenuated intensity of fluorescent light emitted from one (or both) ends of the waveguide, the position of the excitation source relative to the waveguide can be determined by comparing the measured light intensity to a calibrated response curve or mathematical model. Alternatively, excitation light can be pumped into an end of the waveguide, which generates an exponentially-decaying continuous source of fluorescent light along the length of the waveguide. The position of a photodetector oriented to view the side of the waveguide can be uniquely determined by measuring the intensity of the fluorescent light emitted radially at that location.

Ultrafast demagnetization at high temperatures

NASA Astrophysics Data System (ADS)

Hoveyda, F.; Hohenstein, E.; Judge, R.; Smadici, S.

2018-05-01

Time-resolved pump-probe measurements were made at variable heat accumulation in Co/Pd superlattices. Heat accumulation increases the baseline temperature and decreases the equilibrium magnetization. Transient ultrafast demagnetization first develops with higher fluence in parallel with strong equilibrium thermal spin fluctuations. The ultrafast demagnetization is then gradually removed as the equilibrium temperature approaches the Curie temperature. The transient magnetization time-dependence is well fit with the spin-flip scattering model.

Staggered Multiple-PRF Ultrafast Color Doppler.

PubMed

Posada, Daniel; Poree, Jonathan; Pellissier, Arnaud; Chayer, Boris; Tournoux, Francois; Cloutier, Guy; Garcia, Damien

2016-06-01

Color Doppler imaging is an established pulsed ultrasound technique to visualize blood flow non-invasively. High-frame-rate (ultrafast) color Doppler, by emissions of plane or circular wavefronts, allows severalfold increase in frame rates. Conventional and ultrafast color Doppler are both limited by the range-velocity dilemma, which may result in velocity folding (aliasing) for large depths and/or large velocities. We investigated multiple pulse-repetition-frequency (PRF) emissions arranged in a series of staggered intervals to remove aliasing in ultrafast color Doppler. Staggered PRF is an emission process where time delays between successive pulse transmissions change in an alternating way. We tested staggered dual- and triple-PRF ultrafast color Doppler, 1) in vitro in a spinning disc and a free jet flow, and 2) in vivo in a human left ventricle. The in vitro results showed that the Nyquist velocity could be extended to up to 6 times the conventional limit. We found coefficients of determination r(2) ≥ 0.98 between the de-aliased and ground-truth velocities. Consistent de-aliased Doppler images were also obtained in the human left heart. Our results demonstrate that staggered multiple-PRF ultrafast color Doppler is efficient for high-velocity high-frame-rate blood flow imaging. This is particularly relevant for new developments in ultrasound imaging relying on accurate velocity measurements.

A Search for Ultrafast Novae in M31

NASA Astrophysics Data System (ADS)

Sola, Nicole; Rector, Travis A.; Shafter, Allen W.; Horst, Chuck; Igarashi, Amy; Henze, Martin; Pilachowski, Catherine A.

2018-06-01

Numerous surveys in search of extragalactic novae have been completed over the last century. From Local Group surveys it has been estimated that the number of novae that occur in M31 is approximately 65 yr-1 (Darnley et al. 2006), with a total of more than 1000 having been discovered over the past century. A fraction of these are recurrent novae that recur on the timescales of years to decades (Shafter et al. 2015).Novae typically fade from view on timescales of weeks to months. However, Shara et al. (2017) present models that predict the existence of "ultrafast" novae that have two-magnitude decay times (t2) of less than a day. The remarkable recurrent nova M31N 2008-12a has a t2 time of ~2 days (e.g., Darnley et al. 2016). None faster than this have been seen in M31; however, most surveys of extragalactic novae use cadences of a day or longer, meaning such novae could be missed.In October 2017 we completed a two-week search for ultrafast novae in M31 with the WIYN 0.9m telescope. The telescope's Half-Degree Imager provided a field of view of a quarter square degree, which covers most of M31's bulge and part of the disk. Weather hampered observations on some nights, but for most nights we were able to obtain multiple observations of M31 on a near hourly basis. We present the results of our search.

4-D ultrafast shear-wave imaging.

PubMed

Gennisson, Jean-Luc; Provost, Jean; Deffieux, Thomas; Papadacci, Clément; Imbault, Marion; Pernot, Mathieu; Tanter, Mickael

2015-06-01

Over the last ten years, shear wave elastography (SWE) has seen considerable development and is now routinely used in clinics to provide mechanical characterization of tissues to improve diagnosis. The most advanced technique relies on the use of an ultrafast scanner to generate and image shear waves in real time in a 2-D plane at several thousands of frames per second. We have recently introduced 3-D ultrafast ultrasound imaging to acquire with matrix probes the 3-D propagation of shear waves generated by a dedicated radiation pressure transducer in a single acquisition. In this study, we demonstrate 3-D SWE based on ultrafast volumetric imaging in a clinically applicable configuration. A 32 × 32 matrix phased array driven by a customized, programmable, 1024-channel ultrasound system was designed to perform 4-D shear-wave imaging. A matrix phased array was used to generate and control in 3-D the shear waves inside the medium using the acoustic radiation force. The same matrix array was used with 3-D coherent plane wave compounding to perform high-quality ultrafast imaging of the shear wave propagation. Volumetric ultrafast acquisitions were then beamformed in 3-D using a delay-and-sum algorithm. 3-D volumetric maps of the shear modulus were reconstructed using a time-of-flight algorithm based on local multiscale cross-correlation of shear wave profiles in the three main directions using directional filters. Results are first presented in an isotropic homogeneous and elastic breast phantom. Then, a full 3-D stiffness reconstruction of the breast was performed in vivo on healthy volunteers. This new full 3-D ultrafast ultrasound system paves the way toward real-time 3-D SWE.

Interatomic Coulombic Decay: The Mechanism for Rapid Deexcitation of Hollow Atoms.

PubMed

Wilhelm, Richard A; Gruber, Elisabeth; Schwestka, Janine; Kozubek, Roland; Madeira, Teresa I; Marques, José P; Kobus, Jacek; Krasheninnikov, Arkady V; Schleberger, Marika; Aumayr, Friedrich

2017-09-08

The impact of a highly charged ion onto a solid gives rise to charge exchange between the ion and target atoms, so that a slow ion gets neutralized in the vicinity of the surface. Using highly charged Ar and Xe ions and the surface-only material graphene as a target, we show that the neutralization and deexcitation of the ions proceeds on a sub-10 fs time scale. We further demonstrate that a multiple Interatomic Coulombic Decay (ICD) model can describe the observed ultrafast deexcitation. Other deexcitation mechanisms involving nonradiative decay and quasimolecular orbital formation during the impact are not important, as follows from the comparison of our experimental data with the results of first-principles calculations. Our method also enables the estimation of ICD rates directly.

Temporal binning of time-correlated single photon counting data improves exponential decay fits and imaging speed

PubMed Central

Walsh, Alex J.; Sharick, Joe T.; Skala, Melissa C.; Beier, Hope T.

2016-01-01

Time-correlated single photon counting (TCSPC) enables acquisition of fluorescence lifetime decays with high temporal resolution within the fluorescence decay. However, many thousands of photons per pixel are required for accurate lifetime decay curve representation, instrument response deconvolution, and lifetime estimation, particularly for two-component lifetimes. TCSPC imaging speed is inherently limited due to the single photon per laser pulse nature and low fluorescence event efficiencies (<10%) required to reduce bias towards short lifetimes. Here, simulated fluorescence lifetime decays are analyzed by SPCImage and SLIM Curve software to determine the limiting lifetime parameters and photon requirements of fluorescence lifetime decays that can be accurately fit. Data analysis techniques to improve fitting accuracy for low photon count data were evaluated. Temporal binning of the decays from 256 time bins to 42 time bins significantly (p<0.0001) improved fit accuracy in SPCImage and enabled accurate fits with low photon counts (as low as 700 photons/decay), a 6-fold reduction in required photons and therefore improvement in imaging speed. Additionally, reducing the number of free parameters in the fitting algorithm by fixing the lifetimes to known values significantly reduced the lifetime component error from 27.3% to 3.2% in SPCImage (p<0.0001) and from 50.6% to 4.2% in SLIM Curve (p<0.0001). Analysis of nicotinamide adenine dinucleotide–lactate dehydrogenase (NADH-LDH) solutions confirmed temporal binning of TCSPC data and a reduced number of free parameters improves exponential decay fit accuracy in SPCImage. Altogether, temporal binning (in SPCImage) and reduced free parameters are data analysis techniques that enable accurate lifetime estimation from low photon count data and enable TCSPC imaging speeds up to 6x and 300x faster, respectively, than traditional TCSPC analysis. PMID:27446663

Ultrafast laser ablation for targeted atherosclerotic plaque removal

NASA Astrophysics Data System (ADS)

Lanvin, Thomas; Conkey, Donald B.; Descloux, Laurent; Frobert, Aurelien; Valentin, Jeremy; Goy, Jean-Jacques; Cook, Stéphane; Giraud, Marie-Noelle; Psaltis, Demetri

2015-07-01

Coronary artery disease, the main cause of heart disease, develops as immune cells and lipids accumulate into plaques within the coronary arterial wall. As a plaque grows, the tissue layer (fibrous cap) separating it from the blood flow becomes thinner and increasingly susceptible to rupturing and causing a potentially lethal thrombosis. The stabilization and/or treatment of atherosclerotic plaque is required to prevent rupturing and remains an unsolved medical problem. Here we show for the first time targeted, subsurface ablation of atherosclerotic plaque using ultrafast laser pulses. Excised atherosclerotic mouse aortas were ablated with ultrafast near-infrared (NIR) laser pulses. The physical damage was characterized with histological sections of the ablated atherosclerotic arteries from six different mice. The ultrafast ablation system was integrated with optical coherence tomography (OCT) imaging for plaque-specific targeting and monitoring of the resulting ablation volume. We find that ultrafast ablation of plaque just below the surface is possible without causing damage to the fibrous cap, which indicates the potential use of ultrafast ablation for subsurface atherosclerotic plaque removal. We further demonstrate ex vivo subsurface ablation of a plaque volume through a catheter device with the high-energy ultrafast pulse delivered via hollow-core photonic crystal fiber.

Pancreatic tissue assessment using fluorescence and reflectance spectroscopy

NASA Astrophysics Data System (ADS)

Chandra, Malavika; Heidt, David; Simeone, Diane; McKenna, Barbara; Scheiman, James; Mycek, Mary-Ann

2007-07-01

The ability of multi-modal optical spectroscopy to detect signals from pancreatic tissue was demonstrated by studying human pancreatic cancer xenografts in mice and freshly excised human pancreatic tumor tissue. Measured optical spectra and fluorescence decays were correlated with tissue morphological and biochemical properties. The measured spectral features and decay times correlated well with expected pathological differences in normal, pancreatitis and adenocarcinoma tissue states. The observed differences between the fluorescence and reflectance properties of normal, pancreatitis and adenocarcinoma tissue indicate a possible application of multi-modal optical spectroscopy to differentiating between the three tissue classifications.

On the mechanism of non-radiative decay of blue fluorescent protein chromophore: New insight from the excited-state molecular dynamics simulations and potential energy calculations

NASA Astrophysics Data System (ADS)

Zhao, Li; Liu, Jian-Yong; Zhou, Pan-Wang

2017-11-01

A detailed theoretical investigation based on the ab initio on-the-fly surface hopping dynamics simulations and potential energy surfaces calculations has been performed to unveil the mechanism of the photoinduced non-adiabatic relaxation process of the isolated blue fluorescent protein (BFP) chromophore in gas phase. The data analysis presents that the dominant reaction coordinate of the BFP chromophore is driven by a rotation motion around the CC double bridging bond, which is in remarkable difference with a previous result which supports a Hula-Twist rotation pattern. Such behavior is consistent with the double bond rotation pattern of the GFP neutral chromophore. In addition, the dynamics simulations give an estimated decay time of 1.1 ps for the S1 state, which is agrees well with the experimental values measured in proteins. The present work offers a straightforward understanding for the decay mechanism of the BFP chromophore and suggestions of the photochemical properties of analogous protein chromophores. We hope the current work would be helpful for further exploration of the BFP photochemical and photophysical properties in various environments, and can provide guidance and prediction for rational design of the fluorescent proteins catering for different demands.

Ultrafast and low barrier motions in the photoreactions of the green fluorescent protein.

PubMed

van Thor, Jasper J; Georgiev, Georgi Y; Towrie, Michael; Sage, J Timothy

2005-09-30

Green fluorescent protein (GFP) fluoresces efficiently under blue excitation despite major electrostatic rearrangements resulting from photoionization of the chromophore and neutralization of Glu-222. A competing phototransformation process, which ionizes the chromophore and decarboxylates Glu-222, mimics the electrostatic and structural changes in the fluorescence photocycle. Structural and spectroscopic analysis of the cryogenically stabilized photoproduct at 100 K and a structurally annealed intermediate of the phototransformed protein at 170 K reveals distinct structural relaxations involving protein, chromophore, solvent, and photogenerated CO2. Strong structural changes of the 100 K photoproduct after decarboxylation appear exclusively within 15 angstroms of the chromophore and include the electrostatically driven perturbations of Gln-69, Cys-70, and water molecules in an H-bonding network connecting the chromophore. X-ray crystallography to 1.85 angstroms resolution and static and picosecond time-resolved IR spectroscopy identify structural mechanisms common to phototransformation and to the fluorescence photocycle. In particular, the appearance of a 1697 cm(-1) (+) difference band in both photocycle and phototransformation intermediates is a spectroscopic signature for the structural perturbation of Gln-69. This is taken as evidence for an electrostatically driven dynamic response that is common to both photoreaction pathways. The interactions between the chromophore and the perturbed residues and solvent are decreased or removed in the T203H single and T203H/Q69L double mutants, resulting in a strong reduction of the fluorescence quantum yield. This suggests that the electrostatic response to the transient formation of a buried charge in the wild type is important for the bright fluorescence.

A Wide-Field Fluorescence Microscope Extension for Ultrafast Screening of One-Bead One-Compound Libraries Using a Spectral Image Subtraction Approach.

PubMed

Heusermann, Wolf; Ludin, Beat; Pham, Nhan T; Auer, Manfred; Weidemann, Thomas; Hintersteiner, Martin

2016-05-09

The increasing involvement of academic institutions and biotech companies in drug discovery calls for cost-effective methods to identify new bioactive molecules. Affinity-based on-bead screening of combinatorial one-bead one-compound libraries combines a split-mix synthesis design with a simple protein binding assay operating directly at the bead matrix. However, one bottleneck for academic scale on-bead screening is the unavailability of a cheap, automated, and robust screening platform that still provides a quantitative signal related to the amount of target protein binding to individual beads for hit bead ranking. Wide-field fluorescence microscopy has long been considered unsuitable due to significant broad spectrum autofluorescence of the library beads in conjunction with low detection sensitivity. Herein, we demonstrate how such a standard microscope equipped with LED-based excitation and a modern CMOS camera can be successfully used for selecting hit beads. We show that the autofluorescence issue can be overcome by an optical image subtraction approach that yields excellent signal-to-noise ratios for the detection of bead-associated target proteins. A polymer capillary attached to a semiautomated bead-picking device allows the operator to efficiently isolate individual hit beads in less than 20 s. The system can be used for ultrafast screening of >200,000 bead-bound compounds in 1.5 h, thereby making high-throughput screening accessible to a wider group within the scientific community.

Tissue characterization by time-resolved fluorescence spectroscopy of endogenous and exogenous fluorochromes: apparatus design and preliminary results

NASA Astrophysics Data System (ADS)

Glanzmann, Thomas M.; Ballini, Jean-Pierre; Jichlinski, Patrice; van den Bergh, Hubert; Wagnieres, Georges A.

1996-12-01

The biomedical use of an optical fiber-based spectro- temporal fluorometer that can endoscopically record the fluorescence decay of an entire spectrum without scanning is presented. The detector consists of a streak camera coupled to a spectrograph. A mode-locked argon ion pumped dye laser or a nitrogen laser-pumped dye laser are used as pulsed excitation light sources. We measured the fluorescence decays of endogenous fluorophores and of ALA-induced- protoporphyrin IX(PPIX) in an excised human bladder with a carcinoma in situ (CIS). Each autofluorescence decay can be decomposed in at least three exponential components for all tissue samples investigated if the excitation is at 425 nm. The decays of the autofluorescence of all normal sites of the human bladder are similar and they differ significantly from the decays measured on the CIS and the necrotic tissue. The fluorescence of the ALA-induced PPIX in the bladder is monoexponential with a lifetime of 15 (plus or minus 1) ns and this fluorescence lifetime does not change significantly between the normal urothelium and the CIS. A photoproduct of ALA-PPIX with a fluorescence maximum at 670 nm and a lifetime of 8 (plus or minus 1) ns was observed. The measurement of the decay of the autofluorescence allowed to correctly identify a normal tissue site that was classified as abnormal by the measurement of the ALA-PPIX fluorescence intensity.

Ultrafast fiber lasers: practical applications

NASA Astrophysics Data System (ADS)

Pastirk, Igor; Sell, Alexander; Herda, Robert; Brodschelm, Andreas; Zach, Armin

2015-05-01

Over past three decades ultrafast lasers have come a long way from the bulky, demanding and very sensitive scientific research projects to widely available commercial products. For the majority of this period the titanium-sapphire-based ultrafast systems were the workhorse for scientific and emerging industrial and biomedical applications. However the complexity and intrinsic bulkiness of solid state lasers have prevented even larger penetration into wider array of practical applications. With emergence of femtosecond fiber lasers, based primarily on Er-doped and Yb-doped fibers that provide compact, inexpensive and dependable fs and ps pulses, new practical applications have become a reality. The overview of current state of the art ultrafast fiber sources, their basic principles and most prominent applications will be presented, including micromachining and biomedical implementations (ophthalmology) on one end of the pulse energy spectrum and 3D lithography and THz applications on the other.

The Phasor Approach to Fluorescence Lifetime Imaging Analysis

PubMed Central

Digman, Michelle A.; Caiolfa, Valeria R.; Zamai, Moreno; Gratton, Enrico

2008-01-01

Changing the data representation from the classical time delay histogram to the phasor representation provides a global view of the fluorescence decay at each pixel of an image. In the phasor representation we can easily recognize the presence of different molecular species in a pixel or the occurrence of fluorescence resonance energy transfer. The analysis of the fluorescence lifetime imaging microscopy (FLIM) data in the phasor space is done observing clustering of pixels values in specific regions of the phasor plot rather than by fitting the fluorescence decay using exponentials. The analysis is instantaneous since is not based on calculations or nonlinear fitting. The phasor approach has the potential to simplify the way data are analyzed in FLIM, paving the way for the analysis of large data sets and, in general, making the FLIM technique accessible to the nonexpert in spectroscopy and data analysis. PMID:17981902

Metal-enhanced fluorescence of single green fluorescent protein (GFP)

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

Fu Yi; Zhang Jian; Lakowicz, Joseph R.

2008-11-28

The green fluorescent protein (GFP) has emerged as a powerful reporter molecule for monitoring gene expression, protein localization, and protein-protein interaction. However, the detection of low concentrations of GFPs is limited by the weakness of the fluorescent signal and the low photostability. In this report, we observed the proximity of single GFPs to metallic silver nanoparticles increases its fluorescence intensity approximately 6-fold and decreases the decay time. Single protein molecules on the silvered surfaces emitted 10-fold more photons as compared to glass prior to photobleaching. The photostability of single GFP has increased to some extent. Accordingly, we observed longer durationmore » time and suppressed blinking. The single-molecule lifetime histograms indicate the relatively heterogeneous distributions of protein mutants inside the structure.« less

Ultrafast Intramolecular Electron and Proton Transfer in Bis(imino)isoindole Derivatives.

PubMed

Driscoll, Eric; Sorenson, Shayne; Dawlaty, Jahan M

2015-06-04

Concerted motion of electrons and protons in the excited state is pertinent to a wide range of chemical phenomena, including those relevant for solar-to-fuel light harvesting. The excited state dynamics of small proton-bearing molecules are expected to serve as models for better understanding such phenomena. In particular, for designing the next generation of multielectron and multiproton redox catalysts, understanding the dynamics of more than one proton in the excited state is important. Toward this goal, we have measured the ultrafast dynamics of intramolecular excited state proton transfer in a recently synthesized dye with two equivalent transferable protons. We have used a visible ultrafast pump to initiate the proton transfer in the excited state, and have probed the transient absorption of the molecule over a wide bandwidth in the visible range. The measurement shows that the signal which is characteristic of proton transfer emerges within ∼710 fs. To identify whether both protons were transferred in the excited state, we have measured the ultrafast dynamics of a related derivative, where only a single proton was available for transfer. The measured proton transfer time in that molecule was ∼427 fs. The observed dynamics in both cases were reasonably fit with single exponentials. Supported by the ultrafast observations, steady-state fluorescence, and preliminary computations of the relaxed excited states, we argue that the doubly protonated derivative most likely transfers only one of its two protons in the excited state. We have performed calculations of the frontier molecular orbitals in the Franck-Condon region. The calculations show that in both derivatives, the excitation is primarily from the HOMO to LUMO causing a large rearrangement of the electronic charge density immediately after photoexcitation. In particular, charge density is shifted away from the phenolic protons and toward the proton acceptor nitrogens. The proton transfer is

Fluorescence lifetime plate reader: Resolution and precision meet high-throughput

PubMed Central

Petersen, Karl J.; Peterson, Kurt C.; Muretta, Joseph M.; Higgins, Sutton E.; Gillispie, Gregory D.; Thomas, David D.

2014-01-01

We describe a nanosecond time-resolved fluorescence spectrometer that acquires fluorescence decay waveforms from each well of a 384-well microplate in 3 min with signal-to-noise exceeding 400 using direct waveform recording. The instrument combines high-energy pulsed laser sources (5–10 kHz repetition rate) with a photomultiplier and high-speed digitizer (1 GHz) to record a fluorescence decay waveform after each pulse. Waveforms acquired from rhodamine or 5-((2-aminoethyl)amino) naphthalene-1-sulfonic acid dyes in a 384-well plate gave lifetime measurements 5- to 25-fold more precise than the simultaneous intensity measurements. Lifetimes as short as 0.04 ns were acquired by interleaving with an effective sample rate of 5 GHz. Lifetime measurements resolved mixtures of single-exponential dyes with better than 1% accuracy. The fluorescence lifetime plate reader enables multiple-well fluorescence lifetime measurements with an acquisition time of 0.5 s per well, suitable for high-throughput fluorescence lifetime screening applications. PMID:25430092

Plasmonic antennas as design elements for coherent ultrafast nanophotonics.

PubMed

Brinks, Daan; Castro-Lopez, Marta; Hildner, Richard; van Hulst, Niek F

2013-11-12

Broadband excitation of plasmons allows control of light-matter interaction with nanometric precision at femtosecond timescales. Research in the field has spiked in the past decade in an effort to turn ultrafast plasmonics into a diagnostic, microscopy, computational, and engineering tool for this novel nanometric-femtosecond regime. Despite great developments, this goal has yet to materialize. Previous work failed to provide the ability to engineer and control the ultrafast response of a plasmonic system at will, needed to fully realize the potential of ultrafast nanophotonics in physical, biological, and chemical applications. Here, we perform systematic measurements of the coherent response of plasmonic nanoantennas at femtosecond timescales and use them as building blocks in ultrafast plasmonic structures. We determine the coherent response of individual nanoantennas to femtosecond excitation. By mixing localized resonances of characterized antennas, we design coupled plasmonic structures to achieve well-defined ultrafast and phase-stable field dynamics in a predetermined nanoscale hotspot. We present two examples of the application of such structures: control of the spectral amplitude and phase of a pulse in the near field, and ultrafast switching of mutually coherent hotspots. This simple, reproducible and scalable approach transforms ultrafast plasmonics into a straightforward tool for use in fields as diverse as room temperature quantum optics, nanoscale solid-state physics, and quantum biology.

Material processing with fiber based ultrafast pulse delivery

NASA Astrophysics Data System (ADS)

Baumbach, S.; Stockburger, R.; Führa, B.; Zoller, S.; Thum, S.; Moosmann, J.; Maier, D.; Kanal, F.; Russ, S.; Kaiser, E.; Budnicki, A.; Sutter, D. H.; Pricking, S.; Killi, A.

2018-02-01

We report on TRUMPF's ultrafast laser systems equipped with industrialized hollow core fiber laser light cables. Beam guidance in general by means of optical fibers, e.g. for multi kilowatt cw laser systems, has become an integral part of laser-based material processing. One advantage of fiber delivery, among others, is the mechanical separation between laser and processing head. An equally important benefit is given by the fact that the fiber end acts as an opto-mechanical fix-point close to successive optical elements in the processing head. Components like lenses, diffractive optical elements etc. can thus be designed towards higher efficiency which results in better material processing. These aspects gain increasing significance when the laser system operates in fundamental mode which is usually the case for ultrafast lasers. Through the last years beam guidance of ultrafast laser pulses by means of hollow core fiber technology established very rapidly. The combination of TRUMPF's long-term stable ultrafast laser sources, passive fiber coupling, connector and packaging forms a flexible and powerful system for laser based material processing well suited for an industrial environment. In this article we demonstrate common material processing applications with ultrafast lasers realized with TRUMPF's hollow core fiber delivery. The experimental results are contrasted and evaluated against conventional free space propagation in order to illustrate the performance of flexible ultrafast beam delivery.

Coherent Nuclear Wave Packets in Q States by Ultrafast Internal Conversions in Free Base Tetraphenylporphyrin.

PubMed

Kim, So Young; Joo, Taiha

2015-08-06

Persistence of vibrational coherence in electronic transition has been noted especially in biochemical systems. Here, we report the dynamics between electronic excited states in free base tetraphenylporphyrin (H2TPP) by time-resolved fluorescence with high time resolution. Following the photoexcitation of the B state, ultrafast internal conversion occurs to the Qx state directly as well as via the Qy state. Unique and distinct coherent nuclear wave packet motions in the Qx and Qy states are observed through the modulation of the fluorescence intensity in time. The instant, serial internal conversions from the B to the Qy and Qx states generate the coherent wave packets. Theory and experiment show that the observed vibrational modes involve the out-of-plane vibrations of the porphyrin ring that are strongly coupled to the internal conversion of H2TPP.

Compact ultrafast semiconductor disk laser: targeting GFP based nonlinear applications in living organisms

PubMed Central

Aviles-Espinosa, Rodrigo; Filippidis, George; Hamilton, Craig; Malcolm, Graeme; Weingarten, Kurt J.; Südmeyer, Thomas; Barbarin, Yohan; Keller, Ursula; Santos, Susana I.C.O; Artigas, David; Loza-Alvarez, Pablo

2011-01-01

We present a portable ultrafast Semiconductor Disk Laser (SDL) (or vertical extended cavity surface emitting laser—VECSELs), to be used for nonlinear microscopy. The SDL is modelocked using a quantum-dot semiconductor saturable absorber mirror (SESAM), delivering an average output power of 287 mW, with 1.5 ps pulses at 500 MHz and a central wavelength of 965 nm. Specifically, despite the fact of having long pulses and high repetition rates, we demonstrate the potential of this laser for Two-Photon Excited Fluorescence (TPEF) imaging of in vivo Caenorhabditis elegans (C. elegans) expressing Green Fluorescent Protein (GFP) in a set of neuronal processes and cell bodies. Efficient TPEF imaging is achieved due to the fact that this wavelength matches the peak of the two-photon action cross section of this widely used fluorescent marker. The SDL extended versatility is shown by presenting Second Harmonic Generation images of pharynx, uterus, body wall muscles and its potential to be used to excite other different commercial dyes. Importantly this non-expensive, turn-key, compact laser system could be used as a platform to develop portable nonlinear bio-imaging devices. PMID:21483599

Excited state dynamics of the astaxanthin radical cation

NASA Astrophysics Data System (ADS)

Amarie, Sergiu; Förster, Ute; Gildenhoff, Nina; Dreuw, Andreas; Wachtveitl, Josef

2010-07-01

Femtosecond transient absorption spectroscopy in the visible and NIR and ultrafast fluorescence spectroscopy were used to examine the excited state dynamics of astaxanthin and its radical cation. For neutral astaxanthin, two kinetic components corresponding to time constants of 130 fs (decay of the S 2 excited state) and 5.2 ps (nonradiative decay of the S 1 excited state) were sufficient to describe the data. The dynamics of the radical cation proved to be more complex. The main absorption band was shifted to 880 nm (D 0 → D 3 transition), showing a weak additional band at 1320 nm (D 0 → D 1 transition). We found, that D 3 decays to the lower-lying D 2 within 100 fs, followed by a decay to D 1 with a time constant of 0.9 ps. The D 1 state itself exhibited a dual behavior, the majority of the population is transferred to the ground state in 4.9 ps, while a small population decays on a longer timescale of 40 ps. Both transitions from D 1 were found to be fluorescent.

Radiative decay engineering 5: metal-enhanced fluorescence and plasmon emission

PubMed Central

Lakowicz, Joseph R.

2009-01-01

Metallic particles and surfaces display diverse and complex optical properties. Examples include the intense colors of noble metal colloids, surface plasmon resonance absorption by thin metal films, and quenching of excited fluorophores near the metal surfaces. Recently, the interactions of fluorophores with metallic particles and surfaces (metals) have been used to obtain increased fluorescence intensities, to develop assays based on fluorescence quenching by gold colloids, and to obtain directional radiation from fluorophores near thin metal films. For metal-enhanced fluorescence it is difficult to predict whether a particular metal structure, such as a colloid, fractal, or continuous surface, will quench or enhance fluorescence. In the present report we suggest how the effects of metals on fluorescence can be explained using a simple concept, based on radiating plasmons (RPs). The underlying physics may be complex but the concept is simple to understand. According to the RP model, the emission or quenching of a fluorophore near the metal can be predicted from the optical properties of the metal structures as calculated from electrodynamics, Mie theory, and/or Maxwell’s equations. For example, according to Mie theory and the size and shape of the particle, the extinction of metal colloids can be due to either absorption or scattering. Incident energy is dissipated by absorption. Far-field radiation is created by scattering. Based on our model small colloids are expected to quench fluorescence because absorption is dominant over scattering. Larger colloids are expected to enhance fluorescence because the scattering component is dominant over absorption. The ability of a metal’s surface to absorb or reflect light is due to wavenumber matching requirements at the metal–sample interface. Wavenumber matching considerations can also be used to predict whether fluorophores at a given distance from a continuous planar surface will be emitted or quenched. These

Time scales of tunneling decay of a localized state

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

Ban, Yue; Muga, J. G.; Sherman, E. Ya.

2010-12-15

Motivated by recent time-domain experiments on ultrafast atom ionization, we analyze the transients and time scales that characterize, aside from the relatively long lifetime, the decay of a localized state by tunneling. While the tunneling starts immediately, some time is required for the outgoing flux to develop. This short-term behavior depends strongly on the initial state. For the initial state, tightly localized so that the initial transients are dominated by over-the-barrier motion, the time scale for flux propagation through the barrier is close to the Buettiker-Landauer traversal time. Then a quasistationary, slow-decay process follows, which sets ideal conditions for observingmore » diffraction in time at longer times and distances. To define operationally a tunneling time at the barrier edge, we extrapolate backward the propagation of the wave packet that escaped from the potential. This extrapolated time is considerably longer than the time scale of the flux and density buildup at the barrier edge.« less

Time-resolved multicolor two-photon excitation fluorescence microscopy of cells and tissues

NASA Astrophysics Data System (ADS)

Zheng, Wei

2014-11-01

Multilabeling which maps the distribution of different targets is an indispensable technique in many biochemical and biophysical studies. Two-photon excitation fluorescence (TPEF) microscopy of endogenous fluorophores combining with conventional fluorescence labeling techniques such as genetically encoded fluorescent protein (FP) and fluorescent dyes staining could be a powerful tool for imaging living cells. However, the challenge is that the excitation and emission wavelength of these endogenous fluorophores and fluorescent labels are very different. A multi-color ultrafast source is required for the excitation of multiple fluorescence molecules. In this study, we developed a two-photon imaging system with excitations from the pump femtosecond laser and the selected supercontinuum generated from a photonic crystal fiber (PCF). Multiple endogenous fluorophores, fluorescent proteins and fluorescent dyes were excited in their optimal wavelengths simultaneously. A time- and spectral-resolved detection system was used to record the TPEF signals. This detection technique separated the TPEF signals from multiple sources in time and wavelength domains. Cellular organelles such as nucleus, mitochondria, microtubule and endoplasmic reticulum, were clearly revealed in the TPEF images. The simultaneous imaging of multiple fluorophores of cells will greatly aid the study of sub-cellular compartments and protein localization.

Quantum simulation of ultrafast dynamics using trapped ultracold atoms.

PubMed

Senaratne, Ruwan; Rajagopal, Shankari V; Shimasaki, Toshihiko; Dotti, Peter E; Fujiwara, Kurt M; Singh, Kevin; Geiger, Zachary A; Weld, David M

2018-05-25

Ultrafast electronic dynamics are typically studied using pulsed lasers. Here we demonstrate a complementary experimental approach: quantum simulation of ultrafast dynamics using trapped ultracold atoms. Counter-intuitively, this technique emulates some of the fastest processes in atomic physics with some of the slowest, leading to a temporal magnification factor of up to 12 orders of magnitude. In these experiments, time-varying forces on neutral atoms in the ground state of a tunable optical trap emulate the electric fields of a pulsed laser acting on bound charged particles. We demonstrate the correspondence with ultrafast science by a sequence of experiments: nonlinear spectroscopy of a many-body bound state, control of the excitation spectrum by potential shaping, observation of sub-cycle unbinding dynamics during strong few-cycle pulses, and direct measurement of carrier-envelope phase dependence of the response to an ultrafast-equivalent pulse. These results establish cold-atom quantum simulation as a complementary tool for studying ultrafast dynamics.

The influence of the Tbeta level upon fluorescence and laser properties of aromatic compounds.

PubMed

Nijegorodov, N; Winkoun, D P; Nkoma, J S

2004-07-01

The fluorescence and laser properties of seven specially chosen aromatic compounds are studied at 293 degrees C. The quantum yield of fluorescence, gamma, decay times, tauf, of the deaerated and non-deaerated solutions are measured. The oscillator strength, fe, fluorescence rate constants, kf, natural lifetimes, tauT0, and intersystem crossing rate constants, kST, are calculated. Some laser parameters are calculated or measured experimentally. It is found that the position of the Tbeta level plays an important role in the fluorescence and laser properties of aromatic compounds. If the Tbeta level is situated below the Sp level, it decreases the quantum yield of fluorescence and the decay time and increases the threshold of laser action. If, due to some structural changes of a molecule, the Tbeta level is situated higher than the Sp level, then the quantum yield of fluorescence and the decay times are increasing and the threshold of laser action is decreasing. Such influence of the position of the Tbeta level upon fluorescence and laser properties of aromatic compound is explained by the fact that the Sp level mixes with the Tbeta level more readily than with other taupipi* levels.

Ultra-fast Object Recognition from Few Spikes

DTIC Science & Technology

2005-07-06

Computer Science and Artificial Intelligence Laboratory Ultra-fast Object Recognition from Few Spikes Chou Hung, Gabriel Kreiman , Tomaso Poggio...neural code for different kinds of object-related information. *The authors, Chou Hung and Gabriel Kreiman , contributed equally to this work...Supplementary Material is available at http://ramonycajal.mit.edu/ kreiman /resources/ultrafast

Progress in ultrafast laser processing and future prospects

NASA Astrophysics Data System (ADS)

Sugioka, Koji

2017-03-01

The unique characteristics of ultrafast lasers have rapidly revolutionized materials processing after their first demonstration in 1987. The ultrashort pulse width of the laser suppresses heat diffusion to the surroundings of the processed region, which minimizes the formation of a heat-affected zone and thereby enables ultrahigh precision micro- and nanofabrication of various materials. In addition, the extremely high peak intensity can induce nonlinear multiphoton absorption, which extends the diversity of materials that can be processed to transparent materials such as glass. Nonlinear multiphoton absorption enables three-dimensional (3D) micro- and nanofabrication by irradiation with tightly focused femtosecond laser pulses inside transparent materials. Thus, ultrafast lasers are currently widely used for both fundamental research and practical applications. This review presents progress in ultrafast laser processing, including micromachining, surface micro- and nanostructuring, nanoablation, and 3D and volume processing. Advanced technologies that promise to enhance the performance of ultrafast laser processing, such as hybrid additive and subtractive processing, and shaped beam processing are discussed. Commercial and industrial applications of ultrafast laser processing are also introduced. Finally, future prospects of the technology are given with a summary.

3D ultrafast ultrasound imaging in vivo.

PubMed

Provost, Jean; Papadacci, Clement; Arango, Juan Esteban; Imbault, Marion; Fink, Mathias; Gennisson, Jean-Luc; Tanter, Mickael; Pernot, Mathieu

2014-10-07

Very high frame rate ultrasound imaging has recently allowed for the extension of the applications of echography to new fields of study such as the functional imaging of the brain, cardiac electrophysiology, and the quantitative imaging of the intrinsic mechanical properties of tumors, to name a few, non-invasively and in real time. In this study, we present the first implementation of Ultrafast Ultrasound Imaging in 3D based on the use of either diverging or plane waves emanating from a sparse virtual array located behind the probe. It achieves high contrast and resolution while maintaining imaging rates of thousands of volumes per second. A customized portable ultrasound system was developed to sample 1024 independent channels and to drive a 32  ×  32 matrix-array probe. Its ability to track in 3D transient phenomena occurring in the millisecond range within a single ultrafast acquisition was demonstrated for 3D Shear-Wave Imaging, 3D Ultrafast Doppler Imaging, and, finally, 3D Ultrafast combined Tissue and Flow Doppler Imaging. The propagation of shear waves was tracked in a phantom and used to characterize its stiffness. 3D Ultrafast Doppler was used to obtain 3D maps of Pulsed Doppler, Color Doppler, and Power Doppler quantities in a single acquisition and revealed, at thousands of volumes per second, the complex 3D flow patterns occurring in the ventricles of the human heart during an entire cardiac cycle, as well as the 3D in vivo interaction of blood flow and wall motion during the pulse wave in the carotid at the bifurcation. This study demonstrates the potential of 3D Ultrafast Ultrasound Imaging for the 3D mapping of stiffness, tissue motion, and flow in humans in vivo and promises new clinical applications of ultrasound with reduced intra--and inter-observer variability.

Perspective: Ultrafast magnetism and THz spintronics

NASA Astrophysics Data System (ADS)

Walowski, Jakob; Münzenberg, Markus

2016-10-01

This year the discovery of femtosecond demagnetization by laser pulses is 20 years old. For the first time, this milestone work by Bigot and coworkers gave insight directly into the time scales of microscopic interactions that connect the spin and electron system. While intense discussions in the field were fueled by the complexity of the processes in the past, it now became evident that it is a puzzle of many different parts. Rather than providing an overview that has been presented in previous reviews on ultrafast processes in ferromagnets, this perspective will show that with our current depth of knowledge the first applications are developed: THz spintronics and all-optical spin manipulation are becoming more and more feasible. The aim of this perspective is to point out where we can connect the different puzzle pieces of understanding gathered over 20 years to develop novel applications. Based on many observations in a large number of experiments. Differences in the theoretical models arise from the localized and delocalized nature of ferromagnetism. Transport effects are intrinsically non-local in spintronic devices and at interfaces. We review the need for multiscale modeling to address the processes starting from electronic excitation of the spin system on the picometer length scale and sub-femtosecond time scale, to spin wave generation, and towards the modeling of ultrafast phase transitions that altogether determine the response time of the ferromagnetic system. Today, our current understanding gives rise to the first usage of ultrafast spin physics for ultrafast magnetism control: THz spintronic devices. This makes the field of ultrafast spin-dynamics an emerging topic open for many researchers right now.

Perspective: Ultrafast magnetism and THz spintronics

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

Walowski, Jakob; Münzenberg, Markus

This year the discovery of femtosecond demagnetization by laser pulses is 20 years old. For the first time, this milestone work by Bigot and coworkers gave insight directly into the time scales of microscopic interactions that connect the spin and electron system. While intense discussions in the field were fueled by the complexity of the processes in the past, it now became evident that it is a puzzle of many different parts. Rather than providing an overview that has been presented in previous reviews on ultrafast processes in ferromagnets, this perspective will show that with our current depth of knowledgemore » the first applications are developed: THz spintronics and all-optical spin manipulation are becoming more and more feasible. The aim of this perspective is to point out where we can connect the different puzzle pieces of understanding gathered over 20 years to develop novel applications. Based on many observations in a large number of experiments. Differences in the theoretical models arise from the localized and delocalized nature of ferromagnetism. Transport effects are intrinsically non-local in spintronic devices and at interfaces. We review the need for multiscale modeling to address the processes starting from electronic excitation of the spin system on the picometer length scale and sub-femtosecond time scale, to spin wave generation, and towards the modeling of ultrafast phase transitions that altogether determine the response time of the ferromagnetic system. Today, our current understanding gives rise to the first usage of ultrafast spin physics for ultrafast magnetism control: THz spintronic devices. This makes the field of ultrafast spin-dynamics an emerging topic open for many researchers right now.« less

Ultrafast FADC multiplexer

NASA Astrophysics Data System (ADS)

Mirzoyan, R.; Cortina, J.; Lorenz, E.; Martinez, M.; Ostankov, A.; Paneque, D.

2002-10-01

Ultrafast Flash amplitude-to-digital converters (FADCs) are still very expensive. Here we propose a multiplexing scheme allowing one in common trigger mode to read out multiple signal sources by using a single FADC channel. Usual coaxial cables can be used in the multiplexer as analog signal delay elements. The limited bandwidth of the coaxial cable, depending on its type and length will set an upper limit to the number of multiplexed channels. Better bandwidth and the correspondingly higher number of multiplexed channels one can obtain when using the technique of transmission of analog signals via optical fibers. Low-cost vertical cavity surface emitting laser (VCSEL) diodes can be used as converters of fast electrical signals into near infrared light. Multiplexing can be an economically priced solution when one needs ultrafast digitization of hundreds of fast signal channels.

4D multiple-cathode ultrafast electron microscopy

PubMed Central

Baskin, John Spencer; Liu, Haihua; Zewail, Ahmed H.

2014-01-01

Four-dimensional multiple-cathode ultrafast electron microscopy is developed to enable the capture of multiple images at ultrashort time intervals for a single microscopic dynamic process. The dynamic process is initiated in the specimen by one femtosecond light pulse and probed by multiple packets of electrons generated by one UV laser pulse impinging on multiple, spatially distinct, cathode surfaces. Each packet is distinctly recorded, with timing and detector location controlled by the cathode configuration. In the first demonstration, two packets of electrons on each image frame (of the CCD) probe different times, separated by 19 picoseconds, in the evolution of the diffraction of a gold film following femtosecond heating. Future elaborations of this concept to extend its capabilities and expand the range of applications of 4D ultrafast electron microscopy are discussed. The proof-of-principle demonstration reported here provides a path toward the imaging of irreversible ultrafast phenomena of materials, and opens the door to studies involving the single-frame capture of ultrafast dynamics using single-pump/multiple-probe, embedded stroboscopic imaging. PMID:25006261

4D multiple-cathode ultrafast electron microscopy.

PubMed

Baskin, John Spencer; Liu, Haihua; Zewail, Ahmed H

2014-07-22

Four-dimensional multiple-cathode ultrafast electron microscopy is developed to enable the capture of multiple images at ultrashort time intervals for a single microscopic dynamic process. The dynamic process is initiated in the specimen by one femtosecond light pulse and probed by multiple packets of electrons generated by one UV laser pulse impinging on multiple, spatially distinct, cathode surfaces. Each packet is distinctly recorded, with timing and detector location controlled by the cathode configuration. In the first demonstration, two packets of electrons on each image frame (of the CCD) probe different times, separated by 19 picoseconds, in the evolution of the diffraction of a gold film following femtosecond heating. Future elaborations of this concept to extend its capabilities and expand the range of applications of 4D ultrafast electron microscopy are discussed. The proof-of-principle demonstration reported here provides a path toward the imaging of irreversible ultrafast phenomena of materials, and opens the door to studies involving the single-frame capture of ultrafast dynamics using single-pump/multiple-probe, embedded stroboscopic imaging.

Time-resolved fluorescence spectroscopy for chemical sensors

NASA Astrophysics Data System (ADS)

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.

Graphene-clad microfibre saturable absorber for ultrafast fibre lasers.

PubMed

Liu, X M; Yang, H R; Cui, Y D; Chen, G W; Yang, Y; Wu, X Q; Yao, X K; Han, D D; Han, X X; Zeng, C; Guo, J; Li, W L; Cheng, G; Tong, L M

2016-05-16

Graphene, whose absorbance is approximately independent of wavelength, allows broadband light-matter interactions with ultrafast responses. The interband optical absorption of graphene can be saturated readily under strong excitation, thereby enabling scientists to exploit the photonic properties of graphene to realize ultrafast lasers. The evanescent field interaction scheme of the propagating light with graphene covered on a D-shaped fibre or microfibre has been employed extensively because of the nonblocking configuration. Obviously, most of the fibre surface is unused in these techniques. Here, we exploit a graphene-clad microfibre (GCM) saturable absorber in a mode-locked fibre laser for the generation of ultrafast pulses. The proposed all-surface technique can guarantee a higher efficiency of light-graphene interactions than the aforementioned techniques. Our GCM-based saturable absorber can generate ultrafast optical pulses within 1.5 μm. This saturable absorber is compatible with current fibre lasers and has many merits such as low saturation intensities, ultrafast recovery times, and wide wavelength ranges. The proposed saturable absorber will pave the way for graphene-based wideband photonics.

Graphene-clad microfibre saturable absorber for ultrafast fibre lasers

PubMed Central

Liu, X. M.; Yang, H. R.; Cui, Y. D.; Chen, G. W.; Yang, Y.; Wu, X. Q.; Yao, X. K.; Han, D. D.; Han, X. X.; Zeng, C.; Guo, J.; Li, W. L.; Cheng, G.; Tong, L. M.

2016-01-01

Graphene, whose absorbance is approximately independent of wavelength, allows broadband light–matter interactions with ultrafast responses. The interband optical absorption of graphene can be saturated readily under strong excitation, thereby enabling scientists to exploit the photonic properties of graphene to realize ultrafast lasers. The evanescent field interaction scheme of the propagating light with graphene covered on a D-shaped fibre or microfibre has been employed extensively because of the nonblocking configuration. Obviously, most of the fibre surface is unused in these techniques. Here, we exploit a graphene-clad microfibre (GCM) saturable absorber in a mode-locked fibre laser for the generation of ultrafast pulses. The proposed all-surface technique can guarantee a higher efficiency of light–graphene interactions than the aforementioned techniques. Our GCM-based saturable absorber can generate ultrafast optical pulses within 1.5 μm. This saturable absorber is compatible with current fibre lasers and has many merits such as low saturation intensities, ultrafast recovery times, and wide wavelength ranges. The proposed saturable absorber will pave the way for graphene-based wideband photonics. PMID:27181419

Ultrafast electron-optical phonon scattering and quasiparticle lifetime in CVD-grown graphene.

PubMed

Shang, Jingzhi; Yu, Ting; Lin, Jianyi; Gurzadyan, Gagik G

2011-04-26

Ultrafast quasiparticle dynamics in graphene grown by chemical vapor deposition (CVD) has been studied by UV pump/white-light probe spectroscopy. Transient differential transmission spectra of monolayer graphene are observed in the visible probe range (400-650 nm). Kinetics of the quasiparticle (i.e., low-energy single-particle excitation with renormalized energy due to electron-electron Coulomb, electron-optical phonon (e-op), and optical phonon-acoustic phonon (op-ap) interactions) was monitored with 50 fs resolution. Extending the probe range to near-infrared, we find the evolution of quasiparticle relaxation channels from monoexponential e-op scattering to double exponential decay due to e-op and op-ap scattering. Moreover, quasiparticle lifetimes of mono- and randomly stacked graphene films are obtained for the probe photon energies continuously from 1.9 to 2.3 eV. Dependence of quasiparticle decay rate on the probe energy is linear for 10-layer stacked graphene films. This is due to the dominant e-op intervalley scattering and the linear density of states in the probed electronic band. A dimensionless coupling constant W is derived, which characterizes the scattering strength of quasiparticles by lattice points in graphene.

Rigidifying fluorescent linkers by metal-organic framework formation for fluorescence blue shift and quantum yield enhancement.

PubMed

Wei, Zhangwen; Gu, Zhi-Yuan; Arvapally, Ravi K; Chen, Ying-Pin; McDougald, Roy N; Ivy, Joshua F; Yakovenko, Andrey A; Feng, Dawei; Omary, Mohammad A; Zhou, Hong-Cai

2014-06-11

We demonstrate that rigidifying the structure of fluorescent linkers by structurally constraining them in metal-organic frameworks (MOFs) to control their conformation effectively tunes the fluorescence energy and enhances the quantum yield. Thus, a new tetraphenylethylene-based zirconium MOF exhibits a deep-blue fluorescent emission at 470 nm with a unity quantum yield (99.9 ± 0.5%) under Ar, representing ca. 3600 cm(-1) blue shift and doubled radiative decay efficiency vs the linker precursor. An anomalous increase in the fluorescence lifetime and relative intensity takes place upon heating the solid MOF from cryogenic to ambient temperatures. The origin of these unusual photoluminescence properties is attributed to twisted linker conformation, intramolecular hindrance, and framework rigidity.

Ultrafast fluorescence spectroscopy of biologically relevant chromophores using type II difference frequency generation

NASA Astrophysics Data System (ADS)

Léonard, J.; Gelot, T.; Torgasin, K.; Haacke, S.

2011-01-01

A novel femtosecond fluorescence experiment based on type II difference frequency mixing is demonstrated. This approach is particularly interesting for near-UV emitting biological chromophores like amino acids and nucleotides, as the fluorescence is converted into the spectral range where CCD have their highest quantum efficiencies. The method is implemented with a 5-kHz amplified Ti:Sapphire laser system and first results obtained with 2,5-diphenyloxazole (PPO) in ethanol are reported.

Resonant fluorescence for multilevel systems in intense nonmonochromatic fields: possibilities for applications in laser medicine

NASA Astrophysics Data System (ADS)

Karagodova, Tamara Y.

1999-03-01

The theory of resonant fluorescence of multilevel system in two monochromatic intense laser fields has been applied for investigating the temporal decay of magnetic sublevels of an atom. As for two-level system the triplet of resonant fluorescence is observed, for real atom being the multilevel system the multiplet of resonant fluorescence can be observed. The excitation spectra, defining the intensities of lines in the multiplet of resonant fluorescence, and shifts of components of spectra are shown. Typical temporal dependence of fluorescence intensity for magnetic sublevels of an atom having different relaxation constants is shown. The computer simulation of resonant fluorescence for simple systems can help to understand the regularities in temporal decay curves of atherosclerotic plaque, malignant tumor compared to normal surrounding tissue.

Several new directions for ultrafast fiber lasers [Invited].

PubMed

Fu, Walter; Wright, Logan G; Sidorenko, Pavel; Backus, Sterling; Wise, Frank W

2018-04-16

Ultrafast fiber lasers have the potential to make applications of ultrashort pulses widespread - techniques not only for scientists, but also for doctors, manufacturing engineers, and more. Today, this potential is only realized in refractive surgery and some femtosecond micromachining. The existing market for ultrafast lasers remains dominated by solid-state lasers, primarily Ti:sapphire, due to their superior performance. Recent advances show routes to ultrafast fiber sources that provide performance and capabilities equal to, and in some cases beyond, those of Ti:sapphire, in compact, versatile, low-cost devices. In this paper, we discuss the prospects for future ultrafast fiber lasers built on new kinds of pulse generation that capitalize on nonlinear dynamics. We focus primarily on three promising directions: mode-locked oscillators that use nonlinearity to enhance performance; systems that use nonlinear pulse propagation to achieve ultrashort pulses without a mode-locked oscillator; and multimode fiber lasers that exploit nonlinearities in space and time to obtain unparalleled control over an electric field.

Barium Tagging n Solid Xenon for nEXO Neutrinoless Double Beta Decay

NASA Astrophysics Data System (ADS)

Walton, Tim; Chambers, Chris; Craycraft, Adam; Fairbank, William; nEXO Collaboration

2015-04-01

nEXO is a next-generation experiment designed to search for neutrinoless double beta decay of the isotope Xe136 in a liquid xenon time projection chamber. Positive observation of this decay would determine the nature of the neutrino to be a Majorana particle. Since the daughter of this decay is barium (Ba136), detecting the presence of Ba136 at a decay site (called ``barium tagging'') would provide strong rejection of backgrounds in the search for this decay. This would involve detecting a single barium ion from within a macroscopic volume of liquid xenon. This technique may be available for a second phase of the nEXO detector and sensitivity beyond the inverted hierarchy to neutrino oscillations. Several methods of barium tagging are being explored by the nEXO collaboration, but here we present a method of trapping the barium ion/atom (it may neutralize) in solid xenon (SXe) at the end of a cold probe, and then detecting the ion/atom by its fluorescence in the SXe. Our group at CSU has been studying the fluorescence of Ba in SXe by laser excitation, in order to ultimately detect a single Ba +/Ba in a SXe sample. We present studies of fluorescence signals, as well as recent results on imaging small numbers of Ba atoms in SXe, in a focused laser region. This work is supported by grants from the National Science Foundation and the Department of Energy.

On the heterogeneity of fluorescence lifetime of room temperature ionic liquids: onset of a journey for exploring red emitting dyes.

PubMed

Ghosh, Anup; Chatterjee, Tanmay; Mandal, Prasun K

2012-06-25

An excitation and emission wavelength dependent non-exponential fluorescence decay behaviour of room temperature ionic liquids (RTILs) has been noted. Average fluorescence lifetimes have been found to vary by a factor of three or more. Red emitting dyes dissolved in RTILs are found to follow hitherto unobserved single exponential fluorescence decay behaviour.

Space charge effects in ultrafast electron diffraction and imaging

NASA Astrophysics Data System (ADS)

Tao, Zhensheng; Zhang, He; Duxbury, P. M.; Berz, Martin; Ruan, Chong-Yu

2012-02-01

Understanding space charge effects is central for the development of high-brightness ultrafast electron diffraction and microscopy techniques for imaging material transformation with atomic scale detail at the fs to ps timescales. We present methods and results for direct ultrafast photoelectron beam characterization employing a shadow projection imaging technique to investigate the generation of ultrafast, non-uniform, intense photoelectron pulses in a dc photo-gun geometry. Combined with N-particle simulations and an analytical Gaussian model, we elucidate three essential space-charge-led features: the pulse lengthening following a power-law scaling, the broadening of the initial energy distribution, and the virtual cathode threshold. The impacts of these space charge effects on the performance of the next generation high-brightness ultrafast electron diffraction and imaging systems are evaluated.

Mapping the lignin distribution in pretreated sugarcane bagasse by confocal and fluorescence lifetime imaging microscopy

PubMed Central

2013-01-01

Background Delignification pretreatments of biomass and methods to assess their efficacy are crucial for biomass-to-biofuels research and technology. Here, we applied confocal and fluorescence lifetime imaging microscopy (FLIM) using one- and two-photon excitation to map the lignin distribution within bagasse fibers pretreated with acid and alkali. The evaluated spectra and decay times are correlated with previously calculated lignin fractions. We have also investigated the influence of the pretreatment on the lignin distribution in the cell wall by analyzing the changes in the fluorescence characteristics using two-photon excitation. Eucalyptus fibers were also analyzed for comparison. Results Fluorescence spectra and variations of the decay time correlate well with the delignification yield and the lignin distribution. The decay dependences are considered two-exponential, one with a rapid (τ1) and the other with a slow (τ2) decay time. The fastest decay is associated to concentrated lignin in the bagasse and has a low sensitivity to the treatment. The fluorescence decay time became longer with the increase of the alkali concentration used in the treatment, which corresponds to lignin emission in a less concentrated environment. In addition, the two-photon fluorescence spectrum is very sensitive to lignin content and accumulation in the cell wall, broadening with the acid pretreatment and narrowing with the alkali one. Heterogeneity of the pretreated cell wall was observed. Conclusions Our results reveal lignin domains with different concentration levels. The acid pretreatment caused a disorder in the arrangement of lignin and its accumulation in the external border of the cell wall. The alkali pretreatment efficiently removed lignin from the middle of the bagasse fibers, but was less effective in its removal from their surfaces. Our results evidenced a strong correlation between the decay times of the lignin fluorescence and its distribution within the cell

Slow Organic-to-Inorganic Sub-Lattice Thermalization in Methylammonium Lead Halide Perovskites Observed by Ultrafast Photoluminescence

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

Chang, Angela Y.; Cho, Yi-Ju; Chen, Kuan-Chen

2016-05-31

Carrier dynamics in methylammonium lead halide (CH3NH3PbI3-xClx) perovskite thin films, of differing crystal morphology, are examined as functions of temperature and excitation wavelength. At room temperature, long-lived (> nanosecond) transient absorption signals indicate negligible carrier trapping. However, in measurements of ultrafast photoluminescence excited at 400 nm, a heretofore unexplained, large amplitude (50%-60%), 45 ps decay process is observed. This feature persists for temperatures down to the orthorhombic phase transition. Varying pump photon energy reveals that the fast, band-edge photoluminescence (PL) decay only appears for excitation >= 2.38 eV (520 nm), with larger amplitudes for higher pump energies. Lower photon-energy excitationmore » yields slow dynamics consistent with negligible carrier trapping. Further, sub-bandgap two-photon pumping yields identical PL dynamics as direct absorption, signifying sensitivity to the total deposited energy and insensitivity to interfacial effects. Together with first principles electronic structure and ab initio molecular dynamics calculations, the results suggest the fast PL decay stems from excitation of high energy phonon modes associated with the organic sub-lattice that temporarily enhance wavefunction overlap within the inorganic component owing to atomic displacement, thereby transiently changing the PL radiative rate during thermalization. Hence, the fast PL decay relates a characteristic organic-to-inorganic sub-lattice equilibration timescale at optoelectronic-relevant excitation energies.« less

Ultrafast Spectroscopy of Proton-Coupled Electron Transfer (PCET) in Photocatalysis

DTIC Science & Technology

2016-07-08

AFRL-AFOSR-VA-TR-2016-0244 Ultrafast Spectroscopy of Proton-Coupled Electron Transfer (PCET) in Photocatalysis Jahan Dawlaty UNIVERSITY OF SOUTHERN...TITLE AND SUBTITLE Ultrafast Spectroscopy of Proton-Coupled Electron Transfer (PCET) in Photocatalysis 5a. CONTRACT NUMBER 5b. GRANT NUMBER FA9550...298 Back (Rev. 8/98) DISTRIBUTION A: Distribution approved for public release. Final Report: AFOSR YIP Grant FA9550-13-1-0128: Ultrafast Spectroscopy

Giant ultrafast Kerr effect in superconductors

NASA Astrophysics Data System (ADS)

Robson, Charles W.; Fraser, Kieran A.; Biancalana, Fabio

2017-06-01

We study the ultrafast Kerr effect and high-harmonic generation in superconductors by formulating a model for a time-varying electromagnetic pulse normally incident on a thin-film superconductor. It is found that superconductors exhibit exceptionally large χ(3 ) due to the progressive destruction of Cooper pairs, and display high-harmonic generation at low incident intensities, and the highest nonlinear susceptibility of all known materials in the THz regime. Our theory opens up avenues for accessible analytical and numerical studies of the ultrafast dynamics of superconductors.

Diagnostic Performance of Ultrafast Brain MRI for Evaluation of Abusive Head Trauma.

PubMed

Kralik, S F; Yasrebi, M; Supakul, N; Lin, C; Netter, L G; Hicks, R A; Hibbard, R A; Ackerman, L L; Harris, M L; Ho, C Y

2017-04-01

MR imaging with sedation is commonly used to detect intracranial traumatic pathology in the pediatric population. Our purpose was to compare nonsedated ultrafast MR imaging, noncontrast head CT, and standard MR imaging for the detection of intracranial trauma in patients with potential abusive head trauma. A prospective study was performed in 24 pediatric patients who were evaluated for potential abusive head trauma. All patients received noncontrast head CT, ultrafast brain MR imaging without sedation, and standard MR imaging with general anesthesia or an immobilizer, sequentially. Two pediatric neuroradiologists independently reviewed each technique blinded to other modalities for intracranial trauma. We performed interreader agreement and consensus interpretation for standard MR imaging as the criterion standard. Diagnostic accuracy was calculated for ultrafast MR imaging, noncontrast head CT, and combined ultrafast MR imaging and noncontrast head CT. Interreader agreement was moderate for ultrafast MR imaging (κ = 0.42), substantial for noncontrast head CT (κ = 0.63), and nearly perfect for standard MR imaging (κ = 0.86). Forty-two percent of patients had discrepancies between ultrafast MR imaging and standard MR imaging, which included detection of subarachnoid hemorrhage and subdural hemorrhage. Sensitivity, specificity, and positive and negative predictive values were obtained for any traumatic pathology for each examination: ultrafast MR imaging (50%, 100%, 100%, 31%), noncontrast head CT (25%, 100%, 100%, 21%), and a combination of ultrafast MR imaging and noncontrast head CT (60%, 100%, 100%, 33%). Ultrafast MR imaging was more sensitive than noncontrast head CT for the detection of intraparenchymal hemorrhage ( P = .03), and the combination of ultrafast MR imaging and noncontrast head CT was more sensitive than noncontrast head CT alone for intracranial trauma ( P = .02). In abusive head trauma, ultrafast MR imaging, even combined with noncontrast

Unraveling shock-induced chemistry using ultrafast lasers

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

Moore, David Steven

The exquisite time synchronicity between shock and diagnostics needed to unravel chemical events occurring in picoseconds has been achieved using a shaped ultrafast laser pulse to both drive the shocks and interrogate the sample via a multiplicity of optical diagnostics. The shaped laser drive pulse can produce well-controlled shock states of sub-ns duration with sub-10 ps risetimes, sufficient for investigation offast reactions or phase transformations in a thin layer with picosecond time resolution. The shock state is characterized using ultrafast dynamic ellipsometry (UDE) in either planar or Gaussian spatial geometries, the latter allowing measurements of the equation of state ofmore » materials at a range of stresses in a single laser pulse. Time-resolved processes in materials are being interrogated using UDE, ultrafast infrared absorption, ultrafast UV/visible absorption, and femtosecond stimulated Raman spectroscopy. Using these tools we showed that chemistry in an energetic thin film starts only after an induction time of a few tens of ps, an observation that allows differentiation between proposed shock-induced reaction mechanisms. These tools are presently being applied to a variety of energetic and reactive sample systems, from nitromethane and carbon disulfide, to microengineered interfaces in tunable energetic mixtures. Recent results will be presented, and future trends outlined.« less

Direct Characterization of Ultrafast Energy-Time Entangled Photon Pairs.

PubMed

MacLean, Jean-Philippe W; Donohue, John M; Resch, Kevin J

2018-02-02

Energy-time entangled photons are critical in many quantum optical phenomena and have emerged as important elements in quantum information protocols. Entanglement in this degree of freedom often manifests itself on ultrafast time scales, making it very difficult to detect, whether one employs direct or interferometric techniques, as photon-counting detectors have insufficient time resolution. Here, we implement ultrafast photon counters based on nonlinear interactions and strong femtosecond laser pulses to probe energy-time entanglement in this important regime. Using this technique and single-photon spectrometers, we characterize all the spectral and temporal correlations of two entangled photons with femtosecond resolution. This enables the witnessing of energy-time entanglement using uncertainty relations and the direct observation of nonlocal dispersion cancellation on ultrafast time scales. These techniques are essential to understand and control the energy-time degree of freedom of light for ultrafast quantum optics.

Determination of the orientation of fluorescent labels relative to myosin S1 in solution from time-resolved fluorescence anisotropy experiments

NASA Astrophysics Data System (ADS)

van der Heide, Uulke A.; Gerritsen, Hans C.; Trayer, Ian P.; Levine, Yehudi K.

1992-04-01

The time-resolved fluorescence anisotropy of myosin S1 covalently labeled with Eosin-5- maleimide and 1,5-I-AEDANS was measured in solution. Each probe was specifically attached at one SH-group on the S1. The two most reactive SH sites on the heavy chain of the myosin S1 were used. The fluorescence anisotropy was measured at different excitation wavelengths. In this way, several absorption moments were utilized, each having a distinct orientation in the frame of the dye. The orientations of the transition moments in the dyes were determined in a separate experiment using an angle resolved fluorescence depolarization experiment on dyes embedded in stretched matrices of PVA polymers. The anisotropy decay curves exhibit fast (<3 ns) and slow (> 100 ns) components. The slow decay components reflect the motion of the large protein molecules. The fast anisotropy decay are attributed to a fast, but restricted, motion of the bound dye relative to the protein as experiments on free dyes in solution reveal subnanosecond anisotropy decays. The anisotropy decays have been analyzed in terms of a model which describes the restricted motion of the dye molecule relative to the protein and the overall rotation of the dye-protein complex in solution. An important element in the model is the incorporation of the orientational distribution of the dye relative to the protein. The observed anisotropy decays were analyzed using a global target approach in which the experimental data obtained at different excitation wavelengths are fitted simultaneously to the theoretical model. It is important to note that the orientational distribution of the dye relative to the protein, as well as the rotational correlation times of the motions for a dye attached to a given binding site, are independent of the excitation wavelength used. This leads to a reduction in the number of independent parameters optimized by the nonlinear least squares procedure. The orientational distribution of the dye

Ultrafast Ultrasound Imaging With Cascaded Dual-Polarity Waves.

PubMed

Zhang, Yang; Guo, Yuexin; Lee, Wei-Ning

2018-04-01

Ultrafast ultrasound imaging using plane or diverging waves, instead of focused beams, has advanced greatly the development of novel ultrasound imaging methods for evaluating tissue functions beyond anatomical information. However, the sonographic signal-to-noise ratio (SNR) of ultrafast imaging remains limited due to the lack of transmission focusing, and thus insufficient acoustic energy delivery. We hereby propose a new ultrafast ultrasound imaging methodology with cascaded dual-polarity waves (CDWs), which consists of a pulse train with positive and negative polarities. A new coding scheme and a corresponding linear decoding process were thereby designed to obtain the recovered signals with increased amplitude, thus increasing the SNR without sacrificing the frame rate. The newly designed CDW ultrafast ultrasound imaging technique achieved higher quality B-mode images than coherent plane-wave compounding (CPWC) and multiplane wave (MW) imaging in a calibration phantom, ex vivo pork belly, and in vivo human back muscle. CDW imaging shows a significant improvement in the SNR (10.71 dB versus CPWC and 7.62 dB versus MW), penetration depth (36.94% versus CPWC and 35.14% versus MW), and contrast ratio in deep regions (5.97 dB versus CPWC and 5.05 dB versus MW) without compromising other image quality metrics, such as spatial resolution and frame rate. The enhanced image qualities and ultrafast frame rates offered by CDW imaging beget great potential for various novel imaging applications.

A current-assisted CMOS photonic sampler with two taps for fluorescence lifetime sensing

NASA Astrophysics Data System (ADS)

Ingelberts, H.; Kuijk, M.

2016-04-01

Imaging based on fluorescence lifetime is becoming increasingly important in medical and biological applications. State-of- the-art fluorescence lifetime microscopes either use bulky and expensive gated image intensifiers coupled to a CCD or single-photon detectors in a slow scanning setup. Numerous attempts are being made to create compact, cost-effective all- CMOS imagers for fluorescence lifetime sensing. Single-photon avalanche diode (SPAD) imagers can have very good timing resolution and noise characteristics but have low detection efficiency. Another approach is to use CMOS imagers based on demodulation detectors. These imagers can be either very fast or very efficient but it remains a challenge to combine both characteristics. Recently we developed the current-assisted photonic sampler (CAPS) to tackle these problems and in this work, we present a new CAPS with two detection taps that can sample a fluorescence decay in two time windows. In the case of mono-exponential decays, two windows provide enough information to resolve the lifetime. We built an electro-optical setup to characterize the detector and use it for fluorescence lifetime measurements. It consists of a supercontinuum pulsed laser source, an optical system to focus light into the detector and picosecond timing electronics. We describe the structure and operation of the two-tap CAPS and provide basic characterization of the speed performance at multiple wavelengths in the visible and near-infrared spectrum. We also record fluorescence decays of different visible and NIR fluorescent dyes and provide different methods to resolve the fluorescence lifetime.

Ultrafast Manipulation of Magnetic Order with Electrical Pulses

NASA Astrophysics Data System (ADS)

Yang, Yang

During the last 30 years spintronics has been a very rapidly expanding field leading to lots of new interesting physics and applications. As with most technology-oriented fields, spintronics strives to control devices with very low energy consumption and high speed. The combination of spin and electronics inherent to spintronics directly tackles energy efficiency, due to the non-volatility of magnetism. However, speed of operation of spintronic devices is still rather limited ( nanoseconds), due to slow magnetization precessional frequencies. Ultrafast magnetism (or opto-magnetism) is a relatively new field that has been very active in the last 20 years. The main idea is that intense femtosecond laser pulses can be used in order to manipulate the magnetization at very fast time-scales ( 100 femtoseconds). However, the use of femtosecond lasers poses great application challenges such as diffraction limited optical spot sizes which hinders device density, and bulky and expensive integration of femtosecond lasers into devices. In this thesis, our efforts to combine ultrafast magnetism and spintronics are presented. First, we show that the magnetization of ferrimagnetic GdFeCo films can be switched by picosecond electronic heat current pulses. This result shows that a non-thermal distribution of electrons directly excited by laser is not necessary for inducing ultrafast magnetic dynamics. Then, we fabricate photoconductive switch devices on a LT-GaAs substrate, to generate picosecond electrical pulses. Intense electrical pulses with 10ps (FWHM) duration and peak current up to 3A can be generated and delivered into magnetic films. Distinct magnetic dynamics in CoPt films are found between direct optical heating and electrical heating. More importantly, by delivering picosecond electrical pulses into GdFeCo films, we are able to deterministically reverse the magnetization of GdFeCo within 10ps. This is more than one order of magnitude faster than any other electrically

Anisotropic ultrafast response of MoS2 on rippled substrates

NASA Astrophysics Data System (ADS)

Cinquanta, Eugenio; Camellini, Andrea; Martella, Christian; Mennucci, Carlo; Lamperti, Alessio; Della Valle, Giuseppe; Zavelani Rossi, Margherita; Buatier de Mongeot, Francesco; Molle, Alessandro; Stagira, Salvatore

TMDs represent one of the most promising option for new devices characterized by high performances for opto- and nanoelectronics applications. Top-down schemes have been fruitfully exploited for the tuning of TMDs physics by stain engineering in exfoliated flakes. We propose an original bottom-up strategy based on the CVD growth of MoS2 on anisotropic substrates and its characterization by means of pump-probe spectroscopy. The ultrafast response of the rippled MoS2 reveals strongly anisotropic. While the transient absorption emerges as independent from the orientation of the pump beam polarization, the angle between the probe beam polarization and the ripples induces remarkable effects. Within an orthogonal geometry, both the overall intensity of the transient spectrum and the el-ph scattering decay time are halved while the photo-bleaching at 450 nm is blueshifted with respect to the parallel orientation case. Our results demonstrate that the coupling of TMDs with anisotropic substrates is a promising way for the integration of TMDs photonics devices.

Modelling ultrafast laser ablation

NASA Astrophysics Data System (ADS)

Rethfeld, Baerbel; Ivanov, Dmitriy S.; E Garcia, Martin; Anisimov, Sergei I.

2017-05-01

This review is devoted to the study of ultrafast laser ablation of solids and liquids. The ablation of condensed matter under exposure to subpicosecond laser pulses has a number of peculiar properties which distinguish this process from ablation induced by nanosecond and longer laser pulses. The process of ultrafast ablation includes light absorption by electrons in the skin layer, energy transfer from the skin layer to target interior by nonlinear electronic heat conduction, relaxation of the electron and ion temperatures, ultrafast melting, hydrodynamic expansion of heated matter accompanied by the formation of metastable states and subsequent formation of breaks in condensed matter. In case of ultrashort laser excitation, these processes are temporally separated and can thus be studied separately. As for energy absorption, we consider peculiarities of the case of metal irradiation in contrast to dielectrics and semiconductors. We discuss the energy dissipation processes of electronic thermal wave and lattice heating. Different types of phase transitions after ultrashort laser pulse irradiation as melting, vaporization or transitions to warm dense matter are discussed. Also nonthermal phase transitions, directly caused by the electronic excitation before considerable lattice heating, are considered. The final material removal occurs from the physical point of view as expansion of heated matter; here we discuss approaches of hydrodynamics, as well as molecular dynamic simulations directly following the atomic movements. Hybrid approaches tracing the dynamics of excited electrons, energy dissipation and structural dynamics in a combined simulation are reviewed as well.

Optical spectroscopy and tooth decay

NASA Astrophysics Data System (ADS)

Misra, P.; De, T.; Singh, R.

2005-11-01

Optical spectroscopy in the ultraviolet, visible and mid-infrared spectral regions has been used to discriminate between healthy and diseased teeth of patients in the age range 15-75 years. Spectral scans of absorbance versus wavenumber and fluorescence intensity versus wavelength have been recorded and investigated for caries and periodontal disease. Such optical diagnostics can prove very useful in the early detection and treatment of tooth decay.

Ultrafast superresolution fluorescence imaging with spinning disk confocal microscope optics.

PubMed

Hayashi, Shinichi; Okada, Yasushi

2015-05-01

Most current superresolution (SR) microscope techniques surpass the diffraction limit at the expense of temporal resolution, compromising their applications to live-cell imaging. Here we describe a new SR fluorescence microscope based on confocal microscope optics, which we name the spinning disk superresolution microscope (SDSRM). Theoretically, the SDSRM is equivalent to a structured illumination microscope (SIM) and achieves a spatial resolution of 120 nm, double that of the diffraction limit of wide-field fluorescence microscopy. However, the SDSRM is 10 times faster than a conventional SIM because SR signals are recovered by optical demodulation through the stripe pattern of the disk. Therefore a single SR image requires only a single averaged image through the rotating disk. On the basis of this theory, we modified a commercial spinning disk confocal microscope. The improved resolution around 120 nm was confirmed with biological samples. The rapid dynamics of micro-tubules, mitochondria, lysosomes, and endosomes were observed with temporal resolutions of 30-100 frames/s. Because our method requires only small optical modifications, it will enable an easy upgrade from an existing spinning disk confocal to a SR microscope for live-cell imaging. © 2015 Hayashi and Okada. This article is distributed by The American Society for Cell Biology under license from the author(s). Two months after publication it is available to the public under an Attribution–Noncommercial–Share Alike 3.0 Unported Creative Commons License (http://creativecommons.org/licenses/by-nc-sa/3.0).

pH and chloride recordings in living cells using two-photon fluorescence lifetime imaging microscopy

NASA Astrophysics Data System (ADS)

Lahn, Mattes; Hille, Carsten; Koberling, Felix; Kapusta, Peter; Dosche, Carsten

2010-02-01

Today fluorescence lifetime imaging microscopy (FLIM) has become an extremely powerful technique in life sciences. The independency of the fluorescence decay time on fluorescence dye concentration and emission intensity circumvents many artefacts arising from intensity based measurements. To minimize cell damage and improve scan depth, a combination with two-photon (2P) excitation is quite promising. Here, we describe the implementation of a 2P-FLIM setup for biological applications. For that we used a commercial fluorescence lifetime microscope system. 2P-excitation at 780nm was achieved by a non-tuneable, but inexpensive and easily manageable mode-locked fs-fiber laser. Time-resolved fluorescence image acquisition was performed by objective-scanning with the reversed time-correlated single photon counting (TCSPC) technique. We analyzed the suitability of the pH-sensitive dye BCECF and the chloride-sensitive dye MQAE for recordings in an insect tissue. Both parameters are quite important, since they affect a plethora of physiological processes in living tissues. We performed a straight forward in situ calibration method to link the fluorescence decay time with the respective ion concentration and carried out spatially resolved measurements under resting conditions. BCECF still offered only a limited dynamic range regarding fluorescence decay time changes under physiologically pH values. However, MQAE proofed to be well suited to record chloride concentrations in the physiologically relevant range. Subsequently, several chloride transport pathways underlying the intracellular chloride homeostasis were investigated pharmacologically. In conclusion, 2P-FLIM is well suited for ion detection in living tissues due to precise and reproducible decay time measurements in combination with reduced cell and dye damages.

Multi-MHz laser-scanning single-cell fluorescence microscopy by spatiotemporally encoded virtual source array

PubMed Central

Wu, Jianglai; Tang, Anson H. L.; Mok, Aaron T. Y.; Yan, Wenwei; Chan, Godfrey C. F.; Wong, Kenneth K. Y.; Tsia, Kevin K.

2017-01-01

Apart from the spatial resolution enhancement, scaling of temporal resolution, equivalently the imaging throughput, of fluorescence microscopy is of equal importance in advancing cell biology and clinical diagnostics. Yet, this attribute has mostly been overlooked because of the inherent speed limitation of existing imaging strategies. To address the challenge, we employ an all-optical laser-scanning mechanism, enabled by an array of reconfigurable spatiotemporally-encoded virtual sources, to demonstrate ultrafast fluorescence microscopy at line-scan rate as high as 8 MHz. We show that this technique enables high-throughput single-cell microfluidic fluorescence imaging at 75,000 cells/second and high-speed cellular 2D dynamical imaging at 3,000 frames per second, outperforming the state-of-the-art high-speed cameras and the gold-standard laser scanning strategies. Together with its wide compatibility to the existing imaging modalities, this technology could empower new forms of high-throughput and high-speed biological fluorescence microscopy that was once challenged. PMID:28966855

Using fluorescence lifetime microscopy to study the subcellular localization of anthocyanins.

PubMed

Chanoca, Alexandra; Burkel, Brian; Kovinich, Nik; Grotewold, Erich; Eliceiri, Kevin W; Otegui, Marisa S

2016-12-01

Anthocyanins are flavonoid pigments that accumulate in most seed plants. They are synthesized in the cytoplasm but accumulate inside the vacuoles. Anthocyanins are pigmented at the lower vacuolar pH, but in the cytoplasm they can be visualized based on their fluorescence properties. Thus, anthocyanins provide an ideal system for the development of new methods to investigate cytoplasmic pools and association with other molecular components. We have analyzed the fluorescence decay of anthocyanins by fluorescence lifetime imaging microscopy (FLIM), in both in vitro and in vivo conditions, using wild-type and mutant Arabidopsis thaliana seedlings. Within plant cells, the amplitude-weighted mean fluorescence lifetime (τ m ) correlated with distinct subcellular localizations of anthocyanins. The vacuolar pool of anthocyanins exhibited shorter τ m than the cytoplasmic pool. Consistently, lowering the pH of anthocyanins in solution shortened their fluorescence decay. We propose that FLIM is a useful tool for understanding the trafficking of anthocyanins and, potentially, for estimating vacuolar pH inside intact plant cells. © 2016 The Authors The Plant Journal © 2016 John Wiley & Sons Ltd.

Photoinduced Ultrafast Intramolecular Excited-State Energy Transfer in the Silylene-Bridged Biphenyl and Stilbene (SBS) System: A Nonadiabatic Dynamics Point of View.

PubMed

Wang, Jun; Huang, Jing; Du, Likai; Lan, Zhenggang

2015-07-09

The photoinduced intramolecular excited-state energy-transfer (EET) process in conjugated polymers has received a great deal of research interest because of its important role in the light harvesting and energy transport of organic photovoltaic materials in photoelectric devices. In this work, the silylene-bridged biphenyl and stilbene (SBS) system was chosen as a simplified model system to obtain physical insight into the photoinduced intramolecular energy transfer between the different building units of the SBS copolymer. In the SBS system, the vinylbiphenyl and vinylstilbene moieties serve as the donor (D) unit and the acceptor (A) unit, respectively. The ultrafast excited-state dynamics of the SBS system was investigated from the point of view of nonadiabatic dynamics with the surface-hopping method at the TDDFT level. The first two excited states (S1 and S2) are characterized by local excitations at the acceptor (vinylstilbene) and donor (vinylbiphenyl) units, respectively. Ultrafast S2-S1 decay is responsible for the intramolecular D-A excitonic energy transfer. The geometric distortion of the D moiety play an essential role in this EET process, whereas the A moiety remains unchanged during the nonadiabatic dynamics simulation. The present work provides a direct dynamical approach to understand the ultrafast intramolecular energy-transfer dynamics in SBS copolymers and other similar organic photovoltaic copolymers.

Ultrafast Two-Dimensional Infrared Spectroscopy of a Quasifree Rotor: J Scrambling and Perfectly Anticorrelated Cross Peaks

NASA Astrophysics Data System (ADS)

Mandal, Aritra; Ng Pack, Greg; Shah, Parth P.; Erramilli, Shyamsunder; Ziegler, L. D.

2018-03-01

Ultrafast two-dimensional infrared (2DIR) spectra of the N2O ν3 mode in moderately dense SF6 gas exhibit complex line shapes with diagonal and antidiagonal features in contrast to condensed phase vibrational 2DIR spectroscopy. Observed spectra for this quasifree rotor system are well captured by a model that includes all 36 possible rovibrational pathways and treats P (Δ J =-1 ) and R (Δ J =+1 ) branch resonances as distinct Kubo line shape features. Transition frequency correlation decay is due to J scrambling within one to two gas collisions at each density. Studies of supercritical solvation and relaxation at high pressure and temperature are enabled by this methodology.

Fluorescent nanodiamonds as highly stable biomarker for endotoxin verification

NASA Astrophysics Data System (ADS)

Bergmann, Thorsten; Burg, Jan Michael; Lilholt, Maria; Maeder, Ulf; Beer, Sebastian; Salzig, Denise; Ebrahimi, Mehrdad; Czermak, Peter; Fiebich, Martin

2012-03-01

Fluorescent nanodiamonds (ND) provide advantageous properties as a fluorescent biomarker for in vitro and in vivo studies. The maximum fluorescence occurs around 700 nm, they do not show photobleaching or blinking and seem to be nontoxic. After a pretreatment with strong acid fluorescent ND can be functionalized and coupled to endotoxin. Endotoxin is a decay product of bacteria and causes strong immune reactions. Therefore endotoxin has to be removed for most applications. An effective removal procedure is membrane filtration. The endotoxin, coupled to fluorescent ND can be visualized by using confocal microscopy which allows the investigation of the separation mechanisms of the filtration process within the membranes.

Large-area tungsten disulfide for ultrafast photonics.

PubMed

Yan, Peiguang; Chen, Hao; Yin, Jinde; Xu, Zihan; Li, Jiarong; Jiang, Zike; Zhang, Wenfei; Wang, Jinzhang; Li, Irene Ling; Sun, Zhipei; Ruan, Shuangchen

2017-02-02

Two-dimensional (2D) layered transition metal dichalcogenides (TMDs) have attracted significant interest in various optoelectronic applications due to their excellent nonlinear optical properties. One of the most important applications of TMDs is to be employed as an extraordinary optical modulation material (e.g., the saturable absorber (SA)) in ultrafast photonics. The main challenge arises while embedding TMDs into fiber laser systems to generate ultrafast pulse trains and thus constraints their practical applications. Herein, few-layered WS 2 with a large-area was directly transferred on the facet of the pigtail and acted as a SA for erbium-doped fiber laser (EDFL) systems. In our study, WS 2 SA exhibited remarkable nonlinear optical properties (e.g., modulation depth of 15.1% and saturable intensity of 157.6 MW cm -2 ) and was used for ultrafast pulse generation. The soliton pulses with remarkable performances (e.g., ultrashort pulse duration of 1.49 ps, high stability of 71.8 dB, and large pulse average output power of 62.5 mW) could be obtained in a telecommunication band. To the best of our knowledge, the average output power of the mode-locked pulse trains is the highest by employing TMD materials in fiber laser systems. These results indicate that atomically large-area WS 2 could be used as excellent optical modulation materials in ultrafast photonics.

Three-dimensional online surface reconstruction of augmented fluorescence lifetime maps using photometric stereo (Conference Presentation)

NASA Astrophysics Data System (ADS)

Unger, Jakob; Lagarto, Joao; Phipps, Jennifer; Ma, Dinglong; Bec, Julien; Sorger, Jonathan; Farwell, Gregory; Bold, Richard; Marcu, Laura

2017-02-01

Multi-Spectral Time-Resolved Fluorescence Spectroscopy (ms-TRFS) can provide label-free real-time feedback on tissue composition and pathology during surgical procedures by resolving the fluorescence decay dynamics of the tissue. Recently, an ms-TRFS system has been developed in our group, allowing for either point-spectroscopy fluorescence lifetime measurements or dynamic raster tissue scanning by merging a 450 nm aiming beam with the pulsed fluorescence excitation light in a single fiber collection. In order to facilitate an augmented real-time display of fluorescence decay parameters, the lifetime values are back projected to the white light video. The goal of this study is to develop a 3D real-time surface reconstruction aiming for a comprehensive visualization of the decay parameters and providing an enhanced navigation for the surgeon. Using a stereo camera setup, we use a combination of image feature matching and aiming beam stereo segmentation to establish a 3D surface model of the decay parameters. After camera calibration, texture-related features are extracted for both camera images and matched providing a rough estimation of the surface. During the raster scanning, the rough estimation is successively refined in real-time by tracking the aiming beam positions using an advanced segmentation algorithm. The method is evaluated for excised breast tissue specimens showing a high precision and running in real-time with approximately 20 frames per second. The proposed method shows promising potential for intraoperative navigation, i.e. tumor margin assessment. Furthermore, it provides the basis for registering the fluorescence lifetime maps to the tissue surface adapting it to possible tissue deformations.

Carotid Artery Stiffness Assessment by Ultrafast Ultrasound Imaging: Feasibility and Potential Influencing Factors.

PubMed

Pan, Fu-Shun; Yu, Liang; Luo, Jia; Wu, Ri-Dong; Xu, Ming; Liang, Jin-Yu; Zheng, Yan-Ling; Xie, Xiao-Yan

2018-04-19

To evaluate the feasibility of the ultrafast ultrasound pulsed wave velocity (PWV) for carotid stiffness assessment and potential influencing factors. Ultrafast PWV measurements of 442 carotid arteries in 162 consecutive patients (patient group) and 66 healthy volunteers (control group) were performed. High- and very high-frequency transducers were used in 110 carotid segments. The ultrafast PWVs at the beginning and end of systole were automatically measured. The correlations between the intima-media thickness (IMT) and ultrafast PWV and the equipment and carotid factors influencing the utility of ultrafast PWV were analyzed. Each ultrafast PWV acquisition was completed within 1 minute. The intraobserver variability showed mean differences ± SD of 0.12 ± 1.28 m/s for the PWV before systole and 0.06 ± 1.30 m/s for the PWV at the end of systole. Ultrafast PWV measurements were more likely obtained with the very high- frequency transducer when the IMT was less than 1.5 mm (P < .05). A generalized linear mixed-effects model analysis showed that the very high-frequency transducer had a greater ability to obtain a valid carotid ultrafast PWV measurement with an IMT of less than 1.5 mm (P < .05). The IMT was positively correlated with the PWV before systole and at the end of systole (r = 0.207-0.771; all P < .05) in the control group, patient group, and carotid subgroup with an IMT of less than 1.5 mm. A multiple regression analysis showed that the IMT and plaque were important independent factors in predicting failure of the ultrafast PWV (P < .001). The ultrafast PWV is an effective and user-friendly method for evaluating carotid stiffness. The IMT and transducer type are factors influencing the ability to obtain an ultrafast PWV measurement. © 2018 by the American Institute of Ultrasound in Medicine.

Feed-forward motor control of ultrafast, ballistic movements.

PubMed

Kagaya, K; Patek, S N

2016-02-01

To circumvent the limits of muscle, ultrafast movements achieve high power through the use of springs and latches. The time scale of these movements is too short for control through typical neuromuscular mechanisms, thus ultrafast movements are either invariant or controlled prior to movement. We tested whether mantis shrimp (Stomatopoda: Neogonodactylus bredini) vary their ultrafast smashing strikes and, if so, how this control is achieved prior to movement. We collected high-speed images of strike mechanics and electromyograms of the extensor and flexor muscles that control spring compression and latch release. During spring compression, lateral extensor and flexor units were co-activated. The strike initiated several milliseconds after the flexor units ceased, suggesting that flexor activity prevents spring release and determines the timing of strike initiation. We used linear mixed models and Akaike's information criterion to serially evaluate multiple hypotheses for control mechanisms. We found that variation in spring compression and strike angular velocity were statistically explained by spike activity of the extensor muscle. The results show that mantis shrimp can generate kinematically variable strikes and that their kinematics can be changed through adjustments to motor activity prior to the movement, thus supporting an upstream, central-nervous-system-based control of ultrafast movement. Based on these and other findings, we present a shishiodoshi model that illustrates alternative models of control in biological ballistic systems. The discovery of feed-forward control in mantis shrimp sets the stage for the assessment of targets, strategic variation in kinematics and the role of learning in ultrafast animals. © 2016. Published by The Company of Biologists Ltd.

Time-resolved fluorescence of thioredoxin single-tryptophan mutants: modeling experimental results with minimum perturbation mapping

NASA Astrophysics Data System (ADS)

Silva, Norberto D., Jr.; Haydock, Christopher; Prendergast, Franklyn G.

1994-08-01

The time-resolved fluorescence decay of single tryptophan (Trp) proteins is typically described using either a distribution of lifetimes or a sum of two or more exponential terms. A possible interpretation for this fluorescence decay heterogeneity is the existence of different isomeric conformations of Trp about its (chi) +1) and (chi) +2) dihedral angles. Are multiple Trp conformations compatible with the remainder of the protein in its crystallographic configuration or do they require repacking of neighbor side chains? It is conceivable that isomers of the neighbor side chains interconvert slowly on the fluorescence timescale and contribute additional lifetime components to the fluorescence intensity. We have explored this possibility by performing minimum perturbation mapping simulations of Trp 28 and Trp 31 in thioredoxin (TRX) using CHARMm 22. Mappings of Trp 29 and Trp 31 give the TRX Trp residue energy landscape as a function of (chi) +1) and (chi) +2) dihedral angles. Time-resolved fluorescence intensity and anisotropy decay of mutant TRX (W28F and W31F) are measured and interpreted in light of the above simulations. Relevant observables, like order parameters and isomerization rates, can be derived from the minimum perturbation maps and compared with experiment.

Applications of ultrafast laser direct writing: from polarization control to data storage

NASA Astrophysics Data System (ADS)

Donko, A.; Gertus, T.; Brambilla, G.; Beresna, M.

2018-02-01

Ultrafast laser direct writing is a fascinating technology which emerged more than two decades from fundamental studies of material resistance to high-intensity optical fields. Its development saw the discovery of many puzzling phenomena and demonstration of useful applications. Today, ultrafast laser writing is seen as a technology with great potential and is rapidly entering the industrial environment. Whereas, less than 10 years ago, ultrafast lasers were still confined within the research labs. This talk will overview some of the unique features of ultrafast lasers and give examples of its applications in optical data storage, polarization control and optical fibers.

Subnanosecond fluorescence spectroscopy of human serum albumin as a method to estimate the efficiency of the depression therapy

NASA Astrophysics Data System (ADS)

Syrejshchikova, T. I.; Gryzunov, Yu. A.; Smolina, N. V.; Komar, A. A.; Uzbekov, M. G.; Misionzhnik, E. J.; Maksimova, N. M.

2010-05-01

The efficiency of the therapy of psychiatric diseases is estimated using the fluorescence measurements of the conformational changes of human serum albumin in the course of medical treatment. The fluorescence decay curves of the CAPIDAN probe (N-carboxyphenylimide of the dimethylaminonaphthalic acid) in the blood serum are measured. The probe is specifically bound to the albumin drug binding sites and exhibits fluorescence as a reporter ligand. A variation in the conformation of the albumin molecule substantially affects the CAPIDAN fluorescence decay curve on the subnanosecond time scale. A subnanosecond pulsed laser or a Pico-Quant LED excitation source and a fast photon detector with a time resolution of about 50 ps are used for the kinetic measurements. The blood sera of ten patients suffering from depression and treated at the Institute of Psychiatry were preliminary clinically tested. Blood for analysis was taken from each patient prior to the treatment and on the third week of treatment. For ten patients, the analysis of the fluorescence decay curves of the probe in the blood serum using the three-exponential fitting shows that the difference between the amplitudes of the decay function corresponding to the long-lived (9 ns) fluorescence of the probe prior to and after the therapeutic procedure reliably differs from zero at a significance level of 1% ( p < 0.01).

Ultrafast magnetization reversal by picosecond electrical pulses

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

Yang, Yang; Wilson, Richard B.; Gorchon, Jon

The field of spintronics involves the study of both spin and charge transport in solid-state devices. Ultrafast magnetism involves the use of femtosecond laser pulses to manipulate magnetic order on subpicosecond time scales. Here, we unite these phenomena by using picosecond charge current pulses to rapidly excite conduction electrons in magnetic metals. We observe deterministic, repeatable ultrafast reversal of the magnetization of a GdFeCo thin film with a single sub–10-ps electrical pulse. The magnetization reverses in ~10 ps, which is more than one order of magnitude faster than any other electrically controlled magnetic switching, and demonstrates a fundamentally new electricalmore » switching mechanism that does not require spin-polarized currents or spin-transfer/orbit torques. The energy density required for switching is low, projecting to only 4 fJ needed to switch a (20 nm) 3 cell. This discovery introduces a new field of research into ultrafast charge current–driven spintronic phenomena and devices.« less

Ultrafast magnetization reversal by picosecond electrical pulses

DOE PAGES

Yang, Yang; Wilson, Richard B.; Gorchon, Jon; ...

2017-11-03

The field of spintronics involves the study of both spin and charge transport in solid-state devices. Ultrafast magnetism involves the use of femtosecond laser pulses to manipulate magnetic order on subpicosecond time scales. Here, we unite these phenomena by using picosecond charge current pulses to rapidly excite conduction electrons in magnetic metals. We observe deterministic, repeatable ultrafast reversal of the magnetization of a GdFeCo thin film with a single sub–10-ps electrical pulse. The magnetization reverses in ~10 ps, which is more than one order of magnitude faster than any other electrically controlled magnetic switching, and demonstrates a fundamentally new electricalmore » switching mechanism that does not require spin-polarized currents or spin-transfer/orbit torques. The energy density required for switching is low, projecting to only 4 fJ needed to switch a (20 nm) 3 cell. This discovery introduces a new field of research into ultrafast charge current–driven spintronic phenomena and devices.« less

Role of the Heat Sink Layer Ta for Ultrafast Spin Dynamic Process in Amorphous TbFeCo Thin Films

NASA Astrophysics Data System (ADS)

Ren, Y.; Zhang, Z. Z.; Min, T.; Jin, Q. Y.

The ultrafast demagnetization processes (UDP) in Ta (t nm)/TbFeCo (20 nm) films have been studied using the time-resolved magneto-optical Kerr effect (TRMOKE). With a fixed pump fluence of 2 mJ/cm2, for the sample without a Ta underlayer (t=0nm), we observed the UDP showing a two-step decay behavior, with a relatively longer decay time (τ2) around 3.0 ps in the second step due to the equilibrium of spin-lattice relaxation following the 4f occupation. As a 10nm Ta layer is deposited, the two-step demagnetization still exists while τ2 decreases to ˜1.9ps. Nevertheless, the second-step decay (τ2=0ps) disappears as the Ta layer thickness is increased up to 20 nm, only the first-step UDP occurs within 500 fs, followed by a fast recovery process. The rapid magnetization recovery rate strongly depends on the pump fluence. We infer that the Ta layer provides conduction electrons involving the thermal equilibrium of spin-lattice interaction and serves as heat bath taking away energy from spins of TbFeCo alloy film in UDP.

Time-domain laser-induced fluorescence spectroscopy apparatus for clinical diagnostics

NASA Astrophysics Data System (ADS)

Fang, Qiyin; Papaioannou, Thanassis; Jo, Javier A.; Vaitha, Russel; Shastry, Kumar; Marcu, Laura

2004-01-01

We report the design and development of a compact optical fiber-based apparatus for in situ time-resolved laser-induced fluorescence spectroscopy (tr-LIFS) of biological systems. The apparatus is modular, optically robust, and compatible with the clinical environment. It incorporates a dual output imaging spectrograph, a gated multichannel plate photomultiplier (MCP-PMT), an intensified charge-coupled-device (ICCD) camera, and a fast digitizer. It can accommodate various types of light sources and optical fiber probes for selective excitation and remote light delivery/collection as required by different applications. The apparatus allows direct recording of the entire fluorescence decay with high sensitivity (nM range fluorescein dye concentration with signal-to-noise ratio of 46) and with four decades dynamic range. It is capable of resolving a broad range of fluorescence lifetimes from hundreds of picoseconds (as low as 300 ps) using the MCP-PMT coupled to the digitizer to milliseconds using the ICCD. The data acquisition and analysis process is fully automated, enabling fast recording of fluorescence intensity decay across the entire emission spectrum (0.8 s per wavelength or ˜40 s for a 200 nm wavelength range at 5 nm increments). The spectral and temporal responses of the apparatus were calibrated and its performance was validated using fluorescence lifetime standard dyes (Rhodamin B, 9-cyanoanthracene, and rose Bengal) and tissue endogenous fluorophores (elastin, collagen, nicotinamide adenine dinucleotide, and flavin adenine dinucleotide). Fluorescence decay lifetimes and emission spectra of all tested compounds measured with the current tr-LIFS apparatus were found in good agreement with the values reported in the literature. The design and performance of tr-LIFS apparatus have enabled in vivo studies of atherosclerotic plaques and brain tumors.

Measurement of Nanoplasmonic Field Enhancement with Ultrafast Photoemission.

PubMed

Rácz, Péter; Pápa, Zsuzsanna; Márton, István; Budai, Judit; Wróbel, Piotr; Stefaniuk, Tomasz; Prietl, Christine; Krenn, Joachim R; Dombi, Péter

2017-02-08

Probing nanooptical near-fields is a major challenge in plasmonics. Here, we demonstrate an experimental method utilizing ultrafast photoemission from plasmonic nanostructures that is capable of probing the maximum nanoplasmonic field enhancement in any metallic surface environment. Directly measured field enhancement values for various samples are in good agreement with detailed finite-difference time-domain simulations. These results establish ultrafast plasmonic photoelectrons as versatile probes for nanoplasmonic near-fields.

Ultraviolet fluorescence to identify navel oranges with poor peel quality and decay

USDA-ARS?s Scientific Manuscript database

Navel oranges were sorted into four groups under ultraviolet (UV) illumination in commercial packinghouse black light rooms based upon the amount of fluorescence visible on each fruit to determine if fluorescence was predictive of peel quality. The groups corresponded to fruit with: 1) no fluorescen...

Rational material design for ultrafast rechargeable lithium-ion batteries.

PubMed

Tang, Yuxin; Zhang, Yanyan; Li, Wenlong; Ma, Bing; Chen, Xiaodong

2015-10-07

Rechargeable lithium-ion batteries (LIBs) are important electrochemical energy storage devices for consumer electronics and emerging electrical/hybrid vehicles. However, one of the formidable challenges is to develop ultrafast charging LIBs with the rate capability at least one order of magnitude (>10 C) higher than that of the currently commercialized LIBs. This tutorial review presents the state-of-the-art developments in ultrafast charging LIBs by the rational design of materials. First of all, fundamental electrochemistry and related ionic/electronic conduction theories identify that the rate capability of LIBs is kinetically limited by the sluggish solid-state diffusion process in electrode materials. Then, several aspects of the intrinsic materials, materials engineering and processing, and electrode materials architecture design towards maximizing both ionic and electronic conductivity in the electrode with a short diffusion length are deliberated. Finally, the future trends and perspectives for the ultrafast rechargeable LIBs are discussed. Continuous rapid progress in this area is essential and urgent to endow LIBs with ultrafast charging capability to meet huge demands in the near future.

Nonthermal ultrafast optical control of the magnetization in garnet films

NASA Astrophysics Data System (ADS)

Hansteen, Fredrik; Kimel, Alexey; Kirilyuk, Andrei; Rasing, Theo

2006-01-01

We demonstrate coherent optical control of the magnetization in ferrimagnetic garnet films on the femtosecond time scale through a combination of two different ultrafast and nonthermal photomagnetic effects and by employing multiple pump pulses. Linearly polarized laser pulses are shown to create a long-lived modification of the magnetocrystalline anisotropy via optically induced electron transfer between nonequivalent ion sites while circularly polarized pulses additionally act as strong transient magnetic field pulses originating from the nonabsorptive inverse Faraday effect. Due to the slow phonon-magnon interaction in these dielectrics, thermal effects of the laser excitation are clearly distinguished from the ultrafast nonthermal effects and can be seen only on the time scale of nanoseconds for sample temperatures near the Curie point. The reported effects open exciting possibilities for ultrafast manipulation of spins by light, and provide insight into the physics of magnetism on ultrafast time scales.

Mobility and fluorescence of barium ions in xenon gas for the exo experiment

NASA Astrophysics Data System (ADS)

Benitez Medina, Julio Cesar

The Enriched Xenon Observatory (EXO) is an experiment which aims to observe the neutrinoless double beta decay of 136Xe. The measurement of this decay would give information about the absolute neutrino mass and whether or not the neutrino is its own antiparticle. Since this is a very rare decay, the ability to reject background events by detecting the barium ion daughter from the double beta decay would be a major advantage. EXO is currently operating a detector with 200 kg of enriched liquid xenon, and there are plans to build a ton scale xenon detector. Measurements of the purity of liquid xenon in our liquid xenon test cell are reported. These results are relevant to the research on detection of single barium ions by our research group at Colorado State University. Details of the operation of the purity monitor are described. The effects of using a purifier, recirculation and laser ablation on the purity of liquid xenon are discussed. Mobility measurements of barium in xenon gas are reported for the first time. The variation of mobility with xenon gas pressure suggests that a significant fraction of molecular ions are formed when barium ions interact with xenon gas at high pressures. The measured mobility of Ba+ in Xe gas at different pressures is compared with the predicted theoretical value, and deviations are explained by a model that describes the fraction of molecular ions in Xe gas as a function of pressure. The results are useful for the analysis of experiments of fluorescence of Ba+ in xenon gas. It is also important to know the mobility of the ions in order to calculate the time they interact with an excitation laser in fluorescence experiments and in proposed 136 Ba+ daughter detection schemes. This thesis presents results of detection of laser induced fluorescence of Ba+ ions in Xe gas. Measurements of the pressure broadening of the excitation spectra of Ba+ in xenon gas are presented. Nonradiative decays due to gas collisions and optical pumping

Production of low kinetic energy electrons and energetic ion pairs by Intermolecular Coulombic Decay.

PubMed

Hergenhahn, Uwe

2012-12-01

The paper gives an introduction into Interatomic and Intermolecular Coulombic Decay (ICD). ICD is an autoionization process, which contrary to Auger decay involves neighbouring sites of the initial vacancy as an integral part of the decay transition. As a result of ICD, slow electrons are produced which generally are known to be active in radiation damage. The author summarizes the properties of ICD and reviews a number of important experiments performed in recent years. Intermolecular Coulombic Decay can generally take place in weakly bonded aggregates in the presence of ionizing particles or ionizing radiation. Examples collected here mostly use soft X-rays produced by synchrotron radiation to ionize, and use rare-gas clusters, water clusters or solutes in a liquid jet to observe ICD after irradiation. Intermolecular Coulombic Decay is initiated by single ionization into an excited state. The subsequent relaxation proceeds via an ultra-fast energy transfer to a neighbouring site, where a second ionization occurs. Secondary electrons from ICD have clearly been identified in numerous systems. ICD can take place after primary ionization, as the second step of a decay cascade which also involves Auger decay, or after resonant excitation with an energy which exceeds the ionization potential of the system. ICD is expected to play a role whenever particles or radiation with photon energies above the ionization energies for inner valence electrons are present in weakly bonded matter, e.g., biological tissue. The process produces at the same time a slow electron and two charged atomic or molecular fragments, which will lead to structural changes around the ionized site.

Femtosecond coherent nuclear dynamics of excited tetraphenylethylene: Ultrafast transient absorption and ultrafast Raman loss spectroscopic studies

NASA Astrophysics Data System (ADS)

Kayal, Surajit; Roy, Khokan; Umapathy, Siva

2018-01-01

Ultrafast torsional dynamics plays an important role in the photoinduced excited state dynamics. Tetraphenylethylene (TPE), a model system for the molecular motor, executes interesting torsional dynamics upon photoexcitation. The photoreaction of TPE involves ultrafast internal conversion via a nearly planar intermediate state (relaxed state) that further leads to a twisted zwitterionic state. Here, we report the photoinduced structural dynamics of excited TPE during the course of photoisomerization in the condensed phase by ultrafast Raman loss (URLS) and femtosecond transient absorption (TA) spectroscopy. TA measurements on the S1 state reveal step-wise population relaxation from the Franck-Condon (FC) state → relaxed state → twisted state, while the URLS study provides insights on the vibrational dynamics during the course of the reaction. The TA spectral dynamics and vibrational Raman amplitudes within 1 ps reveal vibrational wave packet propagating from the FC state to the relaxed state. Fourier transformation of this oscillation leads to a ˜130 cm-1 low-frequency phenyl torsional mode. Two vibrational marker bands, Cet=Cet stretching (˜1512 cm-1) and Cph=Cph stretching (˜1584 cm-1) modes, appear immediately after photoexcitation in the URLS spectra. The initial red-shift of the Cph=Cph stretching mode with a time constant of ˜400 fs (in butyronitrile) is assigned to the rate of planarization of excited TPE. In addition, the Cet=Cet stretching mode shows initial blue-shift within 1 ps followed by frequency red-shift, suggesting that on the sub-picosecond time scale, structural relaxation is dominated by phenyl torsion rather than the central Cet=Cet twist. Furthermore, the effect of the solvent on the structural dynamics is discussed in the context of ultrafast nuclear dynamics and solute-solvent coupling.

Femtosecond coherent nuclear dynamics of excited tetraphenylethylene: Ultrafast transient absorption and ultrafast Raman loss spectroscopic studies.

PubMed

Kayal, Surajit; Roy, Khokan; Umapathy, Siva

2018-01-14

Ultrafast torsional dynamics plays an important role in the photoinduced excited state dynamics. Tetraphenylethylene (TPE), a model system for the molecular motor, executes interesting torsional dynamics upon photoexcitation. The photoreaction of TPE involves ultrafast internal conversion via a nearly planar intermediate state (relaxed state) that further leads to a twisted zwitterionic state. Here, we report the photoinduced structural dynamics of excited TPE during the course of photoisomerization in the condensed phase by ultrafast Raman loss (URLS) and femtosecond transient absorption (TA) spectroscopy. TA measurements on the S 1 state reveal step-wise population relaxation from the Franck-Condon (FC) state → relaxed state → twisted state, while the URLS study provides insights on the vibrational dynamics during the course of the reaction. The TA spectral dynamics and vibrational Raman amplitudes within 1 ps reveal vibrational wave packet propagating from the FC state to the relaxed state. Fourier transformation of this oscillation leads to a ∼130 cm -1 low-frequency phenyl torsional mode. Two vibrational marker bands, C et =C et stretching (∼1512 cm -1 ) and C ph =C ph stretching (∼1584 cm -1 ) modes, appear immediately after photoexcitation in the URLS spectra. The initial red-shift of the C ph =C ph stretching mode with a time constant of ∼400 fs (in butyronitrile) is assigned to the rate of planarization of excited TPE. In addition, the C et =C et stretching mode shows initial blue-shift within 1 ps followed by frequency red-shift, suggesting that on the sub-picosecond time scale, structural relaxation is dominated by phenyl torsion rather than the central C et =C et twist. Furthermore, the effect of the solvent on the structural dynamics is discussed in the context of ultrafast nuclear dynamics and solute-solvent coupling.

Advanced optic fabrication using ultrafast laser radiation

NASA Astrophysics Data System (ADS)

Taylor, Lauren L.; Qiao, Jun; Qiao, Jie

2016-03-01

Advanced fabrication and finishing techniques are desired for freeform optics and integrated photonics. Methods including grinding, polishing and magnetorheological finishing used for final figuring and polishing of such optics are time consuming, expensive, and may be unsuitable for complex surface features while common photonics fabrication techniques often limit devices to planar geometries. Laser processing has been investigated as an alternative method for optic forming, surface polishing, structure writing, and welding, as direct tuning of laser parameters and flexible beam delivery are advantageous for complex freeform or photonics elements and material-specific processing. Continuous wave and pulsed laser radiation down to the nanosecond regime have been implemented to achieve nanoscale surface finishes through localized material melting, but the temporal extent of the laser-material interaction often results in the formation of a sub-surface heat affected zone. The temporal brevity of ultrafast laser radiation can allow for the direct vaporization of rough surface asperities with minimal melting, offering the potential for smooth, final surface quality with negligible heat affected material. High intensities achieved in focused ultrafast laser radiation can easily induce phase changes in the bulk of materials for processing applications. We have experimentally tested the effectiveness of ultrafast laser radiation as an alternative laser source for surface processing of monocrystalline silicon. Simulation of material heating associated with ultrafast laser-material interaction has been performed and used to investigate optimized processing parameters including repetition rate. The parameter optimization process and results of experimental processing will be presented.

Resolving ultrafast exciton migration in organic solids at the nanoscale

NASA Astrophysics Data System (ADS)

Ginsberg, Naomi

The migration of Frenkel excitons, tightly-bound electron-hole pairs, in photosynthesis and in organic semiconducting films is critical to the efficiency of natural and artificial light harvesting. While these materials exhibit a high degree of structural heterogeneity on the nanoscale, traditional measurements of exciton migration lengths are performed on bulk samples. Since both the characteristic length scales of structural heterogeneity and the reported bulk diffusion lengths are smaller than the optical diffraction limit, we adapt far-field super-resolution fluorescence imaging to uncover the correlations between the structural and energetic landscapes that the excitons explore. By combining the ultrafast super-resolved measurements with exciton hopping simulations we furthermore specify the nature (in addition to the extent) of exciton migration as a function of the intrinsic and ensemble chromophore energy scales that determine a spatio-energetic landscape for migration. In collaboration with: Samuel Penwell, Lucas Ginsberg, University of California, Berkeley and Rodrigo Noriega University of Utah.

Ultrafast decoherence dynamics govern photocarrier generation efficiencies in polymer solar cells

PubMed Central

Vella, Eleonora; Li, Hao; Grégoire, Pascal; Tuladhar, Sachetan M.; Vezie, Michelle S.; Few, Sheridan; Bazán, Claudia M.; Nelson, Jenny; Silva-Acuña, Carlos; Bittner, Eric R.

2016-01-01

All-organic-based photovoltaic solar cells have attracted considerable attention because of their low-cost processing and short energy payback time. In such systems the primary dissociation of an optical excitation into a pair of photocarriers has been recently shown to be extremely rapid and efficient, but the physical reason for this remains unclear. Here, two-dimensional photocurrent excitation spectroscopy, a novel non-linear optical spectroscopy, is used to probe the ultrafast coherent decay of photoexcitations into charge-producing states in a polymer:fullerene based solar cell. The two-dimensional photocurrent spectra are interpreted by introducing a theoretical model for the description of the coupling of the electronic states of the system to an external environment and to the applied laser fields. The experimental data show no cross-peaks in the twodimensional photocurrent spectra, as predicted by the model for coherence times between the exciton and the photocurrent producing states of 20 fs or less. PMID:27412119

Ultrafast non-adiabatic dynamics of methyl substituted ethylenes: the π3s Rydberg state.

PubMed

Wu, Guorong; Boguslavskiy, Andrey E; Schalk, Oliver; Schuurman, Michael S; Stolow, Albert

2011-10-28

Excited state unimolecular reactions of some polyenes exhibit localization of their dynamics at a single ethylenic double bond. Here we present studies of the fundamental photophysical processes in the ethylene unit itself. Combined femtosecond time-resolved photoelectron spectroscopy (TRPES) and ab initio quantum chemical calculations was applied to the study of excited state dynamics in cis-butene, trans-butene, trimethylethylene, and tetramethylethylene, following initial excitation to their respective π3s Rydberg states. The wavelength dependence of the π3s Rydberg state dynamics of tetramethylethylene was investigated in more detail. The π3s Rydberg to ππ(∗) valence state decay rate varies greatly with substituent: the 1,2-di- and tri-methyl substituted ethylenes (cis-butene, trans-butene, and trimethylethylene) show an ultrafast decay (∼20 fs), whereas the fully methylated tetramethylethylene shows a decay rate of 2 to 4 orders of magnitude slower. These observations are rationalized in terms of topographical trends in the relevant potential energy surfaces, as found from ab initio calculations: (1) the barrier between the π3s state and the ππ∗ state increases with increasing methylation, and (2) the π3s∕ππ∗ minimum energy conical intersection displaces monotonically away from the π3s Franck-Condon region with increasing methylation. The use of systematic methylation in combination with TRPES and ab initio computation is emerging as an important tool in discerning the excited state dynamics of unsaturated hydrocarbons.

Ultrafast non-adiabatic dynamics of methyl substituted ethylenes: The π3s Rydberg state

NASA Astrophysics Data System (ADS)

Wu, Guorong; Boguslavskiy, Andrey E.; Schalk, Oliver; Schuurman, Michael S.; Stolow, Albert

2011-10-01

Excited state unimolecular reactions of some polyenes exhibit localization of their dynamics at a single ethylenic double bond. Here we present studies of the fundamental photophysical processes in the ethylene unit itself. Combined femtosecond time-resolved photoelectron spectroscopy (TRPES) and ab initio quantum chemical calculations was applied to the study of excited state dynamics in cis-butene, trans-butene, trimethylethylene, and tetramethylethylene, following initial excitation to their respective π3s Rydberg states. The wavelength dependence of the π3s Rydberg state dynamics of tetramethylethylene was investigated in more detail. The π3s Rydberg to ππ* valence state decay rate varies greatly with substituent: the 1,2-di- and tri-methyl substituted ethylenes (cis-butene, trans-butene, and trimethylethylene) show an ultrafast decay (˜20 fs), whereas the fully methylated tetramethylethylene shows a decay rate of 2 to 4 orders of magnitude slower. These observations are rationalized in terms of topographical trends in the relevant potential energy surfaces, as found from ab initio calculations: (1) the barrier between the π3s state and the ππ* state increases with increasing methylation, and (2) the π3s/ππ* minimum energy conical intersection displaces monotonically away from the π3s Franck-Condon region with increasing methylation. The use of systematic methylation in combination with TRPES and ab initio computation is emerging as an important tool in discerning the excited state dynamics of unsaturated hydrocarbons.

Mapping momentum-dependent electron-phonon coupling and nonequilibrium phonon dynamics with ultrafast electron diffuse scattering

NASA Astrophysics Data System (ADS)

Stern, Mark J.; René de Cotret, Laurent P.; Otto, Martin R.; Chatelain, Robert P.; Boisvert, Jean-Philippe; Sutton, Mark; Siwick, Bradley J.

2018-04-01

Despite their fundamental role in determining material properties, detailed momentum-dependent information on the strength of electron-phonon and phonon-phonon coupling (EPC and PPC, respectively) across the entire Brillouin zone has remained elusive. Here we demonstrate that ultrafast electron diffuse scattering (UEDS) directly provides such information. By exploiting symmetry-based selection rules and time resolution, scattering from different phonon branches can be distinguished even without energy resolution. Using graphite as a model system, we show that UEDS patterns map the relative EPC and PPC strength through their profound sensitivity to photoinduced changes in phonon populations. We measure strong EPC to the K -point TO phonon of A1' symmetry (K -A1' ) and along the entire TO branch between Γ -K , not only to the Γ -E2 g phonon. We also determine that the subsequent phonon relaxation of these strongly coupled optical phonons involve three stages: decay via several identifiable channels to TA and LA phonons (1 -2 ps), intraband thermalization of the non-equilibrium TA/LA phonon populations (30 -40 ps) and interband relaxation of the TA/LA modes (115 ps). Combining UEDS with ultrafast angle-resolved photoelectron spectroscopy will yield a complete picture of the dynamics within and between electron and phonon subsystems, helping to unravel complex phases in which the intertwined nature of these systems has a strong influence on emergent properties.

Metal ion influence on eumelanin fluorescence and structure.

PubMed

Sutter, Jens-Uwe; Birch, David J S

2014-04-10

Melanin has long been thought to have an unworkably weak and complex fluorescence, but here we study its intrinsic fluorescence in order to demonstrate how metal ions can be used to control the rate of formation, constituents and structure of eumelanin formed from the well-known laboratory auto-oxidation of 3,4-dihydroxy-L-phenylalanine (L-DOPA). The effect on eumelanin absorption and fluorescence of a range of solvated metal ions is reported including Cu, Zn, Ni, Na and K. Monovalent cations and Zn have little effect, but the effect of transition metal cations can be considerable. For example, at pH 10, copper ions are shown to accelerate the onset of eumelanin formation, but not the rate of formation once it commences, and simplify the usual complex structure and intrinsic fluorescence of eumelanin in a way that is consistent with an increased abundance of 5,5-dihydroxyindole-2-carboxylic acid (DHICA). The presence of a dominant 6 ns fluorescence decay time at 480 nm, when excited at 450 nm describes a distinct photophysical species, which we tentatively assign to small oligomers. Copper is well-known to normally quench fluorescence, but increasing amounts of copper surprisingly leads to an increase in the fluorescence decay time of eumelanin, while reducing the fluorescence intensity, suggesting copper modification of the excited state. Such results have bearing on diverse areas. The most accepted morphology for melanin is that of a graphite-like sheet structure, and one which readily binds metal ions, an interaction that is thought to have an important, though as yet unclear bearing on several areas of medicine including neurology. There is also increasing interest in bio-mimicry by preparing and labelling sheet structures with metal ions for new electronic and photonic materials.

Metal ion influence on eumelanin fluorescence and structure

NASA Astrophysics Data System (ADS)

Sutter, Jens-Uwe; Birch, David J. S.

2014-06-01

Melanin has long been thought to have an unworkably weak and complex fluorescence, but here we study its intrinsic fluorescence in order to demonstrate how metal ions can be used to control the rate of formation, constituents and structure of eumelanin formed from the well-known laboratory auto-oxidation of 3,4-dihydroxy-L-phenylalanine (L-DOPA). The effect on eumelanin absorption and fluorescence of a range of solvated metal ions is reported including Cu, Zn, Ni, Na and K. Monovalent cations and Zn have little effect, but the effect of transition metal cations can be considerable. For example, at pH 10, copper ions are shown to accelerate the onset of eumelanin formation, but not the rate of formation once it commences, and simplify the usual complex structure and intrinsic fluorescence of eumelanin in a way that is consistent with an increased abundance of 5,5-dihydroxyindole-2-carboxylic acid (DHICA). The presence of a dominant 6 ns fluorescence decay time at 480 nm, when excited at 450 nm describes a distinct photophysical species, which we tentatively assign to small oligomers. Copper is well-known to normally quench fluorescence, but increasing amounts of copper surprisingly leads to an increase in the fluorescence decay time of eumelanin, while reducing the fluorescence intensity, suggesting copper modification of the excited state. Such results have bearing on diverse areas. The most accepted morphology for melanin is that of a graphite-like sheet structure, and one which readily binds metal ions, an interaction that is thought to have an important, though as yet unclear bearing on several areas of medicine including neurology. There is also increasing interest in bio-mimicry by preparing and labelling sheet structures with metal ions for new electronic and photonic materials.

Fast and ultrafast endocytosis.

PubMed

Watanabe, Shigeki; Boucrot, Emmanuel

2017-08-01

Clathrin-mediated endocytosis (CME) is the main endocytic pathway supporting housekeeping functions in cells. However, CME may be too slow to internalize proteins from the cell surface during certain physiological processes such as reaction to stress hormones ('fight-or-flight' reaction), chemotaxis or compensatory endocytosis following exocytosis of synaptic vesicles or hormone-containing vesicles. These processes take place on a millisecond to second timescale and thus require very rapid cellular reaction to prevent overstimulation or exhaustion of the response. There are several fast endocytic processes identified so far: macropinocytosis, activity-dependent bulk endocytosis (ABDE), fast-endophilin-mediated endocytosis (FEME), kiss-and-run and ultrafast endocytosis. All are clathrin-independent and are not constitutively active but may use different molecular mechanisms to rapidly remove receptors and proteins from the cell surface. Here, we review our current understanding of fast and ultrafast endocytosis, their functions, and molecular mechanisms. Copyright © 2017 Elsevier Ltd. All rights reserved.

Modelling multi-pulse population dynamics from ultrafast spectroscopy.

PubMed

van Wilderen, Luuk J G W; Lincoln, Craig N; van Thor, Jasper J

2011-03-21

Current advanced laser, optics and electronics technology allows sensitive recording of molecular dynamics, from single resonance to multi-colour and multi-pulse experiments. Extracting the occurring (bio-) physical relevant pathways via global analysis of experimental data requires a systematic investigation of connectivity schemes. Here we present a Matlab-based toolbox for this purpose. The toolbox has a graphical user interface which facilitates the application of different reaction models to the data to generate the coupled differential equations. Any time-dependent dataset can be analysed to extract time-independent correlations of the observables by using gradient or direct search methods. Specific capabilities (i.e. chirp and instrument response function) for the analysis of ultrafast pump-probe spectroscopic data are included. The inclusion of an extra pulse that interacts with a transient phase can help to disentangle complex interdependent pathways. The modelling of pathways is therefore extended by new theory (which is included in the toolbox) that describes the finite bleach (orientation) effect of single and multiple intense polarised femtosecond pulses on an ensemble of randomly oriented particles in the presence of population decay. For instance, the generally assumed flat-top multimode beam profile is adapted to a more realistic Gaussian shape, exposing the need for several corrections for accurate anisotropy measurements. In addition, the (selective) excitation (photoselection) and anisotropy of populations that interact with single or multiple intense polarised laser pulses is demonstrated as function of power density and beam profile. Using example values of real world experiments it is calculated to what extent this effectively orients the ensemble of particles. Finally, the implementation includes the interaction with multiple pulses in addition to depth averaging in optically dense samples. In summary, we show that mathematical modelling is

Modelling Multi-Pulse Population Dynamics from Ultrafast Spectroscopy

PubMed Central

van Wilderen, Luuk J. G. W.; Lincoln, Craig N.; van Thor, Jasper J.

2011-01-01

Current advanced laser, optics and electronics technology allows sensitive recording of molecular dynamics, from single resonance to multi-colour and multi-pulse experiments. Extracting the occurring (bio-) physical relevant pathways via global analysis of experimental data requires a systematic investigation of connectivity schemes. Here we present a Matlab-based toolbox for this purpose. The toolbox has a graphical user interface which facilitates the application of different reaction models to the data to generate the coupled differential equations. Any time-dependent dataset can be analysed to extract time-independent correlations of the observables by using gradient or direct search methods. Specific capabilities (i.e. chirp and instrument response function) for the analysis of ultrafast pump-probe spectroscopic data are included. The inclusion of an extra pulse that interacts with a transient phase can help to disentangle complex interdependent pathways. The modelling of pathways is therefore extended by new theory (which is included in the toolbox) that describes the finite bleach (orientation) effect of single and multiple intense polarised femtosecond pulses on an ensemble of randomly oriented particles in the presence of population decay. For instance, the generally assumed flat-top multimode beam profile is adapted to a more realistic Gaussian shape, exposing the need for several corrections for accurate anisotropy measurements. In addition, the (selective) excitation (photoselection) and anisotropy of populations that interact with single or multiple intense polarised laser pulses is demonstrated as function of power density and beam profile. Using example values of real world experiments it is calculated to what extent this effectively orients the ensemble of particles. Finally, the implementation includes the interaction with multiple pulses in addition to depth averaging in optically dense samples. In summary, we show that mathematical modelling is

Fluorescence properties of Schiff base - N,N‧-bis(salicylidene) - 1,2-Phenylenediamine in presence of bile acid host

NASA Astrophysics Data System (ADS)

Roy, Nayan; Paul, Pradip C.; Singh, T. Sanjoy

2015-05-01

Fluorescence properties of Schiff base - N,N‧-bis(salicylidene) - 1,2-phenylenediamine (LH2) is used to study the micelles formed by aggregation of different important bile acids like cholic acid, deoxycholic acid, chenodeoxycholic acid and glycocholic acid by steady state and picosecond time-resolved fluorescence spectroscopy. The fluorescence band intensity was found out to increase with concomitant red shift with gradual addition of different bile acids. Binding constant of the probe with different bile acids as well as critical micelle concentration was obtained from the variation of fluorescence intensity on increasing concentration of bile acids in the medium. The increase in fluorescence quantum yields, fluorescence decay times and substantial decrease in nonradiative decay rate constants in bile acids micellar environment points to the restricted motion of the fluorophore inside the micellar subdomains.

Mega-electron-volt ultrafast electron diffraction at SLAC National Accelerator Laboratory.

PubMed

Weathersby, S P; Brown, G; Centurion, M; Chase, T F; Coffee, R; Corbett, J; Eichner, J P; Frisch, J C; Fry, A R; Gühr, M; Hartmann, N; Hast, C; Hettel, R; Jobe, R K; Jongewaard, E N; Lewandowski, J R; Li, R K; Lindenberg, A M; Makasyuk, I; May, J E; McCormick, D; Nguyen, M N; Reid, A H; Shen, X; Sokolowski-Tinten, K; Vecchione, T; Vetter, S L; Wu, J; Yang, J; Dürr, H A; Wang, X J

2015-07-01

Ultrafast electron probes are powerful tools, complementary to x-ray free-electron lasers, used to study structural dynamics in material, chemical, and biological sciences. High brightness, relativistic electron beams with femtosecond pulse duration can resolve details of the dynamic processes on atomic time and length scales. SLAC National Accelerator Laboratory recently launched the Ultrafast Electron Diffraction (UED) and microscopy Initiative aiming at developing the next generation ultrafast electron scattering instruments. As the first stage of the Initiative, a mega-electron-volt (MeV) UED system has been constructed and commissioned to serve ultrafast science experiments and instrumentation development. The system operates at 120-Hz repetition rate with outstanding performance. In this paper, we report on the SLAC MeV UED system and its performance, including the reciprocal space resolution, temporal resolution, and machine stability.

Crystallization Kinetics of an Amorphous Pharmaceutical Compound Using Fluorescence-Lifetime-Imaging Microscopy.

PubMed

Rautaniemi, Kaisa; Vuorimaa-Laukkanen, Elina; Strachan, Clare J; Laaksonen, Timo

2018-05-07

Pharmaceutical scientists are increasingly interested in amorphous drug formulations especially because of their higher dissolution rates. Consequently, the thorough characterization and analysis of these formulations are becoming more and more important for the pharmaceutical industry. Here, fluorescence-lifetime-imaging microscopy (FLIM) was used to monitor the crystallization of an amorphous pharmaceutical compound, indomethacin. Initially, we identified different solid indomethacin forms, amorphous and γ- and α-crystalline, on the basis of their time-resolved fluorescence. All of the studied indomethacin forms showed biexponential decays with characteristic fluorescence lifetimes and amplitudes. Using this information, the crystallization of amorphous indomethacin upon storage in 60 °C was monitored for 10 days with FLIM. The progress of crystallization was detected as lifetime changes both in the FLIM images and in the fluorescence-decay curves extracted from the images. The fluorescence-lifetime amplitudes were used for quantitative analysis of the crystallization process. We also demonstrated that the fluorescence-lifetime distribution of the sample changed during crystallization, and when the sample was not moved between measuring times, the lifetime distribution could also be used for the analysis of the reaction kinetics. Our results clearly show that FLIM is a sensitive and nondestructive method for monitoring solid-state transformations on the surfaces of fluorescent samples.

Rapid Global Fitting of Large Fluorescence Lifetime Imaging Microscopy Datasets

PubMed Central

Warren, Sean C.; Margineanu, Anca; Alibhai, Dominic; Kelly, Douglas J.; Talbot, Clifford; Alexandrov, Yuriy; Munro, Ian; Katan, Matilda

2013-01-01

Fluorescence lifetime imaging (FLIM) is widely applied to obtain quantitative information from fluorescence signals, particularly using Förster Resonant Energy Transfer (FRET) measurements to map, for example, protein-protein interactions. Extracting FRET efficiencies or population fractions typically entails fitting data to complex fluorescence decay models but such experiments are frequently photon constrained, particularly for live cell or in vivo imaging, and this leads to unacceptable errors when analysing data on a pixel-wise basis. Lifetimes and population fractions may, however, be more robustly extracted using global analysis to simultaneously fit the fluorescence decay data of all pixels in an image or dataset to a multi-exponential model under the assumption that the lifetime components are invariant across the image (dataset). This approach is often considered to be prohibitively slow and/or computationally expensive but we present here a computationally efficient global analysis algorithm for the analysis of time-correlated single photon counting (TCSPC) or time-gated FLIM data based on variable projection. It makes efficient use of both computer processor and memory resources, requiring less than a minute to analyse time series and multiwell plate datasets with hundreds of FLIM images on standard personal computers. This lifetime analysis takes account of repetitive excitation, including fluorescence photons excited by earlier pulses contributing to the fit, and is able to accommodate time-varying backgrounds and instrument response functions. We demonstrate that this global approach allows us to readily fit time-resolved fluorescence data to complex models including a four-exponential model of a FRET system, for which the FRET efficiencies of the two species of a bi-exponential donor are linked, and polarisation-resolved lifetime data, where a fluorescence intensity and bi-exponential anisotropy decay model is applied to the analysis of live cell

Ultrafast laser-collision-induced fluorescence in atmospheric pressure plasma

DOE PAGES

Barnat, E. V.; Fierro, A.

2017-03-07

The implementation and demonstration of laser-collision-induced fluorescence (LCIF) generated in atmospheric pressure helium environments is presented in this communication. As collision times are observed to be fast (~10 ns), ultrashort pulse laser excitation (<100 fs) of the 2 3S to 3 3P (388.9 nm) is utilized to initiate the LCIF process. Both neutral-induced and electron-induced components of the LCIF are observed in the helium afterglow plasma as the reduced electric field (E/N) is tuned from <0.1 Td to over 5 Td. Under the discharge conditions presented in this study (640 Torr He), the lower limit of electron density detection ismore » ~10 12 e cm -3. Lastly, the spatial profiles of the 2 3S helium metastable and electrons are presented as functions of E/N to demonstrate the spatial resolving capabilities of the LCIF method.« less

Combination of confocal principle and aperture stop separation improves suppression of crystalline lens fluorescence in an eye model.

PubMed

Klemm, Matthias; Blum, Johannes; Link, Dietmar; Hammer, Martin; Haueisen, Jens; Schweitzer, Dietrich

2016-09-01

Fluorescence lifetime imaging ophthalmoscopy (FLIO) is a new technique to detect changes in the human retina. The autofluorescence decay over time, generated by endogenous fluorophores, is measured in vivo. The strong autofluorescence of the crystalline lens, however, superimposes the intensity decay of the retina fluorescence, as the confocal principle is not able to suppress it sufficiently. Thus, the crystalline lens autofluorescence causes artifacts in the retinal fluorescence lifetimes determined from the intensity decays. Here, we present a new technique to suppress the autofluorescence of the crystalline lens by introducing an annular stop into the detection light path, which we call Schweitzer's principle. The efficacy of annular stops with an outer diameter of 7 mm and inner diameters of 1 to 5 mm are analyzed in an experimental setup using a model eye based on fluorescent dyes. Compared to the confocal principle, Schweitzer's principle with an inner diameter of 3 mm is able to reduce the simulated crystalline lens fluorescence to 4%, while 42% of the simulated retina fluorescence is preserved. Thus, we recommend the implementation of Schweitzer's principle in scanning laser ophthalmoscopes used for fundus autofluorescence measurements, especially the FLIO device, for improved image quality.

Transthoracic Ultrafast Doppler Imaging of Human Left Ventricular Hemodynamic Function

PubMed Central

Osmanski, Bruno-Félix; Maresca, David; Messas, Emmanuel; Tanter, Mickael; Pernot, Mathieu

2016-01-01

Heart diseases can affect intraventricular blood flow patterns. Real-time imaging of blood flow patterns is challenging because it requires both a high frame rate and a large field of view. To date, standard Doppler techniques can only perform blood flow estimation with high temporal resolution within small regions of interest. In this work, we used ultrafast imaging to map in 2D human left ventricular blood flow patterns during the whole cardiac cycle. Cylindrical waves were transmitted at 4800 Hz with a transthoracic phased array probe to achieve ultrafast Doppler imaging of the left ventricle. The high spatio-temporal sampling of ultrafast imaging permits to rely on a much more effective wall filtering and to increase sensitivity when mapping blood flow patterns during the pre-ejection, ejection, early diastole, diastasis and late diastole phases of the heart cycle. The superior sensitivity and temporal resolution of ultrafast Doppler imaging makes it a promising tool for the noninvasive study of intraventricular hemodynamic function. PMID:25073134

Time-resolved UV-excited microarray reader for fluorescence energy transfer (FRET) measurements

NASA Astrophysics Data System (ADS)

Orellana, Adelina; Hokkanen, Ari P.; Pastinen, Tomi; Takkinen, Kristina; Soderlund, Hans

2001-05-01

Analytical systems based on immunochemistry are largely used in medical diagnostics and in biotechnology. There is a significant pressure to develop the present assay formats to become easier to use, faster, and less reagent consuming. Further developments towards high density array--like multianalyte measurement systems would be valuable. To this aim we have studied the applicability of fluorescence resonance energy transfer and time-resolved fluorescence resonance energy transfer in immunoassays on microspots and in microwells. We have used engineered recombinant antibodies detecting the pentameric protein CRP as a model analyte system, and tested different assay formats. We describe also the construction of a time-resolved scanning epifluorometer with which we could measure the FRET interaction between the slow fluorescence decay from europium chelates and its energy transfer to the rapidly decaying fluorophore Cy5.

Excitation energy dependence of excited states dynamics in all- trans-carotenes determined by femtosecond absorption and fluorescence spectroscopy

NASA Astrophysics Data System (ADS)

Kosumi, Daisuke; Yanagi, Kazuhiro; Nishio, Tomohiro; Hashimoto, Hideki; Yoshizawa, Masayuki

2005-06-01

Ultrafast relaxation kinetics in β-carotene and lycopene has been investigated by femtosecond absorption and fluorescence spectroscopies using tunable excitation pulses. The transient signals induced by the photoexcitation with larger excess energy have broader bands and longer lifetimes both in the 11Bu+and21Ag- excited states. The excess vibrational energy remains longer than several picoseconds and slows the relaxation kinetics in carotenoids.

Ultrafast non-radiative dynamics of atomically thin MoSe 2

DOE PAGES

Lin, Ming -Fu; Kochat, Vidya; Krishnamoorthy, Aravind; ...

2017-10-17

Non-radiative energy dissipation in photoexcited materials and resulting atomic dynamics provide a promising pathway to induce structural phase transitions in two-dimensional materials. However, these dynamics have not been explored in detail thus far because of incomplete understanding of interaction between the electronic and atomic degrees of freedom, and a lack of direct experimental methods to quantify real-time atomic motion and lattice temperature. Here, we explore the ultrafast conversion of photoenergy to lattice vibrations in a model bi-layered semiconductor, molybdenum diselenide, MoSe 2. Specifically, we characterize sub-picosecond lattice dynamics initiated by the optical excitation of electronic charge carriers in the highmore » electron-hole plasma density regime. Our results focuses on the first ten picosecond dynamics subsequent to photoexcitation before the onset of heat transfer to the substrate, which occurs on a ~100 picosecond time scale. Photoinduced atomic motion is probed by measuring the time dependent Bragg diffraction of a delayed mega-electronvolt femtosecond electron beam. Transient lattice temperatures are characterized through measurement of Bragg peak intensities and calculation of the Debye-Waller factor (DWF). These measurements show a sub-picosecond decay of Bragg diffraction and a correspondingly rapid rise in lattice temperatures. We estimate a high quantum yield for the conversion of excited charge carrier energy to lattice motion under our experimental conditions, indicative of a strong electron-phonon interaction. First principles nonadiabatic quantum molecular dynamics simulations (NAQMD) on electronically excited MoSe 2 bilayers reproduce the observed picosecond-scale increase in lattice temperature and ultrafast conversion of photoenergy to lattice vibrations. Calculation of excited-state phonon dispersion curves suggests that softened vibrational modes in the excited state are involved in efficient and rapid energy

Ultrafast non-radiative dynamics of atomically thin MoSe 2

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

Lin, Ming -Fu; Kochat, Vidya; Krishnamoorthy, Aravind

Non-radiative energy dissipation in photoexcited materials and resulting atomic dynamics provide a promising pathway to induce structural phase transitions in two-dimensional materials. However, these dynamics have not been explored in detail thus far because of incomplete understanding of interaction between the electronic and atomic degrees of freedom, and a lack of direct experimental methods to quantify real-time atomic motion and lattice temperature. Here, we explore the ultrafast conversion of photoenergy to lattice vibrations in a model bi-layered semiconductor, molybdenum diselenide, MoSe 2. Specifically, we characterize sub-picosecond lattice dynamics initiated by the optical excitation of electronic charge carriers in the highmore » electron-hole plasma density regime. Our results focuses on the first ten picosecond dynamics subsequent to photoexcitation before the onset of heat transfer to the substrate, which occurs on a ~100 picosecond time scale. Photoinduced atomic motion is probed by measuring the time dependent Bragg diffraction of a delayed mega-electronvolt femtosecond electron beam. Transient lattice temperatures are characterized through measurement of Bragg peak intensities and calculation of the Debye-Waller factor (DWF). These measurements show a sub-picosecond decay of Bragg diffraction and a correspondingly rapid rise in lattice temperatures. We estimate a high quantum yield for the conversion of excited charge carrier energy to lattice motion under our experimental conditions, indicative of a strong electron-phonon interaction. First principles nonadiabatic quantum molecular dynamics simulations (NAQMD) on electronically excited MoSe 2 bilayers reproduce the observed picosecond-scale increase in lattice temperature and ultrafast conversion of photoenergy to lattice vibrations. Calculation of excited-state phonon dispersion curves suggests that softened vibrational modes in the excited state are involved in efficient and rapid energy

Direct diode pumped Ti:sapphire ultrafast regenerative amplifier system

DOE PAGES

Backus, Sterling; Durfee, Charles; Lemons, Randy; ...

2017-02-10

Here, we report on a direct diode-pumped Ti:sapphire ultrafast regenerative amplifier laser system producing multi-uJ energies with repetition rate from 50 to 250 kHz. By combining cryogenic cooling of Ti:sapphire with high brightness fiber-coupled 450nm laser diodes, we for the first time demonstrate a power-scalable CW-pumped architecture that can be directly applied to demanding ultrafast applications such as coherent high-harmonic EUV generation without any complex post-amplification pulse compression. Initial results promise a new era for Ti:sapphire amplifiers not only for ultrafast laser applications, but also for tunable CW sources. We discuss the unique challenges to implementation, as well as themore » solutions to these challenges.« less

Direct diode pumped Ti:sapphire ultrafast regenerative amplifier system

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

Backus, Sterling; Durfee, Charles; Lemons, Randy

Here, we report on a direct diode-pumped Ti:sapphire ultrafast regenerative amplifier laser system producing multi-uJ energies with repetition rate from 50 to 250 kHz. By combining cryogenic cooling of Ti:sapphire with high brightness fiber-coupled 450nm laser diodes, we for the first time demonstrate a power-scalable CW-pumped architecture that can be directly applied to demanding ultrafast applications such as coherent high-harmonic EUV generation without any complex post-amplification pulse compression. Initial results promise a new era for Ti:sapphire amplifiers not only for ultrafast laser applications, but also for tunable CW sources. We discuss the unique challenges to implementation, as well as themore » solutions to these challenges.« less

Visualization of Membrane Rafts Using a Perylene Monoimide Derivative and Fluorescence Lifetime Imaging

PubMed Central

Margineanu, Anca; Hotta, Jun-ichi; Van der Auweraer, Mark; Ameloot, Marcel; Stefan, Alina; Beljonne, David; Engelborghs, Yves; Herrmann, Andreas; Müllen, Klaus; De Schryver, Frans C.; Hofkens, Johan

2007-01-01

A new membrane probe, based on the perylene imide chromophore, with excellent photophysical properties (high absorption coefficient, quantum yield (QY) ≈ 1, high photostability) and excited in the visible domain is proposed for the study of membrane rafts. Visualization of separation between the liquid-ordered (Lo) and the liquid-disordered (Ld) phases can be achieved in artificial membranes by fluorescence lifetime imaging due to the different decay times of the membrane probe in the two phases. Rafts on micrometer-scale in cell membranes due to cellular activation can also be observed by this method. The decay time of the dye in the Lo phase is higher than in organic solvents where its QY is 1. This allows proposing a (possible general) mechanism for the decay time increase in the Lo phase, based on the local field effects of the surrounding molecules. For other fluorophores with QY < 1, the suggested mechanism could also contribute, in addition to effects reducing the nonradiative decay pathways, to an increase of the fluorescence decay time in the Lo phase. PMID:17573424

Development of a time-resolved fluorometric method for observing hybridization in living cells using fluorescence resonance energy transfer.

PubMed Central

Tsuji, A; Sato, Y; Hirano, M; Suga, T; Koshimoto, H; Taguchi, T; Ohsuka, S

2001-01-01

We previously showed that a specific kind of mRNA (c-fos) was detected in a living cell under a microscope by introducing two fluorescently labeled oligodeoxynucleotides, each labeled with donor or acceptor, into the cytoplasm, making them hybridize to adjacent locations on c-fos mRNA, and taking images of fluorescence resonance energy transfer (FRET) (A. Tsuji, H. Koshimoto, Y. Sato, M. Hirano. Y. Sei-Iida, S. Kondo, and K. Ishibashi, 2000, Biophys. J. 78:3260-3274). On the formed hybrid, the distance between donor and acceptor becomes close and FRET occurs. To observe small numbers of mRNA in living cells using this method, it is required that FRET fluorescence of hybrid must be distinguished from fluorescence of excess amounts of non-hybridizing probes and from cell autofluorescence. To meet these requirements, we developed a time-resolved method using acceptor fluorescence decays. When a combination of a donor having longer fluorescence lifetime and an acceptor having shorter lifetime is used, the measured fluorescence decays of acceptors under FRET becomes slower than the acceptor fluorescence decay with direct excitation. A combination of Bodipy493/503 and Cy5 was selected as donor and acceptor. When the formed hybrid had a configuration where the target RNA has no single-strand part between the two fluorophores, the acceptor fluorescence of hybrid had a sufficiently longer delay to detect fluorescence of hybrid in the presence of excess amounts of non-hybridizing probes. Spatial separation of 10-12 bases between two fluorophores on the hybrid is also required. The decay is also much slower than cell autofluorescence, and smaller numbers of hybrid were detected with less interference of cell autofluorescence in the cytoplasm of living cells under a time-resolved fluorescence microscope with a time-gated function equipped camera. The present method will be useful when observing induced expressions of mRNA in living cells. PMID:11423432

Ultrafast Spreading Effect Induced Rapid Cell Trapping into Porous Scaffold with Superhydrophilic Surface.

PubMed

Wang, Chenmiao; Qiao, Chunyan; Song, Wenlong; Sun, Hongchen

2015-08-19

In this contribution, superhydrophilic chitosan-based scaffolds with ultrafast spreading property were fabricated and used to improve the trapped efficiency of cells. The ultrafast spreading property allowed cells to be trapped into the internal 3D porous structures of the prepared scaffolds more quickly and effectively. Cell adhesion, growth, and proliferation were also improved, which could be attributed to the combination of UV irradiation and ultrafast spreading property. The construction of ultrafast spreading property on the scaffold surface will offer a novel way to design more effective scaffold in tissue engineering that could largely shorten the therapeutic time for patients.

High Contrast Ultrafast Imaging of the Human Heart

PubMed Central

Papadacci, Clement; Pernot, Mathieu; Couade, Mathieu; Fink, Mathias; Tanter, Mickael

2014-01-01

Non-invasive ultrafast imaging for human cardiac applications is a big challenge to image intrinsic waves such as electromechanical waves or remotely induced shear waves in elastography imaging techniques. In this paper we propose to perform ultrafast imaging of the heart with adapted sector size by using diverging waves emitted from a classical transthoracic cardiac phased array probe. As in ultrafast imaging with plane wave coherent compounding, diverging waves can be summed coherently to obtain high-quality images of the entire heart at high frame rate in a full field-of-view. To image shear waves propagation at high SNR, the field-of-view can be adapted by changing the angular aperture of the transmitted wave. Backscattered echoes from successive circular wave acquisitions are coherently summed at every location in the image to improve the image quality while maintaining very high frame rates. The transmitted diverging waves, angular apertures and subapertures size are tested in simulation and ultrafast coherent compounding is implemented on a commercial scanner. The improvement of the imaging quality is quantified in phantom and in vivo on human heart. Imaging shear wave propagation at 2500 frame/s using 5 diverging waves provides a strong increase of the Signal to noise ratio of the tissue velocity estimates while maintaining a high frame rate. Finally, ultrafast imaging with a 1 to 5 diverging waves is used to image the human heart at a frame rate of 900 frames/s over an entire cardiac cycle. Thanks to spatial coherent compounding, a strong improvement of imaging quality is obtained with a small number of transmitted diverging waves and a high frame rate, which allows imaging the propagation of electromechanical and shear waves with good image quality. PMID:24474135

Catheter-based time-gated near-infrared fluorescence/OCT imaging system

NASA Astrophysics Data System (ADS)

Lu, Yuankang; Abran, Maxime; Cloutier, Guy; Lesage, Frédéric

2018-02-01

We developed a new dual-modality intravascular imaging system based on fast time-gated fluorescence intensity imaging and spectral domain optical coherence tomography (SD-OCT) for the purpose of interventional detection of atherosclerosis. A pulsed supercontinuum laser was used for fluorescence and OCT imaging. A double-clad fiber (DCF)- based side-firing catheter was designed and fabricated to have a 23 μm spot size at a 2.2 mm working distance for OCT imaging. Its single-mode core is used for OCT, while its inner cladding transports fluorescence excitation light and collects fluorescent photons. The combination of OCT and fluorescence imaging was achieved by using a DCF coupler. For fluorescence detection, we used a time-gated technique with a novel single-photon avalanche diode (SPAD) working in an ultra-fast gating mode. A custom-made delay chip was integrated in the system to adjust the delay between the excitation laser pulse and the SPAD gate-ON window. This technique allowed to detect fluorescent photons of interest while rejecting most of the background photons, thus leading to a significantly improved signal to noise ratio (SNR). Experiments were carried out in turbid media mimicking tissue with an indocyanine green (ICG) inclusion (1 mM and 100 μM) to compare the time-gated technique and the conventional continuous detection technique. The gating technique increased twofold depth sensitivity, and tenfold SNR at large distances. The dual-modality imaging capacity of our system was also validated with a silicone-based tissue-mimicking phantom.

Mega-electron-volt ultrafast electron diffraction at SLAC National Accelerator Laboratory

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

Weathersby, S. P.; Brown, G.; Chase, T. F.

Ultrafast electron probes are powerful tools, complementary to x-ray free-electron lasers, used to study structural dynamics in material, chemical, and biological sciences. High brightness, relativistic electron beams with femtosecond pulse duration can resolve details of the dynamic processes on atomic time and length scales. SLAC National Accelerator Laboratory recently launched the Ultrafast Electron Diffraction (UED) and microscopy Initiative aiming at developing the next generation ultrafast electron scattering instruments. As the first stage of the Initiative, a mega-electron-volt (MeV) UED system has been constructed and commissioned to serve ultrafast science experiments and instrumentation development. The system operates at 120-Hz repetition ratemore » with outstanding performance. In this paper, we report on the SLAC MeV UED system and its performance, including the reciprocal space resolution, temporal resolution, and machine stability.« less

Triplet exciton dissociation and electron extraction in graphene-templated pentacene observed with ultrafast spectroscopy.

PubMed

McDonough, Thomas J; Zhang, Lushuai; Roy, Susmit Singha; Kearns, Nicholas M; Arnold, Michael S; Zanni, Martin T; Andrew, Trisha L

2017-02-08

We compare the ultrafast dynamics of singlet fission and charge generation in pentacene films grown on glass and graphene. Pentacene grown on graphene is interesting because it forms large crystals with the long axis of the molecules "lying-down" (parallel to the surface). At low excitation fluence, spectra for pentacene on graphene contain triplet absorptions at 507 and 545 nm and no bleaching at 630 nm, which we show is due to the orientation of the pentacene molecules. We perform the first transient absorption anisotropy measurements on pentacene, observing negative anisotropy of the 507 and 545 nm peaks, consistent with triplet absorption. A broad feature at 853 nm, observed on both glass and graphene, is isotropic, suggesting hole absorption. At high fluence, there are additional features, whose kinetics and anisotropies are not explained by heating, that we assign to charge generation; we propose a polaron pair absorption at 614 nm. The lifetimes are shorter at high fluence for both pentacene on glass and graphene, indicative of triplet-triplet annihilation that likely enhances charge generation. The anisotropy decays more slowly for pentacene on graphene than on glass, in keeping with the smaller domain size observed via atomic force microscopy. Coherent acoustic phonons are observed for pentacene on graphene, which is a consequence of more homogeneous domains. Measuring the ultrafast dynamics of pentacene as a function of molecular orientation, fluence, and polarization provides new insight to previous spectral assignments.

Intravital multiphoton fluorescence imaging and optical manipulation of spinal cord in mice, using a compact fiber laser system.

PubMed

Oshima, Yusuke; Horiuch, Hideki; Honkura, Naoki; Hikita, Atsuhiko; Ogata, Tadanori; Miura, Hiromasa; Imamura, Takeshi

2014-09-01

Near-infrared ultrafast lasers are widely used for multiphoton excited fluorescence microscopy in living animals. Ti:Sapphire lasers are typically used for multiphoton excitation, but their emission wavelength is restricted below 1,000 nm. The aim of this study is to evaluate the performance of a compact Ytterbium-(Yb-) fiber laser at 1,045 nm for multiphoton excited fluorescence microscopy in spinal cord injury. In this study, we employed a custom-designed microscopy system with a compact Yb-fiber laser and evaluated the performance of this system in in vivo imaging of brain cortex and spinal cord in YFP-H transgenic mice. For in vivo imaging of brain cortex, sharp images of basal dendrites, and pyramidal cells expressing EYFP were successfully captured using the Yb-fiber laser in our microscopy system. We also performed in vivo imaging of axon fibers of spinal cord in the transgenic mice. The obtained images were almost as sharp as those obtained using a conventional ultrafast laser system. In addition, laser ablation and multi-color imaging could be performed simultaneously using the Yb-fiber laser. The high-peak pulse Yb-fiber laser is potentially useful for multimodal bioimaging methods based on a multiphoton excited fluorescence microscopy system that incorporates laser ablation techniques. Our results suggest that microscopy systems of this type could be utilized in studies of neuroscience and clinical use in diagnostics and therapeutic tool for spinal cord injury in the future. © 2014 Wiley Periodicals, Inc.

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

PubMed

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

2011-10-01

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

Photophysics of Zinc Porphyrin Aggregates in Dilute Water-Ethanol Solutions.

PubMed

Stevens, Amy L; Joshi, Neeraj K; Paige, Matthew F; Steer, Ronald P

2017-12-14

Dimeric and multimeric aggregates of a model metalloporphyrin, zinc tetraphenylporphyrin (ZnTPP), have been produced in a controlled manner by incrementally increasing the water content of dilute aqueous ethanol solutions. Steady state absorption, fluorescence emission, and fluorescence excitation spectra have been measured to identify the aggregates present as a function of solvent composition. The dynamics of the excited states of the aggregates produced initially by excitation in the Soret region have been measured by ultrafast fluorescence upconversion techniques. Only the monomer produces measurable emission from S 2 with a picosecond lifetime; all Soret-excited aggregates, including the dimer, decay radiationlessly on a femtosecond time scale. The S 1 state is the only significant product of the radiationless decay of the S 2 state of the excited monomer, and the aggregates also produce substantial quantum yields of S 1 fluorescence when initially excited in the Soret region. The resulting fluorescent aggregates all decay on a subnanosecond time scale, likely by a mechanism that involves dissociation of the excited monomer from the excitonic multimer. The ZnTPP dimers excited at their ground state geometries in the Soret region exhibit a dynamic behavior that is quite different from those produced following noncoherent triplet-triplet annihilation under the same conditions. The important implications of these observations in determining the aggregation conditions promoting efficient photon upconversion by excitonic annihilation in a variety of media are thoroughly discussed.

Engineering model for ultrafast laser microprocessing

NASA Astrophysics Data System (ADS)

Audouard, E.; Mottay, E.

2016-03-01

Ultrafast laser micro-machining relies on complex laser-matter interaction processes, leading to a virtually athermal laser ablation. The development of industrial ultrafast laser applications benefits from a better understanding of these processes. To this end, a number of sophisticated scientific models have been developed, providing valuable insights in the physics of the interaction. Yet, from an engineering point of view, they are often difficult to use, and require a number of adjustable parameters. We present a simple engineering model for ultrafast laser processing, applied in various real life applications: percussion drilling, line engraving, and non normal incidence trepanning. The model requires only two global parameters. Analytical results are derived for single pulse percussion drilling or simple pass engraving. Simple assumptions allow to predict the effect of non normal incident beams to obtain key parameters for trepanning drilling. The model is compared to experimental data on stainless steel with a wide range of laser characteristics (time duration, repetition rate, pulse energy) and machining conditions (sample or beam speed). Ablation depth and volume ablation rate are modeled for pulse durations from 100 fs to 1 ps. Trepanning time of 5.4 s with a conicity of 0.15° is obtained for a hole of 900 μm depth and 100 μm diameter.

Thermally activated delayed fluorescence of fluorescein derivative for time-resolved and confocal fluorescence imaging.

PubMed

Xiong, Xiaoqing; Song, Fengling; Wang, Jingyun; Zhang, Yukang; Xue, Yingying; Sun, Liangliang; Jiang, Na; Gao, Pan; Tian, Lu; Peng, Xiaojun

2014-07-09

Compared with fluorescence imaging utilizing fluorophores whose lifetimes are in the order of nanoseconds, time-resolved fluorescence microscopy has more advantages in monitoring target fluorescence. In this work, compound DCF-MPYM, which is based on a fluorescein derivative, showed long-lived luminescence (22.11 μs in deaerated ethanol) and was used in time-resolved fluorescence imaging in living cells. Both nanosecond time-resolved transient difference absorption spectra and time-correlated single-photon counting (TCSPC) were employed to explain the long lifetime of the compound, which is rare in pure organic fluorophores without rare earth metals and heavy atoms. A mechanism of thermally activated delayed fluorescence (TADF) that considers the long wavelength fluorescence, large Stokes shift, and long-lived triplet state of DCF-MPYM was proposed. The energy gap (ΔEST) of DCF-MPYM between the singlet and triplet state was determined to be 28.36 meV by the decay rate of DF as a function of temperature. The ΔE(ST) was small enough to allow efficient intersystem crossing (ISC) and reverse ISC, leading to efficient TADF at room temperature. The straightforward synthesis of DCF-MPYM and wide availability of its starting materials contribute to the excellent potential of the compound to replace luminescent lanthanide complexes in future time-resolved imaging technologies.

Study on Ultrafast Photodynamics of Novel Multilayered Thin Films for Device Applications

DTIC Science & Technology

2004-07-31

study ultrafast phase-transition of VO2 thin film. This part of work was started right after the new laser installed. With better laser output...1-3]. With the purpose of combined effect that the proposed ultrafast phase-transition VO2 thin film deposited on a substrate of heavy metal...second point of focus was to study ultrafast phase-transition of VO2 thin film. This part of work was started right after the new laser installed

Single-shot ultrafast tomographic imaging by spectral multiplexing

NASA Astrophysics Data System (ADS)

Matlis, N. H.; Axley, A.; Leemans, W. P.

2012-10-01

Computed tomography has profoundly impacted science, medicine and technology by using projection measurements scanned over multiple angles to permit cross-sectional imaging of an object. The application of computed tomography to moving or dynamically varying objects, however, has been limited by the temporal resolution of the technique, which is set by the time required to complete the scan. For objects that vary on ultrafast timescales, traditional scanning methods are not an option. Here we present a non-scanning method capable of resolving structure on femtosecond timescales by using spectral multiplexing of a single laser beam to perform tomographic imaging over a continuous range of angles simultaneously. We use this technique to demonstrate the first single-shot ultrafast computed tomography reconstructions and obtain previously inaccessible structure and position information for laser-induced plasma filaments. This development enables real-time tomographic imaging for ultrafast science, and offers a potential solution to the challenging problem of imaging through scattering surfaces.

Circularly polarized attosecond pulse generation and applications to ultrafast magnetism

NASA Astrophysics Data System (ADS)

Bandrauk, André D.; Guo, Jing; Yuan, Kai-Jun

2017-12-01

Attosecond science is a growing new field of research and potential applications which relies on the development of attosecond light sources. Achievements in the generation and application of attosecond pulses enable to investigate electron dynamics in the nonlinear nonperturbative regime of laser-matter interactions on the electron’s natural time scale, the attosecond. In this review, we describe the generation of circularly polarized attosecond pulses and their applications to induce attosecond magnetic fields, new tools for ultrafast magnetism. Simulations are performed on aligned one-electron molecular ions by using nonperturbative nonlinear solutions of the time-dependent Schrödinger equation. We discuss how bichromatic circularly polarized laser pulses with co-rotating or counter-rotating components induce electron-parent ion recollisions, thus producing circularly polarized high-order harmonic generation, the source of circularly polarized attosecond pulses. Ultrafast quantum electron currents created by the generated attosecond pulses give rise to attosecond magnetic field pulses. The results provide a guiding principle for producing circularly polarized attosecond pulses and ultrafast magnetic fields in complex molecular systems for future research in ultrafast magneto-optics.

Ultrafast Growth of High-Quality Monolayer WSe2 on Au.

PubMed

Gao, Yang; Hong, Yi-Lun; Yin, Li-Chang; Wu, Zhangting; Yang, Zhiqing; Chen, Mao-Lin; Liu, Zhibo; Ma, Teng; Sun, Dong-Ming; Ni, Zhenhua; Ma, Xiu-Liang; Cheng, Hui-Ming; Ren, Wencai

2017-08-01

The ultrafast growth of high-quality uniform monolayer WSe 2 is reported with a growth rate of ≈26 µm s -1 by chemical vapor deposition on reusable Au substrate, which is ≈2-3 orders of magnitude faster than those of most 2D transition metal dichalcogenides grown on nonmetal substrates. Such ultrafast growth allows for the fabrication of millimeter-size single-crystal WSe 2 domains in ≈30 s and large-area continuous films in ≈60 s. Importantly, the ultrafast grown WSe 2 shows excellent crystal quality and extraordinary electrical performance comparable to those of the mechanically exfoliated samples, with a high mobility up to ≈143 cm 2 V -1 s -1 and ON/OFF ratio up to 9 × 10 6 at room temperature. Density functional theory calculations reveal that the ultrafast growth of WSe 2 is due to the small energy barriers and exothermic characteristic for the diffusion and attachment of W and Se on the edges of WSe 2 on Au substrate. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrically-driven GHz range ultrafast graphene light emitter (Conference Presentation)

NASA Astrophysics Data System (ADS)

Kim, Youngduck; Gao, Yuanda; Shiue, Ren-Jye; Wang, Lei; Aslan, Ozgur Burak; Kim, Hyungsik; Nemilentsau, Andrei M.; Low, Tony; Taniguchi, Takashi; Watanabe, Kenji; Bae, Myung-Ho; Heinz, Tony F.; Englund, Dirk R.; Hone, James

2017-02-01

Ultrafast electrically driven light emitter is a critical component in the development of the high bandwidth free-space and on-chip optical communications. Traditional semiconductor based light sources for integration to photonic platform have therefore been heavily studied over the past decades. However, there are still challenges such as absence of monolithic on-chip light sources with high bandwidth density, large-scale integration, low-cost, small foot print, and complementary metal-oxide-semiconductor (CMOS) technology compatibility. Here, we demonstrate the first electrically driven ultrafast graphene light emitter that operate up to 10 GHz bandwidth and broadband range (400 1600 nm), which are possible due to the strong coupling of charge carriers in graphene and surface optical phonons in hBN allow the ultrafast energy and heat transfer. In addition, incorporation of atomically thin hexagonal boron nitride (hBN) encapsulation layers enable the stable and practical high performance even under the ambient condition. Therefore, electrically driven ultrafast graphene light emitters paves the way towards the realization of ultrahigh bandwidth density photonic integrated circuits and efficient optical communications networks.

Ultrafast control and monitoring of material properties using terahertz pulses

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

Bowlan, Pamela Renee

These are a set of slides on ultrafast control and monitoring of material properties using terahertz pulses. A few of the topics covered in these slides are: How fast is a femtosecond (fs), Different frequencies probe different properties of molecules or solids, What can a THz pulse do to a material, Ultrafast spectroscopy, Generating and measuring ultrashort THz pulses, Tracking ultrafast spin dynamics in antiferromagnets through spin wave resonances, Coherent two-dimensional THz spectroscopy, and Probing vibrational dynamics at a surface. Conclusions are: Coherent two-dimensional THz spectroscopy: a powerful approach for studying coherence and dynamics of low energy resonances. Applying thismore » to graphene we investigated the very strong THz light mater interaction which dominates over scattering. Useful for studying coupled excitations in multiferroics and monitoring chemical reactions. Also, THz-pump, SHG-probe spectoscopy: an ultrafast, surface sensitive probe of atomic-scale symmetry changes and nonlinear phonon dymanics. We are using this in Bi 2Se 3 to investigate the nonlinear surface phonon dynamics. This is potentially very useful for studying catalysis.« less

Rise-Time of FRET-Acceptor Fluorescence Tracks Protein Folding

PubMed Central

Lindhoud, Simon; Westphal, Adrie H.; van Mierlo, Carlo P. M.; Visser, Antonie J. W. G.; Borst, Jan Willem

2014-01-01

Uniform labeling of proteins with fluorescent donor and acceptor dyes with an equimolar ratio is paramount for accurate determination of Förster resonance energy transfer (FRET) efficiencies. In practice, however, the labeled protein population contains donor-labeled molecules that have no corresponding acceptor. These FRET-inactive donors contaminate the donor fluorescence signal, which leads to underestimation of FRET efficiencies in conventional fluorescence intensity and lifetime-based FRET experiments. Such contamination is avoided if FRET efficiencies are extracted from the rise time of acceptor fluorescence upon donor excitation. The reciprocal value of the rise time of acceptor fluorescence is equal to the decay rate of the FRET-active donor fluorescence. Here, we have determined rise times of sensitized acceptor fluorescence to study the folding of double-labeled apoflavodoxin molecules and show that this approach tracks the characteristics of apoflavodoxinʼs complex folding pathway. PMID:25535076

Theoretical study on ultrafast intersystem crossing of chromium(III) acetylacetonate

NASA Astrophysics Data System (ADS)

Ando, Hideo; Iuchi, Satoru; Sato, Hirofumi

2012-05-01

In the relaxation process from the 4T2g state of chromium(III) acetylacetonate, CrIII(acac)3, ultrafast intersystem crossing (ISC) competes with vibrational relaxation (VR). This contradicts the conventional cascade model, where ISC rates are slower than VR ones. We hence investigate the relaxation process with quantum chemical calculations and excited-state wavepacket simulations to obtain clues about the origins of the ultrafast ISC. It is found that a potential energy curve of the 4T2g state crosses those of the 2T1g states near the Franck-Condon region and their spin-orbit couplings are strong. Consequently, ultrafast ISC between these states is observed in the wavepacket simulation.

Ultrafast demagnetisation dependence on film thickness: A TDDFT calculation

NASA Astrophysics Data System (ADS)

Singh, N.; Sharma, S.

2018-04-01

Ferromagnetic materials when subjected to intense laser pulses leads to reduction of their magnetisation on an ultrafast scale. Here, we perform an ab-initio calculation to study the behavior of ultrafast demagnetisation as a function of film thickness for Nickel as compared to the bulk of the material. In thin films surface formation results in amplification of demagnetisation with the percentage of demagnetisation depending upon the film thickness.

Ultrafast spontaneous emission of copper-doped silicon enhanced by an optical nanocavity.

PubMed

Sumikura, Hisashi; Kuramochi, Eiichi; Taniyama, Hideaki; Notomi, Masaya

2014-05-23

Dopants in silicon (Si) have attracted attention in the fields of photonics and quantum optics. However, the optical characteristics are limited by the small spontaneous emission rate of dopants in Si. This study demonstrates a large increase in the spontaneous emission rate of copper isoelectronic centres (Cu-IECs) doped into Si photonic crystal nanocavities. In a cavity with a quality factor (Q) of ~16,000, the photoluminescence (PL) lifetime of the Cu-IECs is 1.1 ns, which is 30 times shorter than the lifetime of a sample without a cavity. The PL decay rate is increased in proportion to Q/Vc (Vc is the cavity mode volume), which indicates the Purcell effect. This is the first demonstration of a cavity-enhanced ultrafast spontaneous emission from dopants in Si, and it may lead to the development of fast and efficient Si light emitters and Si quantum optical devices based on dopants with efficient optical access.

Ultrafast spontaneous emission of copper-doped silicon enhanced by an optical nanocavity

PubMed Central

SUMIKURA, HISASHI; KURAMOCHI, EIICHI; TANIYAMA, HIDEAKI; NOTOMI, MASAYA

2014-01-01

Dopants in silicon (Si) have attracted attention in the fields of photonics and quantum optics. However, the optical characteristics are limited by the small spontaneous emission rate of dopants in Si. This study demonstrates a large increase in the spontaneous emission rate of copper isoelectronic centres (Cu-IECs) doped into Si photonic crystal nanocavities. In a cavity with a quality factor (Q) of ~16,000, the photoluminescence (PL) lifetime of the Cu-IECs is 1.1 ns, which is 30 times shorter than the lifetime of a sample without a cavity. The PL decay rate is increased in proportion to Q/Vc (Vc is the cavity mode volume), which indicates the Purcell effect. This is the first demonstration of a cavity-enhanced ultrafast spontaneous emission from dopants in Si, and it may lead to the development of fast and efficient Si light emitters and Si quantum optical devices based on dopants with efficient optical access. PMID:24853336

Time-Resolved Fluorescence of Water-Soluble Pyridinium Salt: Sensitive Detection of the Conformational Changes of Bovine Serum Albumin.

PubMed

Li, Lei; Yi, Hua; Jia, Menghui; Chang, Mengfang; Zhou, Zhongneng; Zhang, Sanjun; Pan, Haifeng; Chen, Yan; Chen, Jinquan; Xu, Jianhua

2016-06-20

In this paper, we report a pyridinium salt "turn-on" fluorescent probe, 4-[2-(4-Dimethylamino-phenyl)-vinyl]-1-methylpyridinium iodide (p-DASPMI), and applied its time-resolved fluorescence (TRF) to monitor the protein conformational changes. Both the fluorescence lifetime and quantum yield (QY) of p-DASPMI were increased about two orders of magnitude after binding to the protein bovine serum albumin (BSA). The free p-DASPMI in solution presents an ultrashort fluorescence lifetime (12.4 ps), thus it does not interfere the detection of bound p-DASPMI which has nanosecond fluorescence lifetime. Decay-associated spectra (DAS) show that p-DASPMI molecules bind to subdomains IIA and IIIA of BSA. The TRF decay profiles of p-DASPMI can be described by multi-exponential decay function ([Formula: see text]), and the obtained parameters, such as lifetimes ([Formula: see text]), fractional amplitudes ([Formula: see text]), and fractional intensities ([Formula: see text]), may be used to deduce the conformational changes of BSA. The pH and Cu 2+ induced conformational changes of BSA were investigated through the TRF of p-DASPMI. The results show that the p-DASPMI is a candidate fluorescent probe in studying the conformational changes of proteins through TRF spectroscopy and microscopy in the visible range. © The Author(s) 2016.

Combination of confocal principle and aperture stop separation improves suppression of crystalline lens fluorescence in an eye model

PubMed Central

Klemm, Matthias; Blum, Johannes; Link, Dietmar; Hammer, Martin; Haueisen, Jens; Schweitzer, Dietrich

2016-01-01

Fluorescence lifetime imaging ophthalmoscopy (FLIO) is a new technique to detect changes in the human retina. The autofluorescence decay over time, generated by endogenous fluorophores, is measured in vivo. The strong autofluorescence of the crystalline lens, however, superimposes the intensity decay of the retina fluorescence, as the confocal principle is not able to suppress it sufficiently. Thus, the crystalline lens autofluorescence causes artifacts in the retinal fluorescence lifetimes determined from the intensity decays. Here, we present a new technique to suppress the autofluorescence of the crystalline lens by introducing an annular stop into the detection light path, which we call Schweitzer’s principle. The efficacy of annular stops with an outer diameter of 7 mm and inner diameters of 1 to 5 mm are analyzed in an experimental setup using a model eye based on fluorescent dyes. Compared to the confocal principle, Schweitzer’s principle with an inner diameter of 3 mm is able to reduce the simulated crystalline lens fluorescence to 4%, while 42% of the simulated retina fluorescence is preserved. Thus, we recommend the implementation of Schweitzer’s principle in scanning laser ophthalmoscopes used for fundus autofluorescence measurements, especially the FLIO device, for improved image quality. PMID:27699092

Ultrafast magnetodynamics with free-electron lasers

NASA Astrophysics Data System (ADS)

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

2018-02-01

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

Ultra-fast scintillation properties of β-Ga2O3 single crystals grown by Floating Zone method

NASA Astrophysics Data System (ADS)

He, Nuotian; Tang, Huili; Liu, Bo; Zhu, Zhichao; Li, Qiu; Guo, Chao; Gu, Mu; Xu, Jun; Liu, Jinliang; Xu, Mengxuan; Chen, Liang; Ouyang, Xiaoping

2018-04-01

In this investigation, β-Ga2O3 single crystals were grown by the Floating Zone method. At room temperature, the X-ray excited emission spectrum includes ultraviolet and blue emission bands. The scintillation light output is comparable to the commercial BGO scintillator. The scintillation decay times are composed of the dominant ultra-fast component of 0.368 ns and a small amount of slightly slow components of 8.2 and 182 ns. Such fast component is superior to most commercial inorganic scintillators. In contrast to most semiconductor crystals prepared by solution method such as ZnO, β-Ga2O3 single crystals can be grown by traditional melt-growth method. Thus we can easily obtain large bulk crystals and mass production.

Indirect excitation of ultrafast demagnetization

DOE PAGES

Vodungbo, Boris; Tudu, Bahrati; Perron, Jonathan; ...

2016-01-06

Does the excitation of ultrafast magnetization require direct interaction between the photons of the optical pump pulse and the magnetic layer? Here, we demonstrate unambiguously that this is not the case. For this we have studied the magnetization dynamics of a ferromagnetic cobalt/palladium multilayer capped by an IR-opaque aluminum layer. Upon excitation with an intense femtosecond-short IR laser pulse, the film exhibits the classical ultrafast demagnetization phenomenon although only a negligible number of IR photons penetrate the aluminum layer. In comparison with an uncapped cobalt/palladium reference film, the initial demagnetization of the capped film occurs with a delayed onset andmore » at a slower rate. Both observations are qualitatively in line with energy transport from the aluminum layer into the underlying magnetic film by the excited, hot electrons of the aluminum film. As a result, our data thus confirm recent theoretical predictions.« less

Indirect excitation of ultrafast demagnetization

PubMed Central

Vodungbo, Boris; Tudu, Bahrati; Perron, Jonathan; Delaunay, Renaud; Müller, Leonard; Berntsen, Magnus H.; Grübel, Gerhard; Malinowski, Grégory; Weier, Christian; Gautier, Julien; Lambert, Guillaume; Zeitoun, Philippe; Gutt, Christian; Jal, Emmanuelle; Reid, Alexander H.; Granitzka, Patrick W.; Jaouen, Nicolas; Dakovski, Georgi L.; Moeller, Stefan; Minitti, Michael P.; Mitra, Ankush; Carron, Sebastian; Pfau, Bastian; von Korff Schmising, Clemens; Schneider, Michael; Eisebitt, Stefan; Lüning, Jan

2016-01-01

Does the excitation of ultrafast magnetization require direct interaction between the photons of the optical pump pulse and the magnetic layer? Here, we demonstrate unambiguously that this is not the case. For this we have studied the magnetization dynamics of a ferromagnetic cobalt/palladium multilayer capped by an IR-opaque aluminum layer. Upon excitation with an intense femtosecond-short IR laser pulse, the film exhibits the classical ultrafast demagnetization phenomenon although only a negligible number of IR photons penetrate the aluminum layer. In comparison with an uncapped cobalt/palladium reference film, the initial demagnetization of the capped film occurs with a delayed onset and at a slower rate. Both observations are qualitatively in line with energy transport from the aluminum layer into the underlying magnetic film by the excited, hot electrons of the aluminum film. Our data thus confirm recent theoretical predictions. PMID:26733106

Detection of decay in fresh-cut lettuce using hyperspectral imaging and chlorophyll fluorescence imaging

USDA-ARS?s Scientific Manuscript database

Fresh-cut lettuce sold in modified atmosphere packaging (MAP) is a desirable, but highly perishable product. Decay of tissue can start a few days after processing and may be difficult to detect by quick visual observation. A system for early detection of decay and gradual evaluation of its progress ...

WS2 mode-locked ultrafast fiber laser

PubMed Central

Mao, Dong; Wang, Yadong; Ma, Chaojie; Han, Lei; Jiang, Biqiang; Gan, Xuetao; Hua, Shijia; Zhang, Wending; Mei, Ting; Zhao, Jianlin

2015-01-01

Graphene-like two dimensional materials, such as WS2 and MoS2, are highly anisotropic layered compounds that have attracted growing interest from basic research to practical applications. Similar with MoS2, few-layer WS2 has remarkable physical properties. Here, we demonstrate for the first time that WS2 nanosheets exhibit ultrafast nonlinear saturable absorption property and high optical damage threshold. Soliton mode-locking operations are achieved separately in an erbium-doped fiber laser using two types of WS2-based saturable absorbers, one of which is fabricated by depositing WS2 nanosheets on a D-shaped fiber, while the other is synthesized by mixing WS2 solution with polyvinyl alcohol, and then evaporating them on a substrate. At the maximum pump power of 600 mW, two saturable absorbers can work stably at mode-locking state without damage, indicating that few-layer WS2 is a promising high-power flexible saturable absorber for ultrafast optics. Numerous applications may benefit from the ultrafast nonlinear features of WS2 nanosheets, such as high-power pulsed laser, materials processing, and frequency comb spectroscopy. PMID:25608729

Ultrafast spin exchange-coupling torque via photo-excited charge-transfer processes

DOE PAGES

Ma, X.; Fang, F.; Li, Q.; ...

2015-10-28

In this study, optical control of spin is of central importance in the research of ultrafast spintronic devices utilizing spin dynamics at short time scales. Recently developed optical approaches such as ultrafast demagnetization, spin-transfer and spin-orbit torques open new pathways to manipulate spin through its interaction with photon, orbit, charge or phonon. However, these processes are limited by either the long thermal recovery time or the low-temperature requirement. Here we experimentally demonstrate ultrafast coherent spin precession via optical charge-transfer processes in the exchange-coupled Fe/CoO system at room temperature. The efficiency of spin precession excitation is significantly higher and the recoverymore » time of the exchange-coupling torque is much shorter than for the demagnetization procedure, which is desirable for fast switching. The exchange coupling is a key issue in spin valves and tunnelling junctions, and hence our findings will help promote the development of exchange-coupled device concepts for ultrafast coherent spin manipulation.« less

Ultrafast Ultrasound Imaging Using Combined Transmissions With Cross-Coherence-Based Reconstruction.

PubMed

Zhang, Yang; Guo, Yuexin; Lee, Wei-Ning

2018-02-01

Plane-wave-based ultrafast imaging has become the prevalent technique for non-conventional ultrasound imaging. The image quality, especially in terms of the suppression of artifacts, is generally compromised by reducing the number of transmissions for a higher frame rate. We hereby propose a new ultrafast imaging framework that reduces not only the side lobe artifacts but also the axial lobe artifacts using combined transmissions with a new coherence-based factor. The results from simulations, in vitro wire phantoms, the ex vivo porcine artery, and the in vivo porcine heart show that our proposed methodology greatly reduced the axial lobe artifact by 25±5 dB compared with coherent plane-wave compounding (CPWC), which was considered as the ultrafast imaging standard, and suppressed side lobe artifacts by 15 ± 5 dB compared with CPWC and coherent spherical-wave compounding. The reduction of artifacts in our proposed ultrafast imaging framework led to a better boundary delineation of soft tissues than CPWC.

Phonon-Assisted Ultrafast Charge Transfer at van der Waals Heterostructure Interface.

PubMed

Zheng, Qijing; Saidi, Wissam A; Xie, Yu; Lan, Zhenggang; Prezhdo, Oleg V; Petek, Hrvoje; Zhao, Jin

2017-10-11

The van der Waals (vdW) interfaces of two-dimensional (2D) semiconductor are central to new device concepts and emerging technologies in light-electricity transduction where the efficient charge separation is a key factor. Contrary to general expectation, efficient electron-hole separation can occur in vertically stacked transition-metal dichalcogenide heterostructure bilayers through ultrafast charge transfer between the neighboring layers despite their weak vdW bonding. In this report, we show by ab initio nonadiabatic molecular dynamics calculations, that instead of direct tunneling, the ultrafast interlayer hole transfer is strongly promoted by an adiabatic mechanism through phonon excitation occurring on 20 fs, which is in good agreement with the experiment. The atomic level picture of the phonon-assisted ultrafast mechanism revealed in our study is valuable both for the fundamental understanding of ultrafast charge carrier dynamics at vdW heterointerfaces as well as for the design of novel quasi-2D devices for optoelectronic and photovoltaic applications.

Ultrafast Nanoimaging of the Photoinduced Phase Transition Dynamics in VO2.

PubMed

Dönges, Sven A; Khatib, Omar; O'Callahan, Brian T; Atkin, Joanna M; Park, Jae Hyung; Cobden, David; Raschke, Markus B

2016-05-11

Many phase transitions in correlated matter exhibit spatial inhomogeneities with expected yet unexplored effects on the associated ultrafast dynamics. Here we demonstrate the combination of ultrafast nondegenerate pump-probe spectroscopy with far from equilibrium excitation, and scattering scanning near-field optical microscopy (s-SNOM) for ultrafast nanoimaging. In a femtosecond near-field near-IR (NIR) pump and mid-IR (MIR) probe study, we investigate the photoinduced insulator-to-metal (IMT) transition in nominally homogeneous VO2 microcrystals. With pump fluences as high as 5 mJ/cm(2), we can reach three distinct excitation regimes. We observe a spatial heterogeneity on ∼50-100 nm length scales in the fluence-dependent IMT dynamics ranging from <100 fs to ∼1 ps. These results suggest a high sensitivity of the IMT with respect to small local variations in strain, doping, or defects that are difficult to discern microscopically. We provide a perspective with the distinct requirements and considerations of ultrafast spatiotemporal nanoimaging of phase transitions in quantum materials.

Redox Conditions Affect Ultrafast Exciton Transport in Photosynthetic Pigment-Protein Complexes.

PubMed

Allodi, Marco A; Otto, John P; Sohail, Sara H; Saer, Rafael G; Wood, Ryan E; Rolczynski, Brian S; Massey, Sara C; Ting, Po-Chieh; Blankenship, Robert E; Engel, Gregory S

2018-01-04

Pigment-protein complexes in photosynthetic antennae can suffer oxidative damage from reactive oxygen species generated during solar light harvesting. How the redox environment of a pigment-protein complex affects energy transport on the ultrafast light-harvesting time scale remains poorly understood. Using two-dimensional electronic spectroscopy, we observe differences in femtosecond energy-transfer processes in the Fenna-Matthews-Olson (FMO) antenna complex under different redox conditions. We attribute these differences in the ultrafast dynamics to changes to the system-bath coupling around specific chromophores, and we identify a highly conserved tyrosine/tryptophan chain near the chromophores showing the largest changes. We discuss how the mechanism of tyrosine/tryptophan chain oxidation may contribute to these differences in ultrafast dynamics that can moderate energy transfer to downstream complexes where reactive oxygen species are formed. These results highlight the importance of redox conditions on the ultrafast transport of energy in photosynthesis. Tailoring the redox environment may enable energy transport engineering in synthetic light-harvesting systems.

Ultrafast spin exchange-coupling torque via photo-excited charge-transfer processes

NASA Astrophysics Data System (ADS)

Ma, X.; Fang, F.; Li, Q.; Zhu, J.; Yang, Y.; Wu, Y. Z.; Zhao, H. B.; Lüpke, G.

2015-10-01

Optical control of spin is of central importance in the research of ultrafast spintronic devices utilizing spin dynamics at short time scales. Recently developed optical approaches such as ultrafast demagnetization, spin-transfer and spin-orbit torques open new pathways to manipulate spin through its interaction with photon, orbit, charge or phonon. However, these processes are limited by either the long thermal recovery time or the low-temperature requirement. Here we experimentally demonstrate ultrafast coherent spin precession via optical charge-transfer processes in the exchange-coupled Fe/CoO system at room temperature. The efficiency of spin precession excitation is significantly higher and the recovery time of the exchange-coupling torque is much shorter than for the demagnetization procedure, which is desirable for fast switching. The exchange coupling is a key issue in spin valves and tunnelling junctions, and hence our findings will help promote the development of exchange-coupled device concepts for ultrafast coherent spin manipulation.

The nature of multiphoton fluorescence from red blood cells

NASA Astrophysics Data System (ADS)

Saytashev, Ilyas; Murphy, Michael; Osseiran, Sam; Spence, Dana M.; Evans, Conor L.; Dantus, Marcos

2016-03-01

We report on the nature of multiphoton excited fluorescence observed from human erythrocytes (red blood cells RBC's) and their "ghosts" following 800nm sub-15 fs excitation. The detected optical signal is assigned as two-photon excited fluorescence from hemoglobin. Our findings are supported by wavelength-resolved fluorescence lifetime decay measurements using time-correlated single photon counting system from RBC's, their ghosts as well as in vitro samples of various fluorophores including riboflavin, NADH, NAD(P)H, hemoglobin. We find that low-energy and short-duration pulses allow two-photon imaging of RBC's, but longer more intense pulses lead to their destruction.

Synchronous fluorescence spectroscopic study of solvatochromic curcumin dye

NASA Astrophysics Data System (ADS)

Patra, Digambara; Barakat, Christelle

2011-09-01

Curcumin, the main yellow bioactive component of turmeric, has recently acquired attention by chemists due its wide range of potential biological applications as an antioxidant, an anti-inflammatory, and an anti-carcinogenic agent. This molecule fluoresces weakly and poorly soluble in water. In this detailed study of curcumin in thirteen different solvents, both the absorption and fluorescence spectra of curcumin was found to be broad, however, a narrower and simple synchronous fluorescence spectrum of curcumin was obtained at Δ λ = 10-20 nm. Lippert-Mataga plot of curcumin in different solvents illustrated two sets of linearity which is consistent with the plot of Stokes' shift vs. the ET30. When Stokes's shift in wavenumber scale was replaced by synchronous fluorescence maximum in nanometer scale, the solvent polarity dependency measured by λSFSmax vs. Lippert-Mataga plot or ET30 values offered similar trends as measured via Stokes' shift for protic and aprotic solvents for curcumin. Better linear correlation of λSFSmax vs. π* scale of solvent polarity was found compared to λabsmax or λemmax or Stokes' shift measurements. In Stokes' shift measurement both absorption/excitation as well as emission (fluorescence) spectra are required to compute the Stokes' shift in wavenumber scale, but measurement could be done in a very fast and simple way by taking a single scan of SFS avoiding calculation and obtain information about polarity of the solvent. Curcumin decay properties in all the solvents could be fitted well to a double-exponential decay function.

Synchronous fluorescence spectroscopic study of solvatochromic curcumin dye.

PubMed

Patra, Digambara; Barakat, Christelle

2011-09-01

Curcumin, the main yellow bioactive component of turmeric, has recently acquired attention by chemists due its wide range of potential biological applications as an antioxidant, an anti-inflammatory, and an anti-carcinogenic agent. This molecule fluoresces weakly and poorly soluble in water. In this detailed study of curcumin in thirteen different solvents, both the absorption and fluorescence spectra of curcumin was found to be broad, however, a narrower and simple synchronous fluorescence spectrum of curcumin was obtained at Δλ=10-20 nm. Lippert-Mataga plot of curcumin in different solvents illustrated two sets of linearity which is consistent with the plot of Stokes' shift vs. the ET30. When Stokes's shift in wavenumber scale was replaced by synchronous fluorescence maximum in nanometer scale, the solvent polarity dependency measured by λSFSmax vs. Lippert-Mataga plot or ET30 values offered similar trends as measured via Stokes' shift for protic and aprotic solvents for curcumin. Better linear correlation of λSFSmax vs. π* scale of solvent polarity was found compared to λabsmax or λemmax or Stokes' shift measurements. In Stokes' shift measurement both absorption/excitation as well as emission (fluorescence) spectra are required to compute the Stokes' shift in wavenumber scale, but measurement could be done in a very fast and simple way by taking a single scan of SFS avoiding calculation and obtain information about polarity of the solvent. Curcumin decay properties in all the solvents could be fitted well to a double-exponential decay function. Copyright © 2011 Elsevier B.V. All rights reserved.

Ultrafast Gap Dynamics and Electronic Interactions in a Photoexcited Cuprate Superconductor

DOE PAGES

Parham, S.; Li, H.; Nummy, T. J.; ...

2017-10-20

We perform time- and angle-resolved photoemission spectroscopy (trARPES) on optimally doped Bi 2Sr 2CaCu 2O 8+δ (BSCCO-2212) using sufficient energy resolution (9 meV) to resolve the k-dependent near-nodal gap structure on time scales where the concept of an electronic pseudotemperature is a useful quantity, i.e., after electronic thermalization has occurred. We study the ultrafast evolution of this gap structure, uncovering a very rich landscape of decay rates as a function of angle, temperature, and energy. We explicitly focus on the quasiparticle states at the gap edge as well as on the spectral weight inside the gap that “fills” the gap—understoodmore » as an interaction, or self-energy effect—and we also make high resolution measurements of the nodal states, enabling a direct and accurate measurement of the electronic temperature (or pseudotemperature) of the electrons in the system. Rather than the standard method of interpreting these results using individual quasiparticle scattering rates that vary significantly as a function of angle, temperature, and energy, we show that the entire landscape of relaxations can be understood by modeling the system as following a nonequilibrium, electronic pseudotemperature that controls all electrons in the zone. Furthermore, this model has zero free parameters, as we obtain the crucial information of the SC gap Δ and the gap-filling strength Γ TDoS by connecting to static ARPES measurements. The quantitative and qualitative agreement between data and model suggests that the critical parameters and interactions of the system, including the pairing interactions, follow parametrically from the electronic pseudotemperature. In conclusion, we expect that this concept will be relevant for understanding the ultrafast response of a great variety of electronic materials, even though the electronic pseudotemperature may not be directly measurable.« less

Ultrafast Gap Dynamics and Electronic Interactions in a Photoexcited Cuprate Superconductor

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

Parham, S.; Li, H.; Nummy, T. J.

We perform time- and angle-resolved photoemission spectroscopy (trARPES) on optimally doped Bi 2Sr 2CaCu 2O 8+δ (BSCCO-2212) using sufficient energy resolution (9 meV) to resolve the k-dependent near-nodal gap structure on time scales where the concept of an electronic pseudotemperature is a useful quantity, i.e., after electronic thermalization has occurred. We study the ultrafast evolution of this gap structure, uncovering a very rich landscape of decay rates as a function of angle, temperature, and energy. We explicitly focus on the quasiparticle states at the gap edge as well as on the spectral weight inside the gap that “fills” the gap—understoodmore » as an interaction, or self-energy effect—and we also make high resolution measurements of the nodal states, enabling a direct and accurate measurement of the electronic temperature (or pseudotemperature) of the electrons in the system. Rather than the standard method of interpreting these results using individual quasiparticle scattering rates that vary significantly as a function of angle, temperature, and energy, we show that the entire landscape of relaxations can be understood by modeling the system as following a nonequilibrium, electronic pseudotemperature that controls all electrons in the zone. Furthermore, this model has zero free parameters, as we obtain the crucial information of the SC gap Δ and the gap-filling strength Γ TDoS by connecting to static ARPES measurements. The quantitative and qualitative agreement between data and model suggests that the critical parameters and interactions of the system, including the pairing interactions, follow parametrically from the electronic pseudotemperature. In conclusion, we expect that this concept will be relevant for understanding the ultrafast response of a great variety of electronic materials, even though the electronic pseudotemperature may not be directly measurable.« less

Ultrafast excited-state deactivation of 9-methylhypoxanthine in aqueous solution: A QM/MM MD study.

PubMed

Guo, Xugeng; Yuan, Huijuan; An, Beibei; Zhu, Qiuling; Zhang, Jinglai

2016-04-21

Photoinduced ultrafast non-adiabatic decay of 9-methylhypoxanthine (9MHPX) in aqueous solution was investigated by ab initio surface-hopping dynamics calculations using a combined quantum mechanical/molecular mechanical approach. The absorption spectra of 9MHPX in aqueous solution were also explored by the hybrid cluster-continuum model at the level of time-dependent density functional theory along with the polarizable continuum model (PCM). The static electronic-structure calculations indicate that the absorption spectra of 9MHPX simulated by TD-B3LYP/PCM and TD-X3LYP/PCM can reproduce very well the experimental findings, with the accuracy of about 0.20 eV. According to dynamics simulations, irradiation of 9MHPX populates the bright excited singlet S1 state, which may undergo an ultrafast non-radiative deactivation to the S0 state. The lifetime of the S1 state of 9MHPX in aqueous solution is predicted to be 115.6 fs, slightly longer than that in the gas phase (88.8 fs), suggesting that the solventwater has no significant influence on the excited-state lifetime of 9MHPX. Such a behavior in 9MHPX is distinctly different from its parent hypoxanthine keto-N9H tautomer in which the excited-state lifetime of the latter in watersolution was remarkably enhanced as compared to the gas phase. The significant difference of the photodynamical behaviors between 9MHPX and keto-N9H can be ascribed to their different hydrogen bond environment in aqueous solution.

Ultrafast Graphene Photonics and Optoelectronics

DTIC Science & Technology

2017-04-14

SUBJECT TERMS Graphene, Ultrafast Optical Processin, Terahertz Electronics ; 16. SECURITY CLASSIFICATION OF: 17. LIMITATION OF ABSTRACT SAR 18...Rep, (2016)) Fig. 4. (a) Images of scanning electron microscope for 1D and 2D gratings. (b) Ratio of the real part of the transmitted field

WE-B-210-02: The Advent of Ultrafast Imaging in Biomedical Ultrasound

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

Tanter, M.

In the last fifteen years, the introduction of plane or diverging wave transmissions rather than line by line scanning focused beams has broken the conventional barriers of ultrasound imaging. By using such large field of view transmissions, the frame rate reaches the theoretical limit of physics dictated by the ultrasound speed and an ultrasonic map can be provided typically in tens of micro-seconds (several thousands of frames per second). Interestingly, this leap in frame rate is not only a technological breakthrough but it permits the advent of completely new ultrasound imaging modes, including shear wave elastography, electromechanical wave imaging, ultrafastmore » doppler, ultrafast contrast imaging, and even functional ultrasound imaging of brain activity (fUltrasound) introducing Ultrasound as an emerging full-fledged neuroimaging modality. At ultrafast frame rates, it becomes possible to track in real time the transient vibrations – known as shear waves – propagating through organs. Such “human body seismology” provides quantitative maps of local tissue stiffness whose added value for diagnosis has been recently demonstrated in many fields of radiology (breast, prostate and liver cancer, cardiovascular imaging, …). Today, Supersonic Imagine company is commercializing the first clinical ultrafast ultrasound scanner, Aixplorer with real time Shear Wave Elastography. This is the first example of an ultrafast Ultrasound approach surpassing the research phase and now widely spread in the clinical medical ultrasound community with an installed base of more than 1000 Aixplorer systems in 54 countries worldwide. For blood flow imaging, ultrafast Doppler permits high-precision characterization of complex vascular and cardiac flows. It also gives ultrasound the ability to detect very subtle blood flow in very small vessels. In the brain, such ultrasensitive Doppler paves the way for fUltrasound (functional ultrasound imaging) of brain activity with

Femtosecond x-ray scattering study of ultrafast photoinduced structural dynamics in solvated [ Co ( terpy ) 2 ] 2 +

DOE PAGES

Biasin, Elisa; van Driel, Tim Brandt; Kjær, Kasper S.; ...

2016-06-30

Here, we study the structural dynamics of photoexcited [Co(terpy) 2] 2+ in an aqueous solution with ultrafast x-ray diffuse scattering experiments conducted at the Linac Coherent Light Source. Through direct comparisons with density functional theory calculations, our analysis shows that the photoexcitation event leads to elongation of the Co-N bonds, followed by coherent Co-N bond length oscillations arising from the impulsive excitation of a vibrational mode dominated by the symmetrical stretch of all six Co-N bonds. This mode has a period of 0.33 ps and decays on a subpicosecond time scale. We find that the equilibrium bond-elongated structure of themore » high spin state is established on a single-picosecond time scale and that this state has a lifetime of ~7 ps.« less

Ultrafast Electron Diffraction: How It Works

ScienceCinema

None

2018-01-16

A new technology at SLAC uses high-energy electrons to unravel motions in materials that are faster than a tenth of a trillionth of a second, opening up new research opportunities in ultrafast science.

Ultrafast Electron Diffraction: How It Works

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

None

2015-08-05

A new technology at SLAC uses high-energy electrons to unravel motions in materials that are faster than a tenth of a trillionth of a second, opening up new research opportunities in ultrafast science.

Ultrafast dynamics of differently aligned COOH-DTE-BODIPY conjugates linked to the surface of TiO2

NASA Astrophysics Data System (ADS)

Schweighöfer, Felix; Yüce, Imanuel; Dworak, Lars; Guo, Peng; Zastrow, Marc; Mayer, Kerstin; Barta, Christoph; Liebmann, Diana; Ziebart, Nandor; Rück-Braun, Karola; Wachtveitl, Josef

2018-02-01

The photoinduced dynamics of two DTE-BODIPY conjugates A, B with carboxylic acid anchoring groups coupled to the surface of TiO2 were studied by ultrafast transient absorption spectroscopy. For compound A, with an orthogonal orientation of the BODIPY chromophore and the photoswitchable DTE unit, a charge separated state could not be reliably detected. Nevertheless, besides the energy transfer from the BODIPY to the ring-closed DTE-c, indications for an electron transfer reaction were found by analyzing fluorescence quenching on TiO2 in steady state fluorescence measurements. For compound B with a parallel orientation of chromophore and photoswitch, a charge separated state was conclusively identified for the coupled dyad (TiO2) via the observation of a positive absorption signal (at λ pr  >  610 nm) at later delay times. An electron transfer rate of 7  ×  1010 s-1 can be extracted, indicating slower processes in the dyads in comparison to previously published electron transfer reactions of DTE compounds coupled to TiO2.

Ultrafast dynamics of differently aligned COOH-DTE-BODIPY conjugates linked to the surface of TiO2.

PubMed

Schweighöfer, Felix; Yüce, Imanuel; Dworak, Lars; Guo, Peng; Zastrow, Marc; Mayer, Kerstin; Barta, Christoph; Liebmann, Diana; Ziebart, Nandor; Rück-Braun, Karola; Wachtveitl, Josef

2018-01-05

The photoinduced dynamics of two DTE-BODIPY conjugates A, B with carboxylic acid anchoring groups coupled to the surface of TiO 2 were studied by ultrafast transient absorption spectroscopy. For compound A, with an orthogonal orientation of the BODIPY chromophore and the photoswitchable DTE unit, a charge separated state could not be reliably detected. Nevertheless, besides the energy transfer from the BODIPY to the ring-closed DTE-c, indications for an electron transfer reaction were found by analyzing fluorescence quenching on TiO 2 in steady state fluorescence measurements. For compound B with a parallel orientation of chromophore and photoswitch, a charge separated state was conclusively identified for the coupled dyad (TiO 2 ) via the observation of a positive absorption signal (at λ pr   >  610 nm) at later delay times. An electron transfer rate of 7  ×  10 10 s -1 can be extracted, indicating slower processes in the dyads in comparison to previously published electron transfer reactions of DTE compounds coupled to TiO 2 .

Differentiation of ocular fundus fluorophores by fluorescence lifetime imaging using multiple excitation and emission wavelengths

NASA Astrophysics Data System (ADS)

Hammer, M.; Schweitzer, D.; Schenke, S.; Becker, W.; Bergmann, A.

2006-10-01

Ocular fundus autofluorescence imaging has been introduced into clinical diagnostics recently. It is in use for the observation of the age pigment lipofuscin, a precursor of age - related macular degeneration (AMD). But other fluorophores may be of interest too: The redox pair FAD - FADH II provides information on the retinal energy metabolism, advanced glycation end products (AGE) indicate protein glycation associated with pathologic processes in diabetes as well as AMD, and alterations in the fluorescence of collagen and elastin in connective tissue give us the opportunity to observe fibrosis by fluorescence imaging. This, however, needs techniques able to differentiate particular fluorophores despite limited permissible ocular exposure as well as excitation wavelength (limited by the transmission of the human ocular lens to >400 nm). We present an ophthalmic laser scanning system (SLO), equipped with picosecond laser diodes (FWHM 100 ps, 446 nm or 468 nm respectively) and time correlated single photon counting (TCSPC) in two emission bands (500 - 560 nm and 560 - 700 nm). The decays were fitted by a bi-exponential model. Fluorescence spectra were measured by a fluorescence spectrometer fluorolog. Upon excitation at 446 nm, the fluorescence of AGE, FAD, and lipofuscin were found to peak at 503 nm, 525 nm, and 600 nm respectively. Accordingly, the statistical distribution of the fluorescence decay times was found to depend on the different excitation wavelengths and emission bands used. The use of multiple excitation and emission wavelengths in conjunction with fluorescence lifetime imaging allows us to discriminate between intrinsic fluorophores of the ocular fundus. Taken together with our knowledge on the anatomical structure of the fundus, these findings suggest an association of the short, middle and long fluorescence decay time to the retinal pigment epithelium, the retina, and connective tissue respectively.

Fluorescence kinetics of emission from a small finite volume of a biological system

NASA Astrophysics Data System (ADS)

Dagen, A. J.; Alfano, R. R.; Zilinskas, B. A.; Swenberg, C. E.

1985-07-01

The fluorescence decay, apparent quantum yield and transmission from chromophores constrained to a microscopic volume using a single picosecond laser excitation were measured as a function of incident intensity. The β subunit of phycoeryhthrin aggregate isolated from the photosynthetic antenna system of Nostoc sp. was selected since it contains only four chromophores in a volume of less than 5.6×10 4 Å 3. The non-exponential fluorescence decay profiles were intensity independent for the intensity range studied (5 × 10 13 - 2 × 10 15 photon cm -2 per pulse). The apparent decrease in the relative fluorescence quantum yield and increase of the relative transmission with increasing excitation intensity is attributed to the combined effects of ground state depletion and upper excited state absorption. Evidence suggests that exciton annihilation is absent within isolated β subunits.

Development of Functional Fluorescent Molecular Probes for the Detection of Biological Substances

PubMed Central

Suzuki, Yoshio; Yokoyama, Kenji

2015-01-01

This review is confined to sensors that use fluorescence to transmit biochemical information. Fluorescence is, by far, the most frequently exploited phenomenon for chemical sensors and biosensors. Parameters that define the application of such sensors include intensity, decay time, anisotropy, quenching efficiency, and luminescence energy transfer. To achieve selective (bio)molecular recognition based on these fluorescence phenomena, various fluorescent elements such as small organic molecules, enzymes, antibodies, and oligonucleotides have been designed and synthesized over the past decades. This review describes the immense variety of fluorescent probes that have been designed for the recognitions of ions, small and large molecules, and their biological applications in terms of intracellular fluorescent imaging techniques. PMID:26095660

Novel flashlamp-based time-resolved fluorescence microscope reduces autofluorescence for 30-fold contrast enhancement in environmental samples

NASA Astrophysics Data System (ADS)

Connally, Russell; Veal, Duncan; Piper, James A.

2003-07-01

The abundance of naturally fluorescing components (autofluorophors) encountered in environmentally sourced samples can greatly hinder the detection and identification of fluorescently labeled target using fluorescence microscopy. Time-resolved fluorescence microscopy (TRFM) is a technique that reduces the effects of autofluorescence through precisely controlled time delays. Lanthanide chelates have fluorescence lifetimes many orders of magnitude greater than typical autofluorophors, and persist in their luminescence long after autofluorescence has ceased. An intense short pulse of (UV) light is used to excite fluorescence in the sample and after a short delay period the longer persisting fluorescence from the chelate is captured with an image-intensified CCD camera. The choice of pulsed excitation source for TRFM has a large impact on the price and performance of the instrument. A flashlamp with a short pulse duration was selected for our instrument because of the high spectral energy in the UV region and short pulse length. However, flash output decays with an approximate lifetime of 18μs and the TRFM requires a long-lived chelate to ensure probe fluorescence is still visible after decay of the flash plasma. We synthesized a recently reported fluorescent chelate (BHHCT) and conjugated it to a monoclonal antibody directed against the water-borne parasite Giardia lamblia. Fluorescence lifetime of the construct was determined to be 339μs +/- 14μs and provided a 45-fold enhancement of labeled Giardia over background using a gate delay of 100μs. Despite the sub-optimal decay characteristics of the light pulse, flashlamps have many advantages compared to optical chopper wheels and modulated lasers. Their low cost, lack of vibration, ease of interface and small footprint are important factors to consider in TRFM design.

Quantitative imaging of disease signatures through radioactive decay signal conversion

PubMed Central

Thorek, Daniel LJ; Ogirala, Anuja; Beattie, Bradley J; Grimm, Jan

2013-01-01

In the era of personalized medicine there is an urgent need for in vivo techniques able to sensitively detect and quantify molecular activities. Sensitive imaging of gamma rays is widely used, but radioactive decay is a physical constant and signal is independent of biological interactions. Here we introduce a framework of novel targeted and activatable probes excited by a nuclear decay-derived signal to identify and measure molecular signatures of disease. This was accomplished utilizing Cerenkov luminescence (CL), the light produced by β-emitting radionuclides such as clinical positron emission tomography (PET) tracers. Disease markers were detected using nanoparticles to produce secondary Cerenkov-induced fluorescence. This approach reduces background signal compared to conventional fluorescence imaging. In addition to information from a PET scan, we demonstrate novel medical utility by quantitatively determining prognostically relevant enzymatic activity. This technique can be applied to monitor other markers and facilitates a shift towards activatable nuclear medicine agents. PMID:24013701

High-fidelity optical reporting of neuronal electrical activity with an ultrafast fluorescent voltage sensor

PubMed Central

St-Pierre, François; Marshall, Jesse D; Yang, Ying; Gong, Yiyang; Schnitzer, Mark J; Lin, Michael Z

2015-01-01

Accurate optical reporting of electrical activity in genetically defined neuronal populations is a long-standing goal in neuroscience. Here we describe Accelerated Sensor of Action Potentials 1 (ASAP1), a novel voltage sensor design in which a circularly permuted green fluorescent protein is inserted within an extracellular loop of a voltage-sensing domain, rendering fluorescence responsive to membrane potential. ASAP1 demonstrates on- and off- kinetics of 2.1 and 2.0 ms, reliably detects single action potentials and subthreshold potential changes, and tracks trains of action potential waveforms up to 200 Hz in single trials. With a favorable combination of brightness, dynamic range, and speed, ASAP1 enables continuous monitoring of membrane potential in neurons at KHz frame rates using standard epifluorescence microscopy. PMID:24755780

Ultra-fast framing camera tube

DOEpatents

Kalibjian, Ralph

1981-01-01

An electronic framing camera tube features focal plane image dissection and synchronized restoration of the dissected electron line images to form two-dimensional framed images. Ultra-fast framing is performed by first streaking a two-dimensional electron image across a narrow slit, thereby dissecting the two-dimensional electron image into sequential electron line images. The dissected electron line images are then restored into a framed image by a restorer deflector operated synchronously with the dissector deflector. The number of framed images on the tube's viewing screen is equal to the number of dissecting slits in the tube. The distinguishing features of this ultra-fast framing camera tube are the focal plane dissecting slits, and the synchronously-operated restorer deflector which restores the dissected electron line images into a two-dimensional framed image. The framing camera tube can produce image frames having high spatial resolution of optical events in the sub-100 picosecond range.

The picosecond structure of ultra-fast rogue waves

NASA Astrophysics Data System (ADS)

Klein, Avi; Shahal, Shir; Masri, Gilad; Duadi, Hamootal; Sulimani, Kfir; Lib, Ohad; Steinberg, Hadar; Kolpakov, Stanislav A.; Fridman, Moti

2018-02-01

We investigated ultrafast rogue waves in fiber lasers and found three different patterns of rogue waves: single- peaks, twin-peaks, and triple-peaks. The statistics of the different patterns as a function of the pump power of the laser reveals that the probability for all rogue waves patterns increase close to the laser threshold. We developed a numerical model which prove that the ultrafast rogue waves patterns result from both the polarization mode dispersion in the fiber and the non-instantaneous nature of the saturable absorber. This discovery reveals that there are three different types of rogue waves in fiber lasers: slow, fast, and ultrafast, which relate to three different time-scales and are governed by three different sets of equations: the laser rate equations, the nonlinear Schrodinger equation, and the saturable absorber equations, accordingly. This discovery is highly important for analyzing rogue waves and other extreme events in fiber lasers and can lead to realizing types of rogue waves which were not possible so far such as triangular rogue waves.

Filter-Based Dispersion-Managed Versatile Ultrafast Fibre Laser

PubMed Central

Peng, Junsong; Boscolo, Sonia

2016-01-01

We present the operation of an ultrafast passively mode-locked fibre laser, in which flexible control of the pulse formation mechanism is readily realised by an in-cavity programmable filter the dispersion and bandwidth of which can be software configured. We show that conventional soliton, dispersion-managed (DM) soliton (stretched-pulse) and dissipative soliton mode-locking regimes can be reliably targeted by changing the filter’s dispersion and bandwidth only, while no changes are made to the physical layout of the laser cavity. Numerical simulations are presented which confirm the different nonlinear pulse evolutions inside the laser cavity. The proposed technique holds great potential for achieving a high degree of control over the dynamics and output of ultrafast fibre lasers, in contrast to the traditional method to control the pulse formation mechanism in a DM fibre laser, which involves manual optimisation of the relative length of fibres with opposite-sign dispersion in the cavity. Our versatile ultrafast fibre laser will be attractive for applications requiring different pulse profiles such as in optical signal processing and optical communications. PMID:27183882

Structure and Dynamics with Ultrafast Electron Microscopes

NASA Astrophysics Data System (ADS)

Siwick, Bradley

In this talk I will describe how combining ultrafast lasers and electron microscopes in novel ways makes it possible to directly `watch' the time-evolving structure of condensed matter, both at the level of atomic-scale structural rearrangements in the unit cell and at the level of a material's nano- microstructure. First, I will briefly describe my group's efforts to develop ultrafast electron diffraction using radio- frequency compressed electron pulses in the 100keV range, a system that rivals the capabilities of xray free electron lasers for diffraction experiments. I will give several examples of the new kinds of information that can be gleaned from such experiments. In vanadium dioxide we have mapped the detailed reorganization of the unit cell during the much debated insulator-metal transition. In particular, we have been able to identify and separate lattice structural changes from valence charge density redistribution in the material on the ultrafast timescale. In doing so we uncovered a previously unreported optically accessible phase/state of vanadium dioxide that has monoclinic crystallography like the insulator, but electronic structure and properties that are more like the rutile metal. We have also combined these dynamic structural measurements with broadband ultrafast spectroscopy to make detailed connections between structure and properties for the photoinduced insulator to metal transition. Second, I will show how dynamic transmission electron microscopy (DTEM) can be used to make direct, real space images of nano-microstructural evolution during laser-induced crystallization of amorphous semiconductors at unprecedented spatio-temporal resolution. This is a remarkably complex process that involves several distinct modes of crystal growth and the development of intricate microstructural patterns on the nanosecond to ten microsecond timescales all of which can be imaged directly with DTEM.

Ultrafast Relaxation Dynamics of Au 38 (SC 2 H 4 Ph) 24 Nanoclusters and Effects of Structural Isomerism

DOE PAGES

Zhou, Meng; Tian, Shubo; Zeng, Chenjie; ...

2016-12-22

Structural isomerism in nanoparticles has recently emerged as a new topic and stimulated research interest because the atomic structures of ultrasmall nanoparticles may have great impact on their fundamental properties and applications. We report the correlation between ultrafast relaxation dynamics and atomic structures of two isomers of thiolate-protected Au 38(SC 2H 4Ph) 24. The bi-icosahedral Au 38 (denoted as Au 38Q) with a Au 23 inner core in its atomic structure shows rapid decay (1.5 ps) followed by nanosecond relaxation to the ground state, whereas its structural isomer (Au 38T) exhibits similar relaxation processes, but the rapid decay is acceleratedmore » by ~50% (1.0 ps). The picosecond relaxations in both cases can be assigned to core–shell charge transfer or electronic rearrangement within the metal core. The acceleration of the fast decay in Au38T is ascribed to its unique core structure, which is made up of a mono-icosahedral Au 13 capped by a Au 12 tri-tetrahedron by sharing two atoms. Interestingly, coherent phonon emissions (25 cm –1 for Au 38Q, 27 and 60 cm –1 for Au 38T) are observed in both isomers with pumping in the NIR region. These results illustrate for the first time the importance of atomic structures in the photophysics of same sized gold nanoclusters.« less

Ultrafast Relaxation Dynamics of Au 38 (SC 2 H 4 Ph) 24 Nanoclusters and Effects of Structural Isomerism

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

Zhou, Meng; Tian, Shubo; Zeng, Chenjie

Structural isomerism in nanoparticles has recently emerged as a new topic and stimulated research interest because the atomic structures of ultrasmall nanoparticles may have great impact on their fundamental properties and applications. We report the correlation between ultrafast relaxation dynamics and atomic structures of two isomers of thiolate-protected Au 38(SC 2H 4Ph) 24. The bi-icosahedral Au 38 (denoted as Au 38Q) with a Au 23 inner core in its atomic structure shows rapid decay (1.5 ps) followed by nanosecond relaxation to the ground state, whereas its structural isomer (Au 38T) exhibits similar relaxation processes, but the rapid decay is acceleratedmore » by ~50% (1.0 ps). The picosecond relaxations in both cases can be assigned to core–shell charge transfer or electronic rearrangement within the metal core. The acceleration of the fast decay in Au38T is ascribed to its unique core structure, which is made up of a mono-icosahedral Au 13 capped by a Au 12 tri-tetrahedron by sharing two atoms. Interestingly, coherent phonon emissions (25 cm –1 for Au 38Q, 27 and 60 cm –1 for Au 38T) are observed in both isomers with pumping in the NIR region. These results illustrate for the first time the importance of atomic structures in the photophysics of same sized gold nanoclusters.« less

Ultrafast dynamics of hard tissue ablation using fs-lasers.

PubMed

Domke, Matthias; Wick, Sebastian; Laible, Maike; Rapp, Stephan; Huber, Heinz P; Sroka, Ronald

2018-05-29

Several studies on hard tissue laser ablation demonstrated that ultrafast lasers enable precise material removal without thermal side effects. Although the principle ablation mechanisms have been thoroughly investigated, there are still open questions regarding the influence of material properties on transient dynamics. In this investigation, we applied pump-probe microscopy to record ablation dynamics of biomaterials with different tensile strengths (dentin, chicken bone, gallstone, kidney stones) at delay times between 1 ps and 10 μs. Transient reflectivity changes, pressure and shock wave velocities, and elastic constants were determined. The result revealed that absorption and excitation show the typical well-known transient behaviour of dielectric materials. We observed for all samples a photomechanical laser ablation process, where ultrafast expansion of the excited volume generates pressure waves leading to fragmentation around the excited region. Additionally, we identified tensile-strength-related differences in the size of ablated craters and ejected particles. The elastic constants derived were in agreement with literature values. In conclusion, pressure-wave-assisted material removal seems to be a general mechanism for hard tissue ablation with ultrafast lasers. This photomechanical process increases ablation efficiency and removes heated material, thus ultrafast laser ablation is of interest for clinical application where heating of the tissue must be avoided. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.

Ultrafast Beam Switching Using Coupled VCSELs

NASA Technical Reports Server (NTRS)

Ning, Cun-Zheng; Goorjian, Peter

2001-01-01

We propose a new approach to performing ultrafast beam switching using two coupled Vertical-Cavity Surface-Emitting Lasers (VCSELs). The strategy is demonstrated by numerical simulation, showing a beam switching of 10 deg at 42 GHz.

Quantitative method to assess caries via fluorescence imaging from the perspective of autofluorescence spectral analysis

NASA Astrophysics Data System (ADS)

Chen, Q. G.; Zhu, H. H.; Xu, Y.; Lin, B.; Chen, H.

2015-08-01

A quantitative method to discriminate caries lesions for a fluorescence imaging system is proposed in this paper. The autofluorescence spectral investigation of 39 teeth samples classified by the International Caries Detection and Assessment System levels was performed at 405 nm excitation. The major differences in the different caries lesions focused on the relative spectral intensity range of 565-750 nm. The spectral parameter, defined as the ratio of wavebands at 565-750 nm to the whole spectral range, was calculated. The image component ratio R/(G + B) of color components was statistically computed by considering the spectral parameters (e.g. autofluorescence, optical filter, and spectral sensitivity) in our fluorescence color imaging system. Results showed that the spectral parameter and image component ratio presented a linear relation. Therefore, the image component ratio was graded as <0.66, 0.66-1.06, 1.06-1.62, and >1.62 to quantitatively classify sound, early decay, established decay, and severe decay tissues, respectively. Finally, the fluorescence images of caries were experimentally obtained, and the corresponding image component ratio distribution was compared with the classification result. A method to determine the numerical grades of caries using a fluorescence imaging system was proposed. This method can be applied to similar imaging systems.

The efficiency of non-photochemical fluorescence quenching by cation radicals in photosystem II reaction centers.

PubMed

Paschenko, V Z; Churin, A A; Gorokhov, V V; Grishanova, N P; Korvatovskii, B N; Maksimov, E G; Mamedov, M D

2016-12-01

In a direct experiment, the rate constants of photochemical k p and non-photochemical k p + quenching of the chlorophyll fluorescence have been determined in spinach photosystem II (PS II) membrane fragments, oxygen-evolving PS II core, as well as manganese-depleted PS II particles using pulse fluorimetry. In the dark-adapted reaction center(s) (RC), the fluorescence decay kinetics of the antenna were measured at low-intensity picosecond pulsed excitation. To create a "closed" P680 + Q A - state, RCs were illuminated by high-intensity actinic flash 8 ns prior to the measuring flash. The obtained data were approximated by the sum of two decaying exponents. It was found that the antennae fluorescence quenching efficiency by the oxidized photoactive pigment of RC P680 + was about 1.5 times higher than that of the neutral P680 state. These results were confirmed by a single-photon counting technique, which allowed to resolve the additional slow component of the fluorescence decay. Slow component was assigned to the charge recombination of P680 + Pheo - in PS II RC. Thus, for the first time, the ratio k p + /k p  ≅ 1.5 was found directly. The mechanism of the higher efficiency of non-photochemical quenching comparing to photochemical quenching is discussed.

Spin-controlled ultrafast vertical-cavity surface-emitting lasers

NASA Astrophysics Data System (ADS)

Höpfner, Henning; Lindemann, Markus; Gerhardt, Nils C.; Hofmann, Martin R.

2014-05-01

Spin-controlled semiconductor lasers are highly attractive spintronic devices providing characteristics superior to their conventional purely charge-based counterparts. In particular, spin-controlled vertical-cavity surface emitting lasers (spin-VCSELs) promise to offer lower thresholds, enhanced emission intensity, spin amplification, full polarization control, chirp control and ultrafast dynamics. Most important, the ability to control and modulate the polarization state of the laser emission with extraordinarily high frequencies is very attractive for many applications like broadband optical communication and ultrafast optical switches. We present a novel concept for ultrafast spin-VCSELs which has the potential to overcome the conventional speed limitation for directly modulated lasers by the relaxation oscillation frequency and to reach modulation frequencies significantly above 100 GHz. The concept is based on the coupled spin-photon dynamics in birefringent micro-cavity lasers. By injecting spin-polarized carriers in the VCSEL, oscillations of the coupled spin-photon system can by induced which lead to oscillations of the polarization state of the laser emission. These oscillations are decoupled from conventional relaxation oscillations of the carrier-photon system and can be much faster than these. Utilizing these polarization oscillations is thus a very promising approach to develop ultrafast spin-VCSELs for high speed optical data communication in the near future. Different aspects of the spin and polarization dynamics, its connection to birefringence and bistability in the cavity, controlled switching of the oscillations, and the limitations of this novel approach will be analysed theoretically and experimentally for spin-polarized VCSELs at room temperature.

Ultrafast coherent excitation of a trapped ion qubit for fast gates and photon frequency qubits.

PubMed

Madsen, M J; Moehring, D L; Maunz, P; Kohn, R N; Duan, L-M; Monroe, C

2006-07-28

We demonstrate ultrafast coherent excitation of an atomic qubit stored in the hyperfine levels of a single trapped cadmium ion. Such ultrafast excitation is crucial for entangling networks of remotely located trapped ions through the interference of photon frequency qubits, and is also a key component for realizing ultrafast quantum gates between Coulomb-coupled ions.

Probing ultrafast proton induced dynamics in transparent dielectrics

NASA Astrophysics Data System (ADS)

Taylor, M.; Coughlan, M.; Nersisyan, G.; Senje, L.; Jung, D.; Currell, F.; Riley, D.; Lewis, C. L. S.; Zepf, M.; Dromey, B.

2018-05-01

A scheme has been developed permitting the spatial and temporal characterisation of ultrafast dynamics induced by laser driven proton bursts in transparent dielectrics. Advantage is taken of the high degree of synchronicity between the proton bursts generated during laser-foil target interactions and the probing laser to provide the basis for streaking of the dynamics. Relaxation times of electrons (<10‑12 s) are measured following swift excitation across the optical band gap for various glass samples. A temporal resolution of <500 fs is achieved demonstrating that these ultrafast dynamics can be characterized on a single-shot basis.

Quantum modeling of ultrafast photoinduced charge separation

NASA Astrophysics Data System (ADS)

Rozzi, Carlo Andrea; Troiani, Filippo; Tavernelli, Ivano

2018-01-01

Phenomena involving electron transfer are ubiquitous in nature, photosynthesis and enzymes or protein activity being prominent examples. Their deep understanding thus represents a mandatory scientific goal. Moreover, controlling the separation of photogenerated charges is a crucial prerequisite in many applicative contexts, including quantum electronics, photo-electrochemical water splitting, photocatalytic dye degradation, and energy conversion. In particular, photoinduced charge separation is the pivotal step driving the storage of sun light into electrical or chemical energy. If properly mastered, these processes may also allow us to achieve a better command of information storage at the nanoscale, as required for the development of molecular electronics, optical switching, or quantum technologies, amongst others. In this Topical Review we survey recent progress in the understanding of ultrafast charge separation from photoexcited states. We report the state-of-the-art of the observation and theoretical description of charge separation phenomena in the ultrafast regime mainly focusing on molecular- and nano-sized solar energy conversion systems. In particular, we examine different proposed mechanisms driving ultrafast charge dynamics, with particular regard to the role of quantum coherence and electron-nuclear coupling, and link experimental observations to theoretical approaches based either on model Hamiltonians or on first principles simulations.

Chirped pulse digital holography for measuring the sequence of ultrafast optical wavefronts

NASA Astrophysics Data System (ADS)

Karasawa, Naoki

2018-04-01

Optical setups for measuring the sequence of ultrafast optical wavefronts using a chirped pulse as a reference wave in digital holography are proposed and analyzed. In this method, multiple ultrafast object pulses are used to probe the temporal evolution of ultrafast phenomena and they are interfered with a chirped reference wave to record a digital hologram. Wavefronts at different times can be reconstructed separately from the recorded hologram when the reference pulse can be treated as a quasi-monochromatic wave during the pulse width of each object pulse. The feasibility of this method is demonstrated by numerical simulation.

3D pulsed laser-triggered high-speed microfluidic fluorescence-activated cell sorter

PubMed Central

Chen, Yue; Wu, Ting-Hsiang; Kung, Yu-Chun; Teitell, Michael A.; Chiou, Pei-Yu

2014-01-01

We report a 3D microfluidic pulsed laser-triggered fluorescence-activated cell sorter capable of sorting at a throughput of 23,000 cells sec−1 with 90% purity in high-purity mode and at a throughput of 45,000 cells sec−1 with 45% purity in enrichment mode in one stage and in a single channel. This performance is realized by exciting laser-induced cavitation bubbles in a 3D PDMS microfluidic channel to generate high-speed liquid jets that deflect detected fluorescent cells and particles focused by 3D sheath flows. The ultrafast switching mechanism (20 μsec complete on-off cycle), small liquid jet perturbation volume, and three-dimensional sheath flow focusing for accurate timing control of fast (1.5 m sec−1) passing cells and particles are three critical factors enabling high-purity sorting at high-throughput in this sorter. PMID:23844418

Inhibition of beta-amyloid aggregation by fluorescent dye labels

NASA Astrophysics Data System (ADS)

Amaro, Mariana; Wellbrock, Thorben; Birch, David J. S.; Rolinski, Olaf J.

2014-02-01

The fluorescence decay of beta-amyloid's (Aβ) intrinsic fluorophore tyrosine has been used for sensing the oligomer formation of dye-labelled Aβ monomers and the results compared with previously studied oligomerization of the non-labelled Aβ peptides. It has been demonstrated that two different sized, covalently bound probes 7-diethylaminocoumarin-3-carbonyl and Hilyte Fluor 488 (HLF), alter the rate and character of oligomerization to different extents. The ability of HLF to inhibit formation of highly ordered structures containing beta-sheets was also shown. The implications of our findings for using fluorescence methods in amyloidosis research are discussed and the advantages of this auto-fluorescence approach highlighted.

Ultrafast electronic relaxation in superheated bismuth

NASA Astrophysics Data System (ADS)

Gamaly, E. G.; Rode, A. V.

2013-01-01

Interaction of moving electrons with vibrating ions in the lattice forms the basis for many physical properties from electrical resistivity and electronic heat capacity to superconductivity. In ultrafast laser interaction with matter the electrons are heated much faster than the electron-ion energy equilibration, leading to a two-temperature state with electron temperature far above that of the lattice. The rate of temperature equilibration is governed by the strength of electron-phonon energy coupling, which is conventionally described by a coupling constant, neglecting the dependence on the electron and lattice temperature. The application of this constant to the observations of fast relaxation rate led to a controversial notion of ‘ultra-fast non-thermal melting’ under extreme electronic excitation. Here we provide theoretical grounds for a strong dependence of the electron-phonon relaxation time on the lattice temperature. We show, by taking proper account of temperature dependence, that the heating and restructuring of the lattice occurs much faster than were predicted on the assumption of a constant, temperature independent energy coupling. We applied the temperature-dependent momentum and energy transfer time to experiments on fs-laser excited bismuth to demonstrate that all the observed ultra-fast transformations of the transient state of bismuth are purely thermal in nature. The developed theory, when applied to ultrafast experiments on bismuth, provides interpretation of the whole variety of transient phase relaxation without the non-thermal melting conjecture.

Pump polarization insensitive and efficient laser-diode pumped Yb:KYW ultrafast oscillator.

PubMed

Wang, Sha; Wang, Yan-Biao; Feng, Guo-Ying; Zhou, Shou-Huan

2016-02-01

We theoretically and experimentally report and evaluate a novel split laser-diode (LD) double-end pumped Yb:KYW ultrafast oscillator aimed at improving the performance of an ultrafast laser. Compared to a conventional unpolarized single-LD end-pumped ultrafast laser system, we improve the laser performance such as absorption efficiency, slope efficiency, cw mode-locking threshold, and output power by this new structure LD-pumped Yb:KYW ultrafast laser. Experiments were carried out with a 1 W output fiber-coupled LD. Experimental results show that the absorption increases from 38.7% to 48.4%, laser slope efficiency increases from 18.3% to 24.2%, cw mode-locking threshold decreases 12.7% from 630 to 550 mW in cw mode-locking threshold, and maximum output-power increases 28.5% from 158.4 to 221.5 mW when we switch the pump scheme from an unpolarized single-end pumping structure to a split LD double-end pumping structure.

Multiplane wave imaging increases signal-to-noise ratio in ultrafast ultrasound imaging.

PubMed

Tiran, Elodie; Deffieux, Thomas; Correia, Mafalda; Maresca, David; Osmanski, Bruno-Felix; Sieu, Lim-Anna; Bergel, Antoine; Cohen, Ivan; Pernot, Mathieu; Tanter, Mickael

2015-11-07

Ultrafast imaging using plane or diverging waves has recently enabled new ultrasound imaging modes with improved sensitivity and very high frame rates. Some of these new imaging modalities include shear wave elastography, ultrafast Doppler, ultrafast contrast-enhanced imaging and functional ultrasound imaging. Even though ultrafast imaging already encounters clinical success, increasing even more its penetration depth and signal-to-noise ratio for dedicated applications would be valuable. Ultrafast imaging relies on the coherent compounding of backscattered echoes resulting from successive tilted plane waves emissions; this produces high-resolution ultrasound images with a trade-off between final frame rate, contrast and resolution. In this work, we introduce multiplane wave imaging, a new method that strongly improves ultrafast images signal-to-noise ratio by virtually increasing the emission signal amplitude without compromising the frame rate. This method relies on the successive transmissions of multiple plane waves with differently coded amplitudes and emission angles in a single transmit event. Data from each single plane wave of increased amplitude can then be obtained, by recombining the received data of successive events with the proper coefficients. The benefits of multiplane wave for B-mode, shear wave elastography and ultrafast Doppler imaging are experimentally demonstrated. Multiplane wave with 4 plane waves emissions yields a 5.8  ±  0.5 dB increase in signal-to-noise ratio and approximately 10 mm in penetration in a calibrated ultrasound phantom (0.7 d MHz(-1) cm(-1)). In shear wave elastography, the same multiplane wave configuration yields a 2.07  ±  0.05 fold reduction of the particle velocity standard deviation and a two-fold reduction of the shear wave velocity maps standard deviation. In functional ultrasound imaging, the mapping of cerebral blood volume results in a 3 to 6 dB increase of the contrast-to-noise ratio in deep

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

NASA Astrophysics Data System (ADS)

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

2018-03-01

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

Tuning ultrafast electron injection dynamics at organic-graphene/metal interfaces.

PubMed

Ravikumar, Abhilash; Kladnik, Gregor; Müller, Moritz; Cossaro, Albano; Bavdek, Gregor; Patera, Laerte L; Sánchez-Portal, Daniel; Venkataraman, Latha; Morgante, Alberto; Brivio, Gian Paolo; Cvetko, Dean; Fratesi, Guido

2018-05-03

We compare the ultrafast charge transfer dynamics of molecules on epitaxial graphene and bilayer graphene grown on Ni(111) interfaces through first principles calculations and X-ray resonant photoemission spectroscopy. We use 4,4'-bipyridine as a prototypical molecule for these explorations as the energy level alignment of core-excited molecular orbitals allows ultrafast injection of electrons from a substrate to a molecule on a femtosecond timescale. We show that the ultrafast injection of electrons from the substrate to the molecule is ∼4 times slower on weakly coupled bilayer graphene than on epitaxial graphene. Through our experiments and calculations, we can attribute this to a difference in the density of states close to the Fermi level between graphene and bilayer graphene. We therefore show how graphene coupling with the substrate influences charge transfer dynamics between organic molecules and graphene interfaces.

Linear ultrafast dynamics of plasmon and magnetic resonances in nanoparticles

NASA Astrophysics Data System (ADS)

Lazzarini, Carlo Maria; Tadzio, Levato; Fitzgerald, Jamie M.; Sánchez-Gil, José A.; Giannini, Vincenzo

2017-12-01

In this study we present an analytical description of the ultrafast localized surface plasmon and magnetic resonance dynamics in a single nanoparticle (Ag or Si), driven by an ultrashort (fs time scale) Gaussian pulse. Three possible scenarios have been found depending on the incident field, i.e., pulse duration much shorter than, similar to, and much longer than the localized surface plasmon resonance (LSPR) lifetime. A rich physics arises for τpulse<τLSPR , even in the linear regime. The surface plasmon dynamics is manifested as (i) a temporal delay of the surface plasmon excitation with regard to the freely propagating pulse and as (ii) a negative exponential tail after the exciting pulse is over. In addition, for sub-fs pulses clear oscillations in the near-field decay have been observed. A similar scenario has been observed considering a nonabsorbing Si sphere. Nanoparticle resonance dynamics may lead to a wealth of new phenomena and applications in nanophotonics such as multipole order resonance interference, pulse-induced delay or temporal shaping on the fs scale, high harmonic generation, attosecond near-field pulse sources, and electron acceleration from metasurface or 3D engineered nanostructures.

Development of Scanning Ultrafast Electron Microscope Capability.

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

Collins, Kimberlee Chiyoko; Talin, Albert Alec; Chandler, David W.

Modern semiconductor devices rely on the transport of minority charge carriers. Direct examination of minority carrier lifetimes in real devices with nanometer-scale features requires a measurement method with simultaneously high spatial and temporal resolutions. Achieving nanometer spatial resolutions at sub-nanosecond temporal resolution is possible with pump-probe methods that utilize electrons as probes. Recently, a stroboscopic scanning electron microscope was developed at Caltech, and used to study carrier transport across a Si p-n junction [ 1 , 2 , 3 ] . In this report, we detail our development of a prototype scanning ultrafast electron microscope system at Sandia National Laboratoriesmore » based on the original Caltech design. This effort represents Sandia's first exploration into ultrafast electron microscopy.« less

Ultra-fast ipsilateral DPOAE adaptation not modulated by attention?

NASA Astrophysics Data System (ADS)

Dalhoff, Ernst; Zelle, Dennis; Gummer, Anthony W.

2018-05-01

Efferent stimulation of outer hair cells is supposed to attenuate cochlear amplification of sound waves and is accompanied by reduced DPOAE amplitudes. Recently, a method using two subsequent f2 pulses during presentation of a longer f1 pulse was introduced to measure fast ipsilateral adaptation effects on separated DPOAE components. Compensating primary-tone onsets for their latencies at the f2-tonotopic place, the average adaptation measured in four normal-hearing subjects was 5.0 dB with a time constant below 5 ms. In the present study, two experiments were performed to determine the origin of this ultra-fast ipsilateral adaptation effect. The first experiment measured ultra-fast ipsilateral adaptation using a two-pulse paradigm at three frequencies in the four subjects, while controlling for visual attention of the subjects. The other experiment also controlled for visual attention, but utilized a sequence of f2 short pulses in the presence of a continuous f1 tone to sample ipsilateral adaptation effects with longer time constants in eight subjects. In the first experiment, no significant change in the ultra-fast adaptation between non-directed attention and visual attention could be detected. In contrast, the second experiment revealed significant changes in the magnitude of the slower ipsilateral adaptation in the visual-attention condition. In conclusion, the lack of an attentional influence indicates that the ultra-fast ipsilateral DPOAE adaptation is not solely mediated by the medial olivocochlear reflex.

Imaging the environment of green fluorescent protein.

PubMed Central

Suhling, Klaus; Siegel, Jan; Phillips, David; French, Paul M W; Lévêque-Fort, Sandrine; Webb, Stephen E D; Davis, Daniel M

2002-01-01

An emerging theme in cell biology is that cell surface receptors need to be considered as part of supramolecular complexes of proteins and lipids facilitating specific receptor conformations and distinct distributions, e.g., at the immunological synapse. Thus, a new goal is to develop bioimaging that not only locates proteins in live cells but can also probe their environment. Such a technique is demonstrated here using fluorescence lifetime imaging of green fluorescent protein (GFP). We first show, by time-correlated single-photon counting, that the fluorescence decay of GFP depends on the local refractive index. This is in agreement with the Strickler Berg formula, relating the Einstein A and B coefficients for absorption and spontaneous emission in molecules. We then quantitatively image, by wide-field time-gated fluorescence lifetime imaging, the refractive index of the environment of GFP. This novel approach paves the way for imaging the biophysical environment of specific GFP-tagged proteins in live cells. PMID:12496126

Cross-phase modulation bandwidth in ultrafast fiber wavelength converters

NASA Astrophysics Data System (ADS)

Luís, Ruben S.; Monteiro, Paulo; Teixeira, António

2006-12-01

We propose a novel analytical model for the characterization of fiber cross-phase modulation (XPM) in ultrafast all-optical fiber wavelength converters, operating at modulation frequencies higher than 1THz. The model is used to compare the XPM frequency limitations of a conventional and a highly nonlinear dispersion shifted fiber (HN-DSF) and a bismuth oxide-based fiber, introducing the XPM bandwidth as a design parameter. It is shown that the HN-DSF presents the highest XPM bandwidth, above 1THz, making it the most appropriate for ultrafast wavelength conversion.

Ultrafast excited-state deactivation of 9-methylhypoxanthine in aqueous solution: A QM/MM MD study

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

Guo, Xugeng, E-mail: xgguo@henu.edu.cn, E-mail: zhangjinglai@henu.edu.cn; Yuan, Huijuan; An, Beibei

Photoinduced ultrafast non-adiabatic decay of 9-methylhypoxanthine (9MHPX) in aqueous solution was investigated by ab initio surface-hopping dynamics calculations using a combined quantum mechanical/molecular mechanical approach. The absorption spectra of 9MHPX in aqueous solution were also explored by the hybrid cluster-continuum model at the level of time-dependent density functional theory along with the polarizable continuum model (PCM). The static electronic-structure calculations indicate that the absorption spectra of 9MHPX simulated by TD-B3LYP/PCM and TD-X3LYP/PCM can reproduce very well the experimental findings, with the accuracy of about 0.20 eV. According to dynamics simulations, irradiation of 9MHPX populates the bright excited singlet S{sub 1}more » state, which may undergo an ultrafast non-radiative deactivation to the S{sub 0} state. The lifetime of the S{sub 1} state of 9MHPX in aqueous solution is predicted to be 115.6 fs, slightly longer than that in the gas phase (88.8 fs), suggesting that the solvent water has no significant influence on the excited-state lifetime of 9MHPX. Such a behavior in 9MHPX is distinctly different from its parent hypoxanthine keto-N9H tautomer in which the excited-state lifetime of the latter in water solution was remarkably enhanced as compared to the gas phase. The significant difference of the photodynamical behaviors between 9MHPX and keto-N9H can be ascribed to their different hydrogen bond environment in aqueous solution.« less

Imaging electronic motions by ultrafast electron diffraction

NASA Astrophysics Data System (ADS)

Shao, Hua-Chieh; Starace, Anthony F.

2017-08-01

Recently ultrafast electron diffraction and microscopy have reached unprecedented temporal resolution, and transient structures with atomic precision have been observed in various reactions. It is anticipated that these extraordinary advances will soon allow direct observation of electronic motions during chemical reactions. We therefore performed a series of theoretical investigations and simulations to investigate the imaging of electronic motions in atoms and molecules by ultrafast electron diffraction. Three prototypical electronic motions were considered for hydrogen atoms. For the case of a breathing mode, the electron density expands and contracts periodically, and we show that the time-resolved scattering intensities reflect such changes of the charge radius. For the case of a wiggling mode, the electron oscillates from one side of the nucleus to the other, and we show that the diffraction images exhibit asymmetric angular distributions. The last case is a hybrid mode that involves both breathing and wiggling motions. Owing to the demonstrated ability of ultrafast electrons to image these motions, we have proposed to image a coherent population transfer in lithium atoms using currently available femtosecond electron pulses. A frequency-swept laser pulse adiabatically drives the valence electron of a lithium atom from the 2s to 2p orbitals, and a time-delayed electron pulse maps such motion. Our simulations show that the diffraction images reflect this motion both in the scattering intensities and the angular distributions.

Femtosecond timing measurement and control using ultrafast organic thin films

NASA Astrophysics Data System (ADS)

Naruse, Makoto; Mitsu, Hiroyuki; Furuki, Makoto; Iwasa, Izumi; Sato, Yasuhiro; Tatsuura, Satoshi; Tian, Minquan

2003-12-01

We show a femtosecond timing measurement and control technique using a squarylium dye J-aggregate film, which is an organic thin film that acts as an ultrafast two-dimensional optical switch. Optical pulse timing is directly mapped to space-domain position on the film, and the large area and ultrafast response offer a femtosecond-resolved, large dynamic range, real-time, multichannel timing measurement capability. A timing fluctuation (jitter, wander, and skew) reduction architecture is presented and experimentally demonstrated.

[Assessment of mitochondrial metabolic oxidative state in living cardiomyocytes with spectrally-resolved fluorescence lifetime spectroscopy of NAD(P)H].

PubMed

Cheng, Ying; Ren, Mingming; Niu, Yanyan; Qiao, Jianhua; Aneba, S; Chorvat, D; Chorvatova, A

2009-12-01

The primary function of cardiac mitochondria is the production of ATP to support heart contraction. Examination of the mitochondrial redox state is therefore crucially important to sensitively detect early signs of mitochondrial function in pathophysiological conditions, such as ischemia, diabetes and heart failure. We study fingerprinting of mitochondrial metabolic oxidative state in living cardiomyocytes with spectrally-resolved fluorescence lifetime spectroscopy of NAD(P)H, the principal electron donor in mitochondrial respiration responsible for vital ATP supply. Here NAD(P)H is studied as a marker for non-invasive fluorescent probing of the mitochondrial function. NAD(P) H fluorescence is recorded in cardiac cells following excitation with 375nm UV-light and detection by spectrally-resolved time-correlated single photon counting (TCSPC), based on the simultaneous measurement of the fluorescence spectra and fluorescence lifetimes. Modulation of NADH production and/or mitochondrial respiration is tested to study dynamic characteristics of NAD(P) H fluorescence decay. Our results show that at least a 3-exponential decay model, with 0.4-0.7ns, 1.2-1.9ns and 8.0-13. Ons lifetime pools is necessary to describe cardiomyocyte autofluorescence (AF) within 420-560nm spectral range. Increased mitochondrial NADH production by ketone bodies enhanced the fluorescence intensity, without significant change in fluorescent lifetimes. Rotenone, the inhibitor of Complex I of the mitochondrial respiratory chain, increased AF intensity and shortened the average fluorescence lifetime. Dinitrophenol (DNP), an uncoupling agent of the mitochondrial oxidative phosphorylation, lowered AF intensity, broadened the spectral shoulder at 520 nm and increased the average fluorescence lifetime. These effects are comparable to the study of NADH fluorescence decay in vitro. In the present contribution we demonstrated that spectrally-resolved fluorescence lifetime technique provides promising new

Carbon Atom Hybridization Matters: Ultrafast Humidity Response of Graphdiyne Oxides.

PubMed

Yan, Hailong; Guo, Shuyue; Wu, Fei; Yu, Ping; Liu, Huibiao; Li, Yuliang; Mao, Lanqun

2018-04-03

Graphdiyne oxide (GDO), the oxidized form of graphdiyne (GDY), exhibits an ultrafast humidity response with an unprecedented response speed (ca. 7 ms), which is three times faster than that of graphene oxide (GO) with the same thickness and O/C ratio. The ultrafast humidity response of GDO is considered to benefit from the unique carbon hybridization of GDO, which contains acetylenic bonds that are more electron-withdrawing than ethylenic bonds in GO, consequently giving rise to a faster binding rate with water. This distinctive structure-based property enables the fabrication of a novel GDO-based humidity sensor with an ultrafast response speed and good selectivity against other kinds of gas molecules as well as high sensitivity. These properties allow the sensor to accurately monitor the respiration rate change of human and hypoxic rats. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ultrafast above-threshold dynamics of the radical anion of a prototypical quinone electron-acceptor.

PubMed

Horke, Daniel A; Li, Quansong; Blancafort, Lluís; Verlet, Jan R R

2013-08-01

Quinones feature prominently as electron acceptors in nature. Their electron-transfer reactions are often highly exergonic, for which Marcus theory predicts reduced electron-transfer rates because of a free-energy barrier that occurs in the inverted region. However, the electron-transfer kinetics that involve quinones can appear barrierless. Here, we consider the intrinsic properties of the para-benzoquinone radical anion, which serves as the prototypical electron-transfer reaction product involving a quinone-based acceptor. Using time-resolved photoelectron spectroscopy and ab initio calculations, we show that excitation at 400 and 480 nm yields excited states that are unbound with respect to electron loss. These excited states are shown to decay on a sub-40 fs timescale through a series of conical intersections with lower-lying excited states, ultimately to form the ground anionic state and avoid autodetachment. From an isolated electron-acceptor perspective, this ultrafast stabilization mechanism accounts for the ability of para-benzoquinone to capture and retain electrons.

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

NASA Astrophysics Data System (ADS)

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

2018-02-01

Many aromatic organic molecules exhibit strong and characteristic fluorescence when excited with ultraviolet radiation. As laser excitation in the ultraviolet generates both fluorescence and resonantly enhanced Raman scattering of aromatic vibrational modes, combined Raman and fluorescence instruments have been proposed to search for organic compounds on Mars. In this work the time-resolved fluorescence of a suite of 24 compounds composed of 2-5 ringed alternant, non-alternant, and heterocyclic PAHs was measured. Fluorescence instrumentation with similar specifications to a putative flight instrument was capable of observing the fluorescence decay of these compounds with a sub-ns resolution. Incorporating time-resolved capabilities was also found to increase the ability to discriminate between individual PAHs. Incorporating time-resolved fluorescence capabilities into an ultraviolet gated Raman system intended for a rover or lander can increase the ability to detect and characterize PAHs on planetary surfaces.

Gain-guided soliton fiber laser with high-quality rectangle spectrum for ultrafast time-stretch microscopy.

PubMed

Hu, Song; Yao, Jian; Liu, Meng; Luo, Ai-Ping; Luo, Zhi-Chao; Xu, Wen-Cheng

2016-05-16

The ultrafast time-stretch microscopy has been proposed to enhance the temporal resolution of a microscopy system. The optical source is a key component for ultrafast time-stretch microscopy system. Herein, we reported on the gain-guided soliton fiber laser with high-quality rectangle spectrum for ultrafast time-stretch microscopy. By virtue of the excellent characteristics of the gain-guided soliton, the output power and the 3-dB bandwidth of the stable mode-locked soliton could be up to 3 mW and 33.7 nm with a high-quality rectangle shape, respectively. With the proposed robust optical source, the ultrafast time-stretch microscopy with the 49.6 μm resolution and a scan rate of 11 MHz was achieved without the external optical amplification. The obtained results demonstrated that the gain-guided soliton fiber laser could be used as an alternative high-quality optical source for ultrafast time-stretch microscopy and will introduce some applications in fields such as biology, chemical, and optical sensing.

A colorimetric and ratiometric fluorescent chemosensor for fluoride based on proton transfer.

PubMed

Jia, Chuandong; Wu, Biao; Liang, Jianjun; Huang, Xiaojuan; Yang, Xiao-Juan

2010-01-01

N-Phenyl-N'-(3-quinolinyl)urea (1) has been developed as a highly selective colorimetric and ratiometric fluorescent chemosensor for fluoride ion based on a proton transfer mechanism. Evidences for the mechanism were provided by UV-vis and fluorescence titration and especially (1)H and (19)F NMR experiments. The sensor gave the largest ratiometric fluorescent response reported so far (R(max)/R(min) = 2620) to fluoride. Taking H(+) as the "recovering reagent", the sensor can be reversibly "used" and "recovered" for several cycles with only a slight decay of the response ability.

Discrete decoding based ultrafast multidimensional nuclear magnetic resonance spectroscopy

NASA Astrophysics Data System (ADS)

Wei, Zhiliang; Lin, Liangjie; Ye, Qimiao; Li, Jing; Cai, Shuhui; Chen, Zhong

2015-07-01

The three-dimensional (3D) nuclear magnetic resonance (NMR) spectroscopy constitutes an important and powerful tool in analyzing chemical and biological systems. However, the abundant 3D information arrives at the expense of long acquisition times lasting hours or even days. Therefore, there has been a continuous interest in developing techniques to accelerate recordings of 3D NMR spectra, among which the ultrafast spatiotemporal encoding technique supplies impressive acquisition speed by compressing a multidimensional spectrum in a single scan. However, it tends to suffer from tradeoffs among spectral widths in different dimensions, which deteriorates in cases of NMR spectroscopy with more dimensions. In this study, the discrete decoding is proposed to liberate the ultrafast technique from tradeoffs among spectral widths in different dimensions by focusing decoding on signal-bearing sites. For verifying its feasibility and effectiveness, we utilized the method to generate two different types of 3D spectra. The proposed method is also applicable to cases with more than three dimensions, which, based on the experimental results, may widen applications of the ultrafast technique.

Rippling ultrafast dynamics of suspended 2D monolayers, graphene.

PubMed

Hu, Jianbo; Vanacore, Giovanni M; Cepellotti, Andrea; Marzari, Nicola; Zewail, Ahmed H

2016-10-25

Here, using ultrafast electron crystallography (UEC), we report the observation of rippling dynamics in suspended monolayer graphene, the prototypical and most-studied 2D material. The high scattering cross-section for electron/matter interaction, the atomic-scale spatial resolution, and the ultrafast temporal resolution of UEC represent the key elements that make this technique a unique tool for the dynamic investigation of 2D materials, and nanostructures in general. We find that, at early time after the ultrafast optical excitation, graphene undergoes a lattice expansion on a time scale of 5 ps, which is due to the excitation of short-wavelength in-plane acoustic phonon modes that stretch the graphene plane. On a longer time scale, a slower thermal contraction with a time constant of 50 ps is observed and associated with the excitation of out-of-plane phonon modes, which drive the lattice toward thermal equilibrium with the well-known negative thermal expansion coefficient of graphene. From our results and first-principles lattice dynamics and out-of-equilibrium relaxation calculations, we quantitatively elucidate the deformation dynamics of the graphene unit cell.

Ultrafast Laser System for Producing on-Demand Single-and Multi-Photon Quantum States

DTIC Science & Technology

2015-09-20

14-Mar-2015 Approved for Public Release; Distribution Unlimited Final Report: Ultrafast laser system for producing on-demand single- and multi...Champaign, IL 61820 -7406 14-Mar-2015 ABSTRACT Number of Papers published in peer-reviewed journals: Final Report: Ultrafast laser system for producing

Kinetic Analysis of Benign and Malignant Breast Lesions With Ultrafast Dynamic Contrast-Enhanced MRI: Comparison With Standard Kinetic Assessment.

PubMed

Abe, Hiroyuki; Mori, Naoko; Tsuchiya, Keiko; Schacht, David V; Pineda, Federico D; Jiang, Yulei; Karczmar, Gregory S

2016-11-01

The purposes of this study were to evaluate diagnostic parameters measured with ultrafast MRI acquisition and with standard acquisition and to compare diagnostic utility for differentiating benign from malignant lesions. Ultrafast acquisition is a high-temporal-resolution (7 seconds) imaging technique for obtaining 3D whole-breast images. The dynamic contrast-enhanced 3-T MRI protocol consists of an unenhanced standard and an ultrafast acquisition that includes eight contrast-enhanced ultrafast images and four standard images. Retrospective assessment was performed for 60 patients with 33 malignant and 29 benign lesions. A computer-aided detection system was used to obtain initial enhancement rate and signal enhancement ratio (SER) by means of identification of a voxel showing the highest signal intensity in the first phase of standard imaging. From the same voxel, the enhancement rate at each time point of the ultrafast acquisition and the AUC of the kinetic curve from zero to each time point of ultrafast imaging were obtained. There was a statistically significant difference between benign and malignant lesions in enhancement rate and kinetic AUC for ultrafast imaging and also in initial enhancement rate and SER for standard imaging. ROC analysis showed no significant differences between enhancement rate in ultrafast imaging and SER or initial enhancement rate in standard imaging. Ultrafast imaging is useful for discriminating benign from malignant lesions. The differential utility of ultrafast imaging is comparable to that of standard kinetic assessment in a shorter study time.

Ultrafast structural and electronic dynamics of the metallic phase in a layered manganite

PubMed Central

Piazza, L.; Ma, C.; Yang, H. X.; Mann, A.; Zhu, Y.; Li, J. Q.; Carbone, F.

2013-01-01

The transition between different states in manganites can be driven by various external stimuli. Controlling these transitions with light opens the possibility to investigate the microscopic path through which they evolve. We performed femtosecond (fs) transmission electron microscopy on a bi-layered manganite to study its response to ultrafast photoexcitation. We show that a photoinduced temperature jump launches a pressure wave that provokes coherent oscillations of the lattice parameters, detected via ultrafast electron diffraction. Their impact on the electronic structure are monitored via ultrafast electron energy loss spectroscopy, revealing the dynamics of the different orbitals in response to specific structural distortions. PMID:26913564

Ultrafast photocurrents in monolayer MoS2

NASA Astrophysics Data System (ADS)

Parzinger, Eric; Wurstbauer, Ursula; Holleitner, Alexander W.

Two-dimensional transition metal dichalcogenides such as MoS2 have emerged as interesting materials for optoelectronic devices. In particular, the ultrafast dynamics and lifetimes of photoexcited charge carriers have attracted great interest during the last years. We investigate the photocurrent response of monolayer MoS2 on a picosecond time scale utilizing a recently developed pump-probe spectroscopy technique based on coplanar striplines. We discuss the ultrafast dynamics within MoS2 including photo-thermoelectric currents and the impact of built-in fields due to Schottky barriers as well as the Fermi level pinning at the contact region. We acknowledge support by the ERC via Project 'NanoREAL', the DFG via excellence cluster 'Nanosystems Initiative Munich' (NIM), and through the TUM International Graduate School of Science and Engineering (IGSSE) and BaCaTeC.

Solvent and temperature effects on the decay dynamics of [p-N,N-(dialkylamino)benzylidene]malononitriles

NASA Astrophysics Data System (ADS)

Safarzadeh-Amiri, A.

1986-08-01

The effects of solvent and temperature on the decay kinetics of p-(dialkylamino)benzylidenemalononitrile (1) and julodinemalononitrile (3) has been studied in glycerol and triacetin. The fluorescence decay curves of these compounds were non-exponential and varied slightly with wavelength. This is attributed to the existence of two ground state conformers and to reorientation of the solvent cage around solute molecules. The results were explained in terms of trans → cisphotoisomerization.

Fluorescence correlation spectroscopy of diffusion probed with a Gaussian Lorentzian spatial distribution

NASA Astrophysics Data System (ADS)

Marrocco, Michele

2007-11-01

Fluorescence correlation spectroscopy is fundamental in many physical, chemical and biological studies of molecular diffusion. However, the concept of fluorescence correlation is founded on the assumption that the analytical description of the correlation decay of diffusion can be achieved if the spatial profile of the detected volume obeys a three-dimensional Gaussian distribution. In the present Letter, the analytical result is instead proven for the fundamental Gaussian-Lorentzian profile.

Ultrafast Exciton Delocalization, Localization, and Excimer Formation Dynamics in a Highly Defined Perylene Bisimide Quadruple π-Stack.

PubMed

Kaufmann, Christina; Kim, Woojae; Nowak-Król, Agnieszka; Hong, Yongseok; Kim, Dongho; Würthner, Frank

2018-03-28

An adequately designed, bay-tethered perylene bisimide (PBI) dimer Bis-PBI was synthesized by Pd/Cu-catalyzed Glaser-type oxidative homocoupling of the respective PBI building block. This newly synthesized PBI dimer self-assembles exclusively and with high binding constants of up to 10 6 M -1 into a discrete π-stack of four chromophores. Steady-state absorption and emission spectra show the signatures of H-type excitonic coupling among the dye units. Broadband fluorescence upconversion spectroscopy (FLUPS) reveals an ultrafast dynamics in the optically excited state. An initially coherent Frenkel exciton state that is delocalized over the whole quadruple stack rapidly (τ = ∼200 fs) loses its coherence and relaxes into an excimer state. Comparison with Frenkel exciton dynamics in PBI dimeric and oligomeric H-aggregates demonstrates that in the quadruple stack coherent exciton propagation is absent due to its short length of aggregates, thereby it has only one relaxation pathway to the excimer state. Furthermore, the absence of pump-power dependence in transient absorption experiments suggests that multiexciton cannot be generated in the quadruple stack, which is in line with time-resolved fluorescence measurements.

Direct observation of ultrafast many-body electron dynamics in an ultracold Rydberg gas

PubMed Central

Takei, Nobuyuki; Sommer, Christian; Genes, Claudiu; Pupillo, Guido; Goto, Haruka; Koyasu, Kuniaki; Chiba, Hisashi; Weidemüller, Matthias; Ohmori, Kenji

2016-01-01

Many-body correlations govern a variety of important quantum phenomena such as the emergence of superconductivity and magnetism. Understanding quantum many-body systems is thus one of the central goals of modern sciences. Here we demonstrate an experimental approach towards this goal by utilizing an ultracold Rydberg gas generated with a broadband picosecond laser pulse. We follow the ultrafast evolution of its electronic coherence by time-domain Ramsey interferometry with attosecond precision. The observed electronic coherence shows an ultrafast oscillation with a period of 1 femtosecond, whose phase shift on the attosecond timescale is consistent with many-body correlations among Rydberg atoms beyond mean-field approximations. This coherent and ultrafast many-body dynamics is actively controlled by tuning the orbital size and population of the Rydberg state, as well as the mean atomic distance. Our approach will offer a versatile platform to observe and manipulate non-equilibrium dynamics of quantum many-body systems on the ultrafast timescale. PMID:27849054

Tunneled Mesoporous Carbon Nanofibers with Embedded ZnO Nanoparticles for Ultrafast Lithium Storage.

PubMed

An, Geon-Hyoung; Lee, Do-Young; Ahn, Hyo-Jin

2017-04-12

Carbon and metal oxide composites have received considerable attention as anode materials for Li-ion batteries (LIBs) owing to their excellent cycling stability and high specific capacity based on the chemical and physical stability of carbon and the high theoretical specific capacity of metal oxides. However, efforts to obtain ultrafast cycling stability in carbon and metal oxide composites at high current density for practical applications still face important challenges because of the longer Li-ion diffusion pathway, which leads to poor ultrafast performance during cycling. Here, tunneled mesoporous carbon nanofibers with embedded ZnO nanoparticles (TMCNF/ZnO) are synthesized by electrospinning, carbonization, and postcalcination. The optimized TMCNF/ZnO shows improved electrochemical performance, delivering outstanding ultrafast cycling stability, indicating a higher specific capacity than previously reported ZnO-based anode materials in LIBs. Therefore, the unique architecture of TMCNF/ZnO has potential for use as an anode material in ultrafast LIBs.

Ultrafast dynamics of electrons in ammonia.

PubMed

Vöhringer, Peter

2015-04-01

Solvated electrons were first discovered in solutions of metals in liquid ammonia. The physical and chemical properties of these species have been studied extensively for many decades using an arsenal of electrochemical, spectroscopic, and theoretical techniques. Yet, in contrast to their hydrated counterpart, the ultrafast dynamics of ammoniated electrons remained completely unexplored until quite recently. Femtosecond pump-probe spectroscopy on metal-ammonia solutions and femtosecond multiphoton ionization spectroscopy on the neat ammonia solvent have provided new insights into the optical properties and the reactivities of this fascinating species. This article reviews the nature of the optical transition, which gives the metal-ammonia solutions their characteristic blue appearance, in terms of ultrafast relaxation processes involving bound and continuum excited states. The recombination processes following the injection of an electron via photoionization of the solvent are discussed in the context of the electronic structure of the liquid and the anionic defect associated with the solvated electron.

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

NASA Astrophysics Data System (ADS)

Joo, Taiha

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

Ultrafast photoinduced charge separation in metal-semiconductor nanohybrids.

PubMed

Mongin, Denis; Shaviv, Ehud; Maioli, Paolo; Crut, Aurélien; Banin, Uri; Del Fatti, Natalia; Vallée, Fabrice

2012-08-28

Hybrid nano-objects formed by two or more disparate materials are among the most promising and versatile nanosystems. A key parameter in their properties is interaction between their components. In this context we have investigated ultrafast charge separation in semiconductor-metal nanohybrids using a model system of gold-tipped CdS nanorods in a matchstick architecture. Experiments are performed using an optical time-resolved pump-probe technique, exciting either the semiconductor or the metal component of the particles, and probing the light-induced change of their optical response. Electron-hole pairs photoexcited in the semiconductor part of the nanohybrids are shown to undergo rapid charge separation with the electron transferred to the metal part on a sub-20 fs time scale. This ultrafast gold charging leads to a transient red-shift and broadening of the metal surface plasmon resonance, in agreement with results for free clusters but in contrast to observation for static charging of gold nanoparticles in liquid environments. Quantitative comparison with a theoretical model is in excellent agreement with the experimental results, confirming photoexcitation of one electron-hole pair per nanohybrid followed by ultrafast charge separation. The results also point to the utilization of such metal-semiconductor nanohybrids in light-harvesting applications and in photocatalysis.

Advanced Instrumentation for Ultrafast Science at the LCLS

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

Berrah, Nora

2015-10-13

This grant supported a Single Investigator and Small Group Research (SISGR) application to enable multi-user research in Ultrafast Science using the Linac Coherent Light Source (LCLS), the world’s first hard x-ray free electron laser (FEL) which lased for the first time at 1.5 Å on April 20, 2009. The goal of our proposal was to enable a New Era of Science by requesting funds to purchase and build Advanced Instrumentation for Ultrafast Science (AIUS), to utilize the intense, short x-ray pulses produced by the LCLS. The proposed instrumentation will allow peer review selected users to probe the ultrasmall and capture themore » ultrafast. These tools will expand on the investment already made in the construction of the light source and its instrumentation in both the LCLS and LUSI projects. The AIUS will provide researchers in the AMO, Chemical, Biological and Condensed Matter communities with greater flexibility in defining their scientific agenda at the LCLS. The proposed instrumentation will complement and significantly augment the present AMO instrument (funded through the LCLS project) through detectors and capabilities not included in the initial suite of instrumentation at the facility. We have built all of the instrumentations and they have been utilized by scientists. Please see report attached.« less

Photon gating in four-dimensional ultrafast electron microscopy.

PubMed

Hassan, Mohammed T; Liu, Haihua; Baskin, John Spencer; Zewail, Ahmed H

2015-10-20

Ultrafast electron microscopy (UEM) is a pivotal tool for imaging of nanoscale structural dynamics with subparticle resolution on the time scale of atomic motion. Photon-induced near-field electron microscopy (PINEM), a key UEM technique, involves the detection of electrons that have gained energy from a femtosecond optical pulse via photon-electron coupling on nanostructures. PINEM has been applied in various fields of study, from materials science to biological imaging, exploiting the unique spatial, energy, and temporal characteristics of the PINEM electrons gained by interaction with a "single" light pulse. The further potential of photon-gated PINEM electrons in probing ultrafast dynamics of matter and the optical gating of electrons by invoking a "second" optical pulse has previously been proposed and examined theoretically in our group. Here, we experimentally demonstrate this photon-gating technique, and, through diffraction, visualize the phase transition dynamics in vanadium dioxide nanoparticles. With optical gating of PINEM electrons, imaging temporal resolution was improved by a factor of 3 or better, being limited only by the optical pulse widths. This work enables the combination of the high spatial resolution of electron microscopy and the ultrafast temporal response of the optical pulses, which provides a promising approach to attain the resolution of few femtoseconds and attoseconds in UEM.

Photon gating in four-dimensional ultrafast electron microscopy

PubMed Central

Hassan, Mohammed T.; Liu, Haihua; Baskin, John Spencer; Zewail, Ahmed H.

2015-01-01

Ultrafast electron microscopy (UEM) is a pivotal tool for imaging of nanoscale structural dynamics with subparticle resolution on the time scale of atomic motion. Photon-induced near-field electron microscopy (PINEM), a key UEM technique, involves the detection of electrons that have gained energy from a femtosecond optical pulse via photon–electron coupling on nanostructures. PINEM has been applied in various fields of study, from materials science to biological imaging, exploiting the unique spatial, energy, and temporal characteristics of the PINEM electrons gained by interaction with a “single” light pulse. The further potential of photon-gated PINEM electrons in probing ultrafast dynamics of matter and the optical gating of electrons by invoking a “second” optical pulse has previously been proposed and examined theoretically in our group. Here, we experimentally demonstrate this photon-gating technique, and, through diffraction, visualize the phase transition dynamics in vanadium dioxide nanoparticles. With optical gating of PINEM electrons, imaging temporal resolution was improved by a factor of 3 or better, being limited only by the optical pulse widths. This work enables the combination of the high spatial resolution of electron microscopy and the ultrafast temporal response of the optical pulses, which provides a promising approach to attain the resolution of few femtoseconds and attoseconds in UEM. PMID:26438835

Ultrafast dynamic response of single crystal β-HMX

NASA Astrophysics Data System (ADS)

Zaug, Joseph M.; Armstrong, Michael R.; Crowhurst, Jonathan C.; Radousky, Harry B.; Ferranti, Louis; Swan, Raymond; Gross, Rick; Teslich, Nick E.; Wall, Mark A.; Austin, Ryan A.; Fried, Laurence E.

2017-01-01

We report results from ultrafast compression experiments conducted on β-HMX single crystals. Results consist of nominally 12 picosecond time-resolved wave profile data, (ultrafast time domain interferometry -TDI measurements), that were analyzed to determine high-velocity wave speeds as a function of piston velocity. TDI results are used to validate calculations of anisotropic stress-strain behavior of shocked loaded energetic materials. Our previous results derived using a 350 ps duration compression drive revealed anisotropic elastic wave response in single crystal β-HMX from (110) and (010) impact planes. Here we present results using a 1.05 ns duration compression drive with a 950 ps interferometry window to extend knowledge of the anisotropic dynamic response of β-HMX within eight microns of the initial impact plane. We observe two distinct wave profiles from (010) and three wave profiles from (010) impact planes. The (110) impact plane wave speeds typically exceed (010) impact plane wave speeds at the same piston velocities. The development of multiple hydrodynamic wave profiles begins at 20 GPa for the (110) impact plane and 28 GPa for the (10) impact plane. We compare our ultrafast TDI results with previous gun and plate impact results on β-HMX and PBX9501.

Feasibility of UltraFast Doppler in Post-operative Evaluation of Hepatic Artery in Recipients following Liver Transplantation.

PubMed

Kim, Se-Young; Kim, Kyoung Won; Choi, Sang Hyun; Kwon, Jae Hyun; Song, Gi-Won; Kwon, Heon-Ju; Yun, Young Ju; Lee, Jeongjin; Lee, Sung-Gyu

2017-11-01

To determine the feasibility of using UltraFast Doppler in post-operative evaluation of the hepatic artery (HA) after liver transplantation (LT), we evaluated 283 simultaneous conventional and UltraFast Doppler sessions in 126 recipients over a 2-mo period after LT, using an Aixplorer scanner The Doppler indexes of the HA (peak systolic velocity [PSV], end-diastolic velocity [EDV], resistive index [RI] and systolic acceleration time [SAT]) by retrospective analysis of retrieved waves from UltraFast Doppler clips were compared with those obtained by conventional spectral Doppler. Correlation, performance in diagnosing the pathologic wave, examination time and reproducibility were evaluated. The PSV, EDV, RI and SAT of spectral and UltraFast Doppler measurements exhibited excellent correlation with favorable diagnostic performance. During the bedside examination, the mean time spent for UltraFast clip storing was significantly shorter than that for conventional Doppler US measurements. Both conventional and UltraFast Doppler exhibited good to excellent inter-analysis consistency. In conclusion, compared with conventional spectral Doppler, UltraFast Doppler values correlated excellently and yielded acceptable pathologic wave diagnostic performance with reduced examination time at the bedside and excellent reproducibility. Copyright © 2017 World Federation for Ultrasound in Medicine & Biology. Published by Elsevier Inc. All rights reserved.

High-speed ultrafast laser machining with tertiary beam positioning (Conference Presentation)

NASA Astrophysics Data System (ADS)

Yang, Chuan; Zhang, Haibin

2017-03-01

For an industrial laser application, high process throughput and low average cost of ownership are critical to commercial success. Benefiting from high peak power, nonlinear absorption and small-achievable spot size, ultrafast lasers offer advantages of minimal heat affected zone, great taper and sidewall quality, and small via capability that exceeds the limits of their predecessors in via drilling for electronic packaging. In the past decade, ultrafast lasers have both grown in power and reduced in cost. For example, recently, disk and fiber technology have both shown stable operation in the 50W to 200W range, mostly at high repetition rate (beyond 500 kHz) that helps avoid detrimental nonlinear effects. However, to effectively and efficiently scale the throughput with the fast-growing power capability of the ultrafast lasers while keeping the beneficial laser-material interactions is very challenging, mainly because of the bottleneck imposed by the inertia-related acceleration limit and servo gain bandwidth when only stages and galvanometers are being used. On the other side, inertia-free scanning solutions like acoustic optics and electronic optical deflectors have small scan field, and therefore not suitable for large-panel processing. Our recent system developments combine stages, galvanometers, and AODs into a coordinated tertiary architecture for high bandwidth and meanwhile large field beam positioning. Synchronized three-level movements allow extremely fast local speed and continuous motion over the whole stage travel range. We present the via drilling results from such ultrafast system with up to 3MHz pulse to pulse random access, enabling high quality low cost ultrafast machining with emerging high average power laser sources.

Ultrafast Photodetection in the Quantum Wells of Single AlGaAs/GaAs-Based Nanowires.

PubMed

Erhard, N; Zenger, S; Morkötter, S; Rudolph, D; Weiss, M; Krenner, H J; Karl, H; Abstreiter, G; Finley, J J; Koblmüller, G; Holleitner, A W

2015-10-14

We investigate the ultrafast optoelectronic properties of single Al0.3Ga0.7As/GaAs core-shell nanowires. The nanowires contain GaAs-based quantum wells. For a resonant excitation of the quantum wells, we find a picosecond photocurrent which is consistent with an ultrafast lateral expansion of the photogenerated charge carriers. This Dember-effect does not occur for an excitation of the GaAs-based core of the nanowires. Instead, the core exhibits an ultrafast displacement current and a photothermoelectric current at the metal Schottky contacts. Our results uncover the optoelectronic dynamics in semiconductor core-shell nanowires comprising quantum wells, and they demonstrate the possibility to use the low-dimensional quantum well states therein for ultrafast photoswitches and photodetectors.

Active substrates improving sensitivity in biomedical fluorescence microscopy

NASA Astrophysics Data System (ADS)

Le Moal, E.; Leveque-Fort, S.; Fort, E.; Lacharme, J.-P.; Fontaine-Aupart, M.-P.; Ricolleau, C.

2005-08-01

Fluorescence is widely used as a spectroscopic tool or for biomedical imaging, in particular for DNA chips. In some cases, detection of very low molecular concentrations and precise localization of biomarkers are limited by the weakness of the fluorescence signal. We present a new method based on sample substrates that improve fluorescence detection sensitivity. These active substrates consist in glass slides covered with metal (gold or silver) and dielectric (alumina) films and can directly be used with common microscope set-up. Fluorescence enhancement affects both excitation and decay rates and is strongly dependant on the distance to the metal surface. Furthermore, fluorescence collection is improved since fluorophore emission lobes are advantageously modified close to a reflective surface. Finally, additional improvements are achieved by structuring the metallic layer. Substrates morphology was mapped by Atomic Force Microscopy (AFM). Substrates optical properties were studied using mono- and bi-photonic fluorescence microscopy with time resolution. An original set-up was implemented for spatial radiation pattern's measurement. Detection improvement was then tested on commercial devices. Several biomedical applications are presented. Enhancement by two orders of magnitude are achieved for DNA chips and signal-to-noise ratio is greatly increased for cells imaging.

Quantitative fluorescence measurements performed on typical matrix molecules in matrix-assisted laser desorption/ionisation

NASA Astrophysics Data System (ADS)

Allwood, D. A.; Dyer, P. E.

2000-11-01

Fundamental photophysical parameters have been determined for several molecules that are commonly used as matrices, e.g. ferulic acid, within matrix-assisted laser desorption/ionization (MALDI) mass spectrometry. Fluorescence quantum efficiencies ( φqe), singlet decay rates ( kl), vibrationless ground-singlet transition energies and average fluorescence wavelengths have been obtained from solid and solution samples by quantitative optical measurements. This new data will assist in modelling calculations of MALDI processes and in highlighting desirable characteristics of MALDI matrices. φqe may be as high as 0.59 whilst the radiative decay rate ( kf) appears to be within the (0.8-4)×10 8 s -1 range. Interestingly, α-cyano-4-hydroxycinnamic acid (α-CHC) has a very low φqe and fast non-radiative decay rate which would imply a rapid and efficient thermalisation of electronic excitation. This is in keeping with observations that α-CHC exhibits low threshold fluences for ion detection and the low fluences at which α-CHC tends to fragment.

Teaching laser-induced fluorescence of plant leaves

NASA Astrophysics Data System (ADS)

Lenk, Sándor; Gádoros, Patrik; Kocsányi, László; Barócsi, Attila

2016-11-01

Plants convert carbon dioxide into sugars using the energy of sunlight. Absorbed light unused for conversion is dissipated primarily as heat with a small fraction re-emitted as fluorescence at longer wavelengths. One can use the latter to estimate photosynthetic activity. The illumination of intact leaves with strong light after keeping them in dark for tens of minutes results in a rapid increase followed by a slow decay of fluorescence emission from the fluorophore chlorophyll-a, called the Kautsky effect. This paper describes a laboratory practice that introduces students of physics or engineering into this research field. It begins with the spectral measurement of the fluorescence emitted by a plant leaf upon UV excitation. Then it focuses on the red and far-red components of the fluorescence emission spectrum characteristic to the chlorophyll-a molecule and presents an inexpensive demonstration of the Kautsky effect. As researchers use more complex measurement techniques and tools, the practice ends up with the demonstration of an intelligent fluorosensor, a compact tool developed for plant physiological research and horticulture applications together with a brief interpretation of some important fluorescence parameters.

Clinical results of fluorescence lifetime imaging in ophthalmology

NASA Astrophysics Data System (ADS)

Schweitzer, D.; Quick, S.; Klemm, M.; Hammer, M.; Jentsch, S.; Dawczynski, J.; Becker, W.

2009-07-01

A laser scanner ophthalmoscope was developed for in vivo fluorescence lifetime measurements at the human retina. Measurements were performed in 30 degree fundus images. The fundus was excited by pulses of 75 ps (FWHM). The dynamic fluorescence was detected in two spectral channels K1(490-560nm), K2(560-700 nm) by time-correlated single photon counting. The decay of fluorescence was three-exponentially. Local and global alterations in lifetimes were found between healthy subjects and patients suffering from age-related macular degeneration, diabetic retinopathy, and vessel occlusion. The lifetimes T1, T2, and T3 in both channels are changed to longer values in AMD and diabetic retinopathy in comparison with healthy subjects. The lifetime T2 in K1 is most sensitive to metabolic alterations in branch arterial vessel occlusion.

Compact ultrafast semiconductor disk laser for nonlinear imaging in living organisms

NASA Astrophysics Data System (ADS)

Aviles-Espinosa, Rodrigo; Filippidis, G.; Hamilton, Craig; Malcolm, Graeme; Weingarten, Kurt J.; Südmeyer, Thomas; Barbarin, Yohan; Keller, Ursula; Artigas, David; Loza-Alvarez, Pablo

2011-03-01

Ultrashort pulsed laser systems (such as Ti:sapphire) have been used in nonlinear microscopy during the last years. However, its implementation is not straight forward as they are maintenance-intensive, bulky and expensive. These limitations have prevented their wide-spread use for nonlinear imaging, especially in "real-life" biomedical applications. In this work we present the suitability of a compact ultrafast semiconductor disk laser source, with a footprint of 140x240x70 mm, to be used for nonlinear microscopy. The modelocking mechanism of the laser is based on a quantumdot semiconductor saturable absorber mirror (SESAM). The laser delivers an average output power of 287 mW with 1.5 ps pulses at 500 MHz, corresponding to a peak power of 0.4 kW. Its center wavelength is 965 nm which is ideally suited for two-photon excitation of the widely used Green Fluorescent Protein (GFP) marker as it virtually matches its twophoton action cross section. We reveal that it is possible to obtain two photon excited fluorescence images of GFP labeled neurons and secondharmonic generation images of pharynx and body wall muscles in living C. elegans nematodes. Our results demonstrate that this compact laser is well suited for long-term time-lapse imaging of living samples as very low powers provide a bright signal. Importantly this non expensive, turn-key, compact laser system could be used as a platform to develop portable nonlinear bio-imaging devices, facilitating its wide-spread adoption in "real-life" applications.

Femtosecond laser spectroscopy of the rhodopsin photochromic reaction: a concept for ultrafast optical molecular switch creation (ultrafast reversible photoreaction of rhodopsin).

PubMed

Smitienko, Olga; Nadtochenko, Victor; Feldman, Tatiana; Balatskaya, Maria; Shelaev, Ivan; Gostev, Fedor; Sarkisov, Oleg; Ostrovsky, Mikhail

2014-11-11

Ultrafast reverse photoreaction of visual pigment rhodopsin in the femtosecond time range at room temperature is demonstrated. Femtosecond two-pump probe experiments with a time resolution of 25 fs have been performed. The first рump pulse at 500 nm initiated cis-trans photoisomerization of rhodopsin chromophore, 11-cis retinal, which resulted in the formation of the primary ground-state photoproduct within a mere 200 fs. The second pump pulse at 620 nm with a varying delay of 200 to 3750 fs relative to the first рump pulse, initiated the reverse phototransition of the primary photoproduct to rhodopsin. The results of this photoconversion have been observed on the differential spectra obtained after the action of two pump pulses at a time delay of 100 ps. It was found that optical density decreased at 560 nm in the spectral region of bathorhodopsin absorption and increased at 480 nm, where rhodopsin absorbs. Rhodopsin photoswitching efficiency shows oscillations as a function of the time delay between two рump pulses. The quantum yield of reverse photoreaction initiated by the second pump pulse falls within the range 15%±1%. The molecular mechanism of the ultrafast reversible photoreaction of visual pigment rhodopsin may be used as a concept for the development of an ultrafast optical molecular switch.

Ultrafast Unzipping of a Beta-Hairpin Peptide

NASA Astrophysics Data System (ADS)

Zinth, W.; Schrader, T. E.; Schreier, W. J.; Koller, F. O.; Cordes, T.; Babitzki, G.; Denschlag, R.; Tavan, P.; Löweneck, M.; Dong, Shou-Liang; Moroder, L.; Renner, C.

Light induced switching of a beta-hairpin structure is investigated by femtosecond IR spectroscopy. While the unzipping process comprises ultrafast kinetics and is finished within 1 ns, the folding into the hairpin structure is a much slower process.

Ultrafast all-optical control of the magnetization in magnetic dielectrics

NASA Astrophysics Data System (ADS)

Kirilyuk, Andrei; Kimel, Alexey; Hansteen, Fredrik; Rasing, Theo; Pisarev, Roman V.

2006-08-01

The purpose of this review is to summarize the recent progress on laser-induced magnetization dynamics in magnetic dielectrics. Due to the slow phonon-magnon interaction in these materials, direct thermal effects of the laser excitation can only be seen on the time scale of almost a nanosecond and thus are clearly distinguished from the ultrafast nonthermal effects. However, laser pulses are shown to indirectly modify the magnetic anisotropy in rare-earth orthoferrites via the crystal field, and to bring about spin reorientation within a few picoseconds. More interesting, however, are the direct nonthermal effects of light on spin systems. We demonstrate coherent optical control of the magnetization in ferrimagnetic garnet films on a femtosecond time scale through a combination of two different ultrafast and nonthermal photomagnetic effects and by employing multiple pump pulses. Linearly polarized laser pulses are shown to create a long-lived modification of the magnetocrystalline anisotropy via optically induced electron transfer between nonequivalent ion sites. In addition, circularly polarized pulses are shown to act as strong transient magnetic field pulses originating from the nonabsorptive inverse Faraday effect. An all-optical scheme of excitation and detection of different antiferromagnetic resonance modes with frequencies of up to 500GHz will be discussed as well. The reported effects open new and exciting possibilities for ultrafast manipulation of spins by light and provide new insight into the physics of magnetism on ultrafast time scales.

Drug/protein interactions studied by time-resolved fluorescence spectroscopy

NASA Astrophysics Data System (ADS)

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.

Rejection of fluorescence background in resonance and spontaneous Raman microspectroscopy.

PubMed

Smith, Zachary J; Knorr, Florian; Pagba, Cynthia V; Wachsmann-Hogiu, Sebastian

2011-05-18

Raman spectroscopy is often plagued by a strong fluorescent background, particularly for biological samples. If a sample is excited with a train of ultrafast pulses, a system that can temporally separate spectrally overlapping signals on a picosecond timescale can isolate promptly arriving Raman scattered light from late-arriving fluorescence light. Here we discuss the construction and operation of a complex nonlinear optical system that uses all-optical switching in the form of a low-power optical Kerr gate to isolate Raman and fluorescence signals. A single 808 nm laser with 2.4 W of average power and 80 MHz repetition rate is split, with approximately 200 mW of 808 nm light being converted to < 5 mW of 404 nm light sent to the sample to excite Raman scattering. The remaining unconverted 808 nm light is then sent to a nonlinear medium where it acts as the pump for the all-optical shutter. The shutter opens and closes in 800 fs with a peak efficiency of approximately 5%. Using this system we are able to successfully separate Raman and fluorescence signals at an 80 MHz repetition rate using pulse energies and average powers that remain biologically safe. Because the system has no spare capacity in terms of optical power, we detail several design and alignment considerations that aid in maximizing the throughput of the system. We also discuss our protocol for obtaining the spatial and temporal overlap of the signal and pump beams within the Kerr medium, as well as a detailed protocol for spectral acquisition. Finally, we report a few representative results of Raman spectra obtained in the presence of strong fluorescence using our time-gating system.

An Ultrafast Switchable Terahertz Polarization Modulator Based on III-V Semiconductor Nanowires.

PubMed

Baig, Sarwat A; Boland, Jessica L; Damry, Djamshid A; Tan, H Hoe; Jagadish, Chennupati; Joyce, Hannah J; Johnston, Michael B

2017-04-12

Progress in the terahertz (THz) region of the electromagnetic spectrum is undergoing major advances, with advanced THz sources and detectors being developed at a rapid pace. Yet, ultrafast THz communication is still to be realized, owing to the lack of practical and effective THz modulators. Here, we present a novel ultrafast active THz polarization modulator based on GaAs semiconductor nanowires arranged in a wire-grid configuration. We utilize an optical pump-terahertz probe spectroscopy system and vary the polarization of the optical pump beam to demonstrate ultrafast THz modulation with a switching time of less than 5 ps and a modulation depth of -8 dB. We achieve an extinction of over 13% and a dynamic range of -9 dB, comparable to microsecond-switchable graphene- and metamaterial-based THz modulators, and surpassing the performance of optically switchable carbon nanotube THz polarizers. We show a broad bandwidth for THz modulation between 0.1 and 4 THz. Thus, this work presents the first THz modulator which combines not only a large modulation depth but also a broad bandwidth and picosecond time resolution for THz intensity and phase modulation, making it an ideal candidate for ultrafast THz communication.

Ultrafast electron diffraction with megahertz MeV electron pulses from a superconducting radio-frequency photoinjector

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

Feng, L. W.; Lin, L.; Huang, S. L.

We report ultrafast relativistic electron diffraction operating at the megahertz repetition rate where the electron beam is produced in a superconducting radio-frequency (rf) photoinjector. We show that the beam quality is sufficiently high to provide clear diffraction patterns from gold and aluminium samples. With the number of electrons, several orders of magnitude higher than that from a normal conducting photocathode rf gun, such high repetition rate ultrafast MeV electron diffraction may open up many new opportunities in ultrafast science.

Emissive H-Aggregates of an Ultrafast Molecular Rotor: A Promising Platform for Sensing Heparin.

PubMed

Mudliar, Niyati H; Singh, Prabhat K

2016-11-23

Constructing "turn on" fluorescent probes for heparin, a most widely used anticoagulant in clinics, from commercially available materials is of great importance, but remains challenging. Here, we report the formation of a rarely observed emissive H-aggregate of an ultrafast molecular rotor dye, Thioflavin-T, in the presence of heparin, which provides an excellent platform for simple, economic and rapid fluorescence turn-on sensing of heparin. Generally, H-aggregates are considered as serious problem in the field of biomolecular sensing, owing to their poorly emissive nature resulting from excitonic interaction. To the best of our knowledge, this is the first report, where contrastingly, the turn-on emission from the H-aggregates has been utilized in the biomolecule sensing scheme, and enables a very efficient and selective detection of a vital biomolecule and a drug with its extensive medical applications, i.e., heparin. Our sensor system offers several advantages including, emission in the biologically advantageous red-region, dual sensing, i.e., both by fluorimetry and colorimetry, and most importantly constructed from in-expensive commercially available dye molecule, which is expected to impart a large impact on the sensing field of heparin. Our system displays good performance in complex biological media of serum samples. The novel Thioflavin-T aggregate emission could be also used to probe the interaction of heparin with its only clinically approved antidote, Protamine.

Rippling ultrafast dynamics of suspended 2D monolayers, graphene

PubMed Central

Hu, Jianbo; Vanacore, Giovanni M.; Cepellotti, Andrea; Marzari, Nicola; Zewail, Ahmed H.

2016-01-01

Here, using ultrafast electron crystallography (UEC), we report the observation of rippling dynamics in suspended monolayer graphene, the prototypical and most-studied 2D material. The high scattering cross-section for electron/matter interaction, the atomic-scale spatial resolution, and the ultrafast temporal resolution of UEC represent the key elements that make this technique a unique tool for the dynamic investigation of 2D materials, and nanostructures in general. We find that, at early time after the ultrafast optical excitation, graphene undergoes a lattice expansion on a time scale of 5 ps, which is due to the excitation of short-wavelength in-plane acoustic phonon modes that stretch the graphene plane. On a longer time scale, a slower thermal contraction with a time constant of 50 ps is observed and associated with the excitation of out-of-plane phonon modes, which drive the lattice toward thermal equilibrium with the well-known negative thermal expansion coefficient of graphene. From our results and first-principles lattice dynamics and out-of-equilibrium relaxation calculations, we quantitatively elucidate the deformation dynamics of the graphene unit cell. PMID:27791028

Interpretation of the fluorescence signatures from vegetation

NASA Astrophysics Data System (ADS)

Buschmann, C.

Vegetation emits fluorescence as part of the energy taken up by absorption %of solar radiation from UV to the visible. This fluorescence consists of light with low intensity (only few percents of the reflected light) emitted from the leaves. The fluorescence emission of a green leaf is characterized by four bands with maxima in the blue (440 nm), green (520 nm), red (690 nm) and far red (740 nm) spectral region. The intensity of fluorescence in the maxima of the emission spectrum varies depending on the following six basic parameters which must be taken into account for the interpretation of fluorescence signatures from vegetation: (a) content of the fluorophores (ferulic acid, chlorophyll a), (b) temperature of the leaf, (c) penetration of excitation light into the leaf, (d) emission of fluorescence from the leaf (re-absorption inside the leaf tissue), (e) photosynthetic activity of the leaf, (f) non-radiative decay (heat production) parallel to the fluorescence The ratios between the intensities of the maxima (F440/F690, F440/F520, F690/F740) are used as characteristic fluorescence parameter. The wide range of changes of these ratios caused by differences in the leaf tissue (aerial interspaces, variegated/homogeneous green leaves), various types of stress (UV, photoinhibition, sun exposure, heat, water deficiency, N-deficiency) and chemicals (inhibitors, fertilizers) can be explained by changes of the six basic parameters. It will be shown that the interpretation of the fluorescence signatures, in most cases, must be based on a complex consideration of more than one of the basic parameters.

Ultrafast Dynamics of Energetic Materials

DTIC Science & Technology

2014-01-23

redistributed in condensed-phase materials. In this subproject we developed a technique termed three-dimensional IR- Raman spectroscopy that allowed us to...Fang, 2011, “The distribution of local enhancement factors in surface enhanced Raman -active substrates and the vibrational dynamics in the liquid phase...3. (invited) “Vibrational energy and molecular thermometers in liquids: Ultrafast IR- Raman spectroscopy”, Brandt C. Pein and Dana D. Dlott, To

Demonstration of Two-Atom Entanglement with Ultrafast Optical Pulses

NASA Astrophysics Data System (ADS)

Wong-Campos, J. D.; Moses, S. A.; Johnson, K. G.; Monroe, C.

2017-12-01

We demonstrate quantum entanglement of two trapped atomic ion qubits using a sequence of ultrafast laser pulses. Unlike previous demonstrations of entanglement mediated by the Coulomb interaction, this scheme does not require confinement to the Lamb-Dicke regime and can be less sensitive to ambient noise due to its speed. To elucidate the physics of an ultrafast phase gate, we generate a high entanglement rate using just ten pulses, each of ˜20 ps duration, and demonstrate an entangled Bell state with (76 ±1 )% fidelity. These results pave the way for entanglement operations within a large collection of qubits by exciting only local modes of motion.

Demonstration of Two-Atom Entanglement with Ultrafast Optical Pulses.

PubMed

Wong-Campos, J D; Moses, S A; Johnson, K G; Monroe, C

2017-12-08

We demonstrate quantum entanglement of two trapped atomic ion qubits using a sequence of ultrafast laser pulses. Unlike previous demonstrations of entanglement mediated by the Coulomb interaction, this scheme does not require confinement to the Lamb-Dicke regime and can be less sensitive to ambient noise due to its speed. To elucidate the physics of an ultrafast phase gate, we generate a high entanglement rate using just ten pulses, each of ∼20  ps duration, and demonstrate an entangled Bell state with (76±1)% fidelity. These results pave the way for entanglement operations within a large collection of qubits by exciting only local modes of motion.

Ultrafast electron dynamics in phenylalanine initiated by attosecond pulses.

PubMed

Calegari, F; Ayuso, D; Trabattoni, A; Belshaw, L; De Camillis, S; Anumula, S; Frassetto, F; Poletto, L; Palacios, A; Decleva, P; Greenwood, J B; Martín, F; Nisoli, M

2014-10-17

In the past decade, attosecond technology has opened up the investigation of ultrafast electronic processes in atoms, simple molecules, and solids. Here, we report the application of isolated attosecond pulses to prompt ionization of the amino acid phenylalanine and the subsequent detection of ultrafast dynamics on a sub-4.5-femtosecond temporal scale, which is shorter than the vibrational response of the molecule. The ability to initiate and observe such electronic dynamics in polyatomic molecules represents a crucial step forward in attosecond science, which is progressively moving toward the investigation of more and more complex systems. Copyright © 2014, American Association for the Advancement of Science.

Terahertz emission from ultrafast spin-charge current at a Rashba interface

NASA Astrophysics Data System (ADS)

Zhang, Qi; Jungfleisch, Matthias Benjamin; Zhang, Wei; Pearson, John E.; Wen, Haidan; Hoffmann, Axel

Ultrafast broadband terahertz (THz) radiation is highly desired in various fields from fundamental research in condensed matter physics to bio-chemical detection. Conventional ultrafast THz sources rely on either nonlinear optical effects or ultrafast charge currents in semiconductors. Recently, however, it was realized that ultrabroad-band THz radiation can be produced highly effectively by novel spintronics-based emitters that also make use of the electron's spin degree of freedom. Those THz-emitters convert a spin current flow into a terahertz electromagnetic pulse via the inverse spin-Hall effect. In contrast to this bulk conversion process, we demonstrate here that a femtosecond spin current pulse launched from a CoFeB layer can also generate terahertz transients efficiently at a two-dimensional Rashba interface between two non-magnetic materials, i.e., Ag/Bi. Those interfaces have been proven to be efficient means for spin- and charge current interconversion.

Ultrafast selective transport of alkali metal ions in metal organic frameworks with subnanometer pores

PubMed Central

Zhang, Huacheng; Hou, Jue; Hu, Yaoxin; Wang, Peiyao; Ou, Ranwen; Jiang, Lei; Liu, Jefferson Zhe; Freeman, Benny D.; Hill, Anita J.; Wang, Huanting

2018-01-01

Porous membranes with ultrafast ion permeation and high ion selectivity are highly desirable for efficient mineral separation, water purification, and energy conversion, but it is still a huge challenge to efficiently separate monatomic ions of the same valence and similar sizes using synthetic membranes. We report metal organic framework (MOF) membranes, including ZIF-8 and UiO-66 membranes with uniform subnanometer pores consisting of angstrom-sized windows and nanometer-sized cavities for ultrafast selective transport of alkali metal ions. The angstrom-sized windows acted as ion selectivity filters for selection of alkali metal ions, whereas the nanometer-sized cavities functioned as ion conductive pores for ultrafast ion transport. The ZIF-8 and UiO-66 membranes showed a LiCl/RbCl selectivity of ~4.6 and ~1.8, respectively, which are much greater than the LiCl/RbCl selectivity of 0.6 to 0.8 measured in traditional porous membranes. Molecular dynamics simulations suggested that ultrafast and selective ion transport in ZIF-8 was associated with partial dehydration effects. This study reveals ultrafast and selective transport of monovalent ions in subnanometer MOF pores and opens up a new avenue to develop unique MOF platforms for efficient ion separations in the future. PMID:29487910

Ultrafast selective transport of alkali metal ions in metal organic frameworks with subnanometer pores.

PubMed

Zhang, Huacheng; Hou, Jue; Hu, Yaoxin; Wang, Peiyao; Ou, Ranwen; Jiang, Lei; Liu, Jefferson Zhe; Freeman, Benny D; Hill, Anita J; Wang, Huanting

2018-02-01

Porous membranes with ultrafast ion permeation and high ion selectivity are highly desirable for efficient mineral separation, water purification, and energy conversion, but it is still a huge challenge to efficiently separate monatomic ions of the same valence and similar sizes using synthetic membranes. We report metal organic framework (MOF) membranes, including ZIF-8 and UiO-66 membranes with uniform subnanometer pores consisting of angstrom-sized windows and nanometer-sized cavities for ultrafast selective transport of alkali metal ions. The angstrom-sized windows acted as ion selectivity filters for selection of alkali metal ions, whereas the nanometer-sized cavities functioned as ion conductive pores for ultrafast ion transport. The ZIF-8 and UiO-66 membranes showed a LiCl/RbCl selectivity of ~4.6 and ~1.8, respectively, which are much greater than the LiCl/RbCl selectivity of 0.6 to 0.8 measured in traditional porous membranes. Molecular dynamics simulations suggested that ultrafast and selective ion transport in ZIF-8 was associated with partial dehydration effects. This study reveals ultrafast and selective transport of monovalent ions in subnanometer MOF pores and opens up a new avenue to develop unique MOF platforms for efficient ion separations in the future.

Modeling ultrafast exciton migration within the electron donor domains of bulk heterojunction organic photovoltaics

DOE PAGES

Bednarz, Mateusz; Lapin, Joel; McGillicuddy, Ryan; ...

2017-02-21

Recent experimental studies revealed that charge carriers harvested by bulk heterojunction organic photovoltaics can be collected on ultrafast time scales. To investigate ultrafast exciton mobility, we construct simple, nonatomistic models of a common polymeric electron donor material. We first explore the relationship between the magnitude of energetic noise in the model Hamiltonian and the spatial extent of resulting eigenstates. We then employ a quantum master equation approach to simulate migration of chromophore-localized initial excited states. Excitons initially localized on a single chromophore at the center of the model delocalize down polymer chains and across pi-stacked chromophores through a coherent, wavelikemore » mechanism during the first few tens of femtoseconds. We explore the dependence of this coherent delocalization on coupling strength and on the magnitude of energetic noise. At longer times we observe continued migration toward a uniform population distribution that proceeds through an incoherent, diffusive mechanism. A series of simulations modeling exciton harvesting in domains of varying size demonstrates that smaller domains enhance ultrafast exciton harvesting yield. Finally, our nonatomistic model falls short of quantitative accuracy but demonstrates that excitons are mobile within electron donor domains on ultrafast time scales and that coherent exciton transport can enhance ultrafast exciton harvesting.« less

Modeling ultrafast exciton migration within the electron donor domains of bulk heterojunction organic photovoltaics

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

Bednarz, Mateusz; Lapin, Joel; McGillicuddy, Ryan

Recent experimental studies revealed that charge carriers harvested by bulk heterojunction organic photovoltaics can be collected on ultrafast time scales. To investigate ultrafast exciton mobility, we construct simple, nonatomistic models of a common polymeric electron donor material. We first explore the relationship between the magnitude of energetic noise in the model Hamiltonian and the spatial extent of resulting eigenstates. We then employ a quantum master equation approach to simulate migration of chromophore-localized initial excited states. Excitons initially localized on a single chromophore at the center of the model delocalize down polymer chains and across pi-stacked chromophores through a coherent, wavelikemore » mechanism during the first few tens of femtoseconds. We explore the dependence of this coherent delocalization on coupling strength and on the magnitude of energetic noise. At longer times we observe continued migration toward a uniform population distribution that proceeds through an incoherent, diffusive mechanism. A series of simulations modeling exciton harvesting in domains of varying size demonstrates that smaller domains enhance ultrafast exciton harvesting yield. Finally, our nonatomistic model falls short of quantitative accuracy but demonstrates that excitons are mobile within electron donor domains on ultrafast time scales and that coherent exciton transport can enhance ultrafast exciton harvesting.« less

Linking fluorescence induction curve and biomass in herbicide screening.

PubMed

Christensen, Martin G; Teicher, Harald B; Streibig, Jens C

2003-12-01

A suite of dose-response bioassays with white mustard (Sinapis alba L) and sugar beet (Beta vulgaris L) in the greenhouse and with three herbicides was used to analyse how the fluorescence induction curves (Kautsky curves) were affected by the herbicides. Bentazone, a photosystem II (PSII) inhibitor, completely blocked the normal fluorescence decay after the P-step. In contrast, fluorescence decay was still obvious for flurochloridone, a PDS inhibitor, and glyphosate, an EPSP inhibitor, which indicated that PSII inhibition was incomplete. From the numerous parameters that can be derived from OJIP-steps of the Kautsky curve the relative changes at the J-step [Fvj = (Fm - Fj)/Fm] was selected to be a common response parameter for the herbicides and yielded consistent dose-response relationships. Four hours after treatment, the response Fvj on the doses of bentazone and flurochloridone could be measured. For glyphosate, the changes of the Kautsky curve could similarly be detected 4 h after treatment in sugar beet, but only after 24 hs in S alba. The best prediction of biomass in relation to Fvj was found for bentazone. The experiments were conducted between May and August 2002 and showed that the ambient temperature and solar radiation in the greenhouse could affect dose-response relationships. If the Kautsky curve parameters should be used to predict the outcome of herbicide screening experiments in the greenhouse, where ambient radiation and temperature can only partly be controlled, it is imperative that the chosen fluorescence parameters can be used to predict accurately the resulting biomass used in classical bioassays.

Low damage electrical modification of 4H-SiC via ultrafast laser irradiation

NASA Astrophysics Data System (ADS)

Ahn, Minhyung; Cahyadi, Rico; Wendorf, Joseph; Bowen, Willie; Torralva, Ben; Yalisove, Steven; Phillips, Jamie

2018-04-01

The electrical properties of 4H-SiC under ultrafast laser irradiation in the low fluence regime (<0.50 J/cm2) are presented. The appearance of high spatial frequency laser induced periodic surface structures is observed at a fluence near 0.25 J/cm2 and above, with variability in environments like in air, nitrogen, and a vacuum. In addition to the formation of periodic surface structures, ultrafast laser irradiation results in possible surface oxidation and amorphization of the material. Lateral conductance exhibits orders of magnitude increase, which is attributed to either surface conduction or modification of electrical contact properties, depending on the initial material conductivity. Schottky barrier formation on ultrafast laser irradiated 4H-SiC shows an increase in the barrier height, an increase in the ideality factor, and sub-bandgap photovoltaic responses, suggesting the formation of photo-active point defects. The results suggest that the ultrafast laser irradiation technique provides a means of engineering spatially localized structural and electronic modification of wide bandgap materials such as 4H-SiC with relatively low surface damage via low temperature processing.

Ultrafast Three-Dimensional X-ray Imaging of Deformation Modes in ZnO Nanocrystals.

PubMed

Cherukara, Mathew J; Sasikumar, Kiran; Cha, Wonsuk; Narayanan, Badri; Leake, Steven J; Dufresne, Eric M; Peterka, Tom; McNulty, Ian; Wen, Haidan; Sankaranarayanan, Subramanian K R S; Harder, Ross J

2017-02-08

Imaging the dynamical response of materials following ultrafast excitation can reveal energy transduction mechanisms and their dissipation pathways, as well as material stability under conditions far from equilibrium. Such dynamical behavior is challenging to characterize, especially operando at nanoscopic spatiotemporal scales. In this letter, we use X-ray coherent diffractive imaging to show that ultrafast laser excitation of a ZnO nanocrystal induces a rich set of deformation dynamics including characteristic "hard" or inhomogeneous and "soft" or homogeneous modes at different time scales, corresponding respectively to the propagation of acoustic phonons and resonant oscillation of the crystal. By integrating the 3D nanocrystal structure obtained from the ultrafast X-ray measurements with a continuum thermo-electro-mechanical finite element model, we elucidate the deformation mechanisms following laser excitation, in particular, a torsional mode that generates a 50% greater electric potential gradient than that resulting from the flexural mode. Understanding of the time-dependence of these mechanisms on ultrafast scales has significant implications for development of new materials for nanoscale power generation.

Ultrafast Three-Dimensional X-ray Imaging of Deformation Modes in ZnO Nanocrystals

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

Cherukara, Mathew J.; Sasikumar, Kiran; Cha, Wonsuk

Imaging the dynamical response of materials following ultrafast excitation can reveal energy transduction mechanisms and their dissipation pathways, as well as material stability under conditions far from equilibrium. Such dynamical behaviour is challenging to characterize, especially operando at nanoscopic spatiotemporal scales. In this letter, we use x-ray coherent diffractive imaging to show that ultrafast laser excitation of a ZnO nanocrystal induces a rich set of deformation dynamics including characteristic ‘hard’ or inhomogeneous and ‘soft’ or homogeneous modes at different time scales, corresponding respectively to the propagation of acoustic phonons and resonant oscillation of the crystal. By integrating the 3D nanocrystalmore » structure obtained from the ultrafast x-ray measurements with a continuum thermo-electro-mechanical finite element model, we elucidate the deformation mechanisms following laser excitation, in particular, a torsional mode that generates a 50% greater electric potential gradient than that resulting from the flexural mode. Furthermore, understanding of the time-dependence of these mechanisms on ultrafast scales has significant implications for development of new materials for nanoscale power generation.« less

Ultrafast Three-Dimensional X-ray Imaging of Deformation Modes in ZnO Nanocrystals

DOE PAGES

Cherukara, Mathew J.; Sasikumar, Kiran; Cha, Wonsuk; ...

2016-12-27

Imaging the dynamical response of materials following ultrafast excitation can reveal energy transduction mechanisms and their dissipation pathways, as well as material stability under conditions far from equilibrium. Such dynamical behaviour is challenging to characterize, especially operando at nanoscopic spatiotemporal scales. In this letter, we use x-ray coherent diffractive imaging to show that ultrafast laser excitation of a ZnO nanocrystal induces a rich set of deformation dynamics including characteristic ‘hard’ or inhomogeneous and ‘soft’ or homogeneous modes at different time scales, corresponding respectively to the propagation of acoustic phonons and resonant oscillation of the crystal. By integrating the 3D nanocrystalmore » structure obtained from the ultrafast x-ray measurements with a continuum thermo-electro-mechanical finite element model, we elucidate the deformation mechanisms following laser excitation, in particular, a torsional mode that generates a 50% greater electric potential gradient than that resulting from the flexural mode. Furthermore, understanding of the time-dependence of these mechanisms on ultrafast scales has significant implications for development of new materials for nanoscale power generation.« less

Diiodobodipy-styrylbodipy Dyads: Preparation and Study of the Intersystem Crossing and Fluorescence Resonance Energy Transfer.

PubMed

Wang, Zhijia; Xie, Yun; Xu, Kejing; Zhao, Jianzhang; Glusac, Ksenija D

2015-07-02

2,6-Diiodobodipy-styrylbodipy dyads were prepared to study the competing intersystem crossing (ISC) and the fluorescence-resonance-energy-transfer (FRET), and its effect on the photophysical property of the dyads. In the dyads, 2,6-diiodobodipy moiety was used as singlet energy donor and the spin converter for triplet state formation, whereas the styrylbodipy was used as singlet and triplet energy acceptors, thus the competition between the ISC and FRET processes is established. The photophysical properties were studied with steady-state UV-vis absorption and fluorescence spectroscopy, electrochemical characterization, and femto/nanosecond time-resolved transient absorption spectroscopies. FRET was confirmed with steady state fluorescence quenching and fluorescence excitation spectra and ultrafast transient absorption spectroscopy (kFRET = 5.0 × 10(10) s(-1)). The singlet oxygen quantum yield (ΦΔ = 0.19) of the dyad was reduced as compared with that of the reference spin converter (2,6-diiodobodipy, ΦΔ = 0.85), thus the ISC was substantially inhibited by FRET. Photoinduced intramolecular electron transfer (ET) was studied by electrochemical data and fluorescence quenching. Intermolecular triplet energy transfer was studied with nanosecond transient absorption spectroscopy as an efficient (ΦTTET = 92%) and fast process (kTTET = 5.2 × 10(4) s(-1)). These results are useful for designing organic triplet photosensitizers and for the study of the photophysical properties.

Ultrafast investigation of photoinduced charge transfer in aminoanthraquinone pharmaceutical product

NASA Astrophysics Data System (ADS)

Zhang, Song; Sun, Simei; Zhou, Miaomiao; Wang, Lian; Zhang, Bing

2017-02-01

We investigated the mechanism of intramolecular charge transfer and the following radiationless dynamics of the excited states of 1-aminoanthraquinone using steady state and time-resolved absorption spectroscopy combined with quantum chemical calculations. Following photoexcitation with 460 nm, conformational relaxation via twisting of the amino group, charge transfer and the intersystem crossing (ISC) processes have been established to be the major relaxation pathways responsible for the ultrafast nonradiative of the excited S1 state. Intramolecular proton transfer, which could be induced by intramolecular hydrogen bonding is inspected and excluded. Time-dependent density functional theory (TDDFT) calculations reveal the change of the dipole moments of the S0 and S1 states along the twisted coordinate of the amino group, indicating the mechanism of twisted intra-molecular charge transfer (TICT). The timescale of TICT is measured to be 5 ps due to the conformational relaxation and a barrier on the S1 potential surface. The ISC from the S1 state to the triplet manifold is a main deactivation pathway with the decay time of 28 ps. Our results observed here have yield a physically intuitive and complete picture of the photoinduced charge transfer and radiationless dynamics in anthraquinone pharmaceutial products.

Detailed Study of BSA Adsorption on Micro- and Nanocrystalline Diamond/β-SiC Composite Gradient Films by Time-Resolved Fluorescence Microscopy.

PubMed

Handschuh-Wang, Stephan; Wang, Tao; Druzhinin, Sergey I; Wesner, Daniel; Jiang, Xin; Schönherr, Holger

2017-01-24

The adsorption of bovine serum albumin (BSA) on micro- and nanocrystalline diamond/β-SiC composite films synthesized using the hot filament chemical vapor deposition (HFCVD) technique has been investigated by confocal fluorescence lifetime imaging microscopy. BSA labeled with fluorescein isothiocyanate (FITC) was employed as a probe. The BSA FITC conjugate was found to preferentially adsorb on both O-/OH-terminated microcrystalline and nanocrystalline diamond compared to the OH-terminated β-SiC, resulting in an increasing amount of BSA adsorbed to the gradient surfaces with an increasing diamond/β-SiC ratio. The different strength of adsorption (>30 times for diamond with a grain size of 570 nm) coincides with different surface energy parameters and differing conformational changes upon adsorption. Fluorescence data of the adsorbed BSA FITC on the gradient film with different diamond coverage show a four-exponential decay with decay times of 3.71, 2.54, 0.66, and 0.13 ns for a grain size of 570 nm. The different decay times are attributed to the fluorescence of thiourea fluorescein residuals of linked FITC distributed in BSA with different dye-dye and dye-surface distances. The longest decay time was found to correlate linearly with the diamond grain size. The fluorescence of BSA FITC undergoes external dynamic fluorescence quenching on the diamond surface by H- and/or sp 2 -defects and/or by amorphous carbon or graphite phases. An acceleration of the internal fluorescence concentration quenching in BSA FITC because of structural changes of albumin due to adsorption, is concluded to be a secondary contributor. These results suggest that the micro- and nanocrystalline diamond/β-SiC composite gradient films can be utilized to spatially control protein adsorption and diamond crystallite size, which facilitates systematic studies at these interesting (bio)interfaces.

Extracting the time scales of conformational dynamics from single-molecule single-photon fluorescence statistics.

PubMed

Shang, Jianyuan; Geva, Eitan

2007-04-26

The quenching rate of a fluorophore attached to a macromolecule can be rather sensitive to its conformational state. The decay of the corresponding fluorescence lifetime autocorrelation function can therefore provide unique information on the time scales of conformational dynamics. The conventional way of measuring the fluorescence lifetime autocorrelation function involves evaluating it from the distribution of delay times between photoexcitation and photon emission. However, the time resolution of this procedure is limited by the time window required for collecting enough photons in order to establish this distribution with sufficient signal-to-noise ratio. Yang and Xie have recently proposed an approach for improving the time resolution, which is based on the argument that the autocorrelation function of the delay time between photoexcitation and photon emission is proportional to the autocorrelation function of the square of the fluorescence lifetime [Yang, H.; Xie, X. S. J. Chem. Phys. 2002, 117, 10965]. In this paper, we show that the delay-time autocorrelation function is equal to the autocorrelation function of the square of the fluorescence lifetime divided by the autocorrelation function of the fluorescence lifetime. We examine the conditions under which the delay-time autocorrelation function is approximately proportional to the autocorrelation function of the square of the fluorescence lifetime. We also investigate the correlation between the decay of the delay-time autocorrelation function and the time scales of conformational dynamics. The results are demonstrated via applications to a two-state model and an off-lattice model of a polypeptide.

Online multispectral fluorescence lifetime values estimation and overlay onto tissue white-light video frames

NASA Astrophysics Data System (ADS)

Gorpas, Dimitris; Ma, Dinglong; Bec, Julien; Yankelevich, Diego R.; Marcu, Laura

2016-03-01

Fluorescence lifetime imaging has been shown to be a robust technique for biochemical and functional characterization of tissues and to present great potential for intraoperative tissue diagnosis and guidance of surgical procedures. We report a technique for real-time mapping of fluorescence parameters (i.e. lifetime values) onto the location from where the fluorescence measurements were taken. This is achieved by merging a 450 nm aiming beam generated by a diode laser with the excitation light in a single delivery/collection fiber and by continuously imaging the region of interest with a color CMOS camera. The interrogated locations are then extracted from the acquired frames via color-based segmentation of the aiming beam. Assuming a Gaussian profile of the imaged aiming beam, the segmentation results are fitted to ellipses that are dynamically scaled at the full width of three automatically estimated thresholds (50%, 75%, 90%) of the Gaussian distribution's maximum value. This enables the dynamic augmentation of the white-light video frames with the corresponding fluorescence decay parameters. A fluorescence phantom and fresh tissue samples were used to evaluate this method with motorized and hand-held scanning measurements. At 640x512 pixels resolution the area of interest augmented with fluorescence decay parameters can be imaged at an average 34 frames per second. The developed method has the potential to become a valuable tool for real-time display of optical spectroscopy data during continuous scanning applications that subsequently can be used for tissue characterization and diagnosis.

Determination of biological activity from fluorescence-lifetime measurements in Saccharomyces cerevisiae

NASA Astrophysics Data System (ADS)

Rudek, F.; Baselt, T.; Lempe, B.; Taudt, C.; Hartmann, P.

2015-03-01

The importance of fluorescence lifetime measurement as an optical analysis tool is growing. Many applications already exist in order to determine the fluorescence lifetime, but the majority of these require the addition of fluorescence-active substances to enable measurements. Every usage of such foreign materials has an associated risk. This paper investigates the use of auto-fluorescing substances in Saccharomyces cerevisiae (Baker's yeast) as a risk free alternative to fluorescence-active substance enabled measurements. The experimental setup uses a nitrogen laser with a pulse length of 350 ps and a wavelength of 337 nm. The excited sample emits light due to fluorescence of NADH/NADPH and collagen. A fast photodiode collects the light at the output of an appropriate high-pass edge-filter at 400 nm. Fluorescence lifetimes can be determined from the decay of the measurement signals, which in turn characterizes the individual materials and their surrounding environment. Information about the quantity of the fluorescence active substances can also be measured based on the received signal intensity. The correlation between the fluorescence lifetime and the metabolic state of Saccharomyces cerevisiae was investigated and is presented here.

Simple and robust generation of ultrafast laser pulse trains using polarization-independent parallel-aligned thin films

NASA Astrophysics Data System (ADS)

Wang, Andong; Jiang, Lan; Li, Xiaowei; Wang, Zhi; Du, Kun; Lu, Yongfeng

2018-05-01

Ultrafast laser pulse temporal shaping has been widely applied in various important applications such as laser materials processing, coherent control of chemical reactions, and ultrafast imaging. However, temporal pulse shaping has been limited to only-in-lab technique due to the high cost, low damage threshold, and polarization dependence. Herein we propose a novel design of ultrafast laser pulse train generation device, which consists of multiple polarization-independent parallel-aligned thin films. Various pulse trains with controllable temporal profile can be generated flexibly by multi-reflections within the splitting films. Compared with other pulse train generation techniques, this method has advantages of compact structure, low cost, high damage threshold and polarization independence. These advantages endow it with high potential for broad utilization in ultrafast applications.

Fluorescence lifetime as a new parameter in analytical cytology measurements

NASA Astrophysics Data System (ADS)

Steinkamp, John A.; Deka, Chiranjit; Lehnert, Bruce E.; Crissman, Harry A.

1996-05-01

A phase-sensitive flow cytometer has been developed to quantify fluorescence decay lifetimes on fluorochrome-labeled cells/particles. This instrument combines flow cytometry (FCM) and frequency-domain fluorescence spectroscopy measurement principles to provide unique capabilities for making phase-resolved lifetime measurements, while preserving conventional FCM capabilities. Cells are analyzed as they intersect a high-frequency, intensity-modulated (sine wave) laser excitation beam. Fluorescence signals are processed by conventional and phase-sensitive signal detection electronics and displayed as frequency distribution histograms. In this study we describe results of fluorescence intensity and lifetime measurements on fluorescently labeled particles, cells, and chromosomes. Examples of measurements on intrinsic cellular autofluorescence, cells labeled with immunofluorescence markers for cell- surface antigens, mitochondria stains, and on cellular DNA and protein binding fluorochromes will be presented to illustrate unique differences in measured lifetimes and changes caused by fluorescence quenching. This innovative technology will be used to probe fluorochrome/molecular interactions in the microenvironment of cells/chromosomes as a new parameter and thus expand the researchers' understanding of biochemical processes and structural features at the cellular and molecular level.

Single-electron pulses for ultrafast diffraction

PubMed Central

Aidelsburger, M.; Kirchner, F. O.; Krausz, F.; Baum, P.

2010-01-01

Visualization of atomic-scale structural motion by ultrafast electron diffraction and microscopy requires electron packets of shortest duration and highest coherence. We report on the generation and application of single-electron pulses for this purpose. Photoelectric emission from metal surfaces is studied with tunable ultraviolet pulses in the femtosecond regime. The bandwidth, efficiency, coherence, and electron pulse duration are investigated in dependence on excitation wavelength, intensity, and laser bandwidth. At photon energies close to the cathode’s work function, the electron pulse duration shortens significantly and approaches a threshold that is determined by interplay of the optical pulse width and the acceleration field. An optimized choice of laser wavelength and bandwidth results in sub-100-fs electron pulses. We demonstrate single-electron diffraction from polycrystalline diamond films and reveal the favorable influences of matched photon energies on the coherence volume of single-electron wave packets. We discuss the consequences of our findings for the physics of the photoelectric effect and for applications of single-electron pulses in ultrafast 4D imaging of structural dynamics. PMID:21041681

Ultrafast dynamics of multi-exciton state coupled to coherent vibration in zinc chlorin aggregates for artificial photosynthesis.

PubMed

Shi, Tongchao; Liu, Zhengzheng; Miyatake, Tomohiro; Tamiaki, Hitoshi; Kobayashi, Takayoshi; Zhang, Zeyu; Du, Juan; Leng, Yuxin

2017-11-27

Ultrafast vibronic dynamics induced by the interaction of the Frenkel exciton with the coherent molecular vibrations in a layer-structured zinc chlorin aggregates prepared for artificial photosynthesis have been studied by 7.1 fs real-time vibrational spectroscopy with multi-spectrum detection. The fast decay of 100 ± 5fs is ascribed to the relaxation from the higher multi-exciton state (MES) to the one-exciton state, and the slow one of 863 ± 70fs is assigned to the relaxation from Q-exciton state to the dark nonfluorescent charge-transfer (CT) state, respectively. In addition, the wavelength dependences of the exciton-vibration coupling strength are found to follow the zeroth derivative of the transient absorption spectra of the exciton. It could be explained in term of the transition dipole moment modulated by dynamic intensity borrowing between the B transition and the Q transition through the vibronic interactions.

Parametric spectro-temporal analyzer (PASTA) for ultrafast optical performance monitoring

NASA Astrophysics Data System (ADS)

Zhang, Chi; Wong, Kenneth K. Y.

2013-12-01

Ultrafast optical spectrum monitoring is one of the most challenging tasks in observing ultrafast phenomena, such as the spectroscopy, dynamic observation of the laser cavity, and spectral encoded imaging systems. However, conventional method such as optical spectrum analyzer (OSA) spatially disperses the spectrum, but the space-to-time mapping is realized by mechanical rotation of a grating, so are incapable of operating at high speed. Besides the spatial dispersion, temporal dispersion provided by dispersive fiber can also stretches the spectrum in time domain in an ultrafast manner, but is primarily confined in measuring short pulses. In view of these constraints, here we present a real-time spectrum analyzer called parametric spectro-temporal analyzer (PASTA), which is based on the time-lens focusing mechanism. It achieves a 100-MHz frame rate and can measure arbitrary waveforms. For the first time, we observe the dynamic spectrum of an ultrafast swept-source: Fourier domain mode-locked (FDML) laser, and the spectrum evolution of a laser cavity during its stabilizing process. In addition to the basic single-lens structure, the multi-lens configurations (e.g. telescope or wide-angle scope) will provide a versatile operating condition, which can zoom in to achieve 0.05-nm resolution and zoom out to achieve 10-nm observation range, namely 17 times zoom in/out ratio. In view of the goal of achieving spectrum analysis with fine accuracy, PASTA provides a promising path to study the real-time spectrum of some dynamic phenomena and non-repetitive events, with orders of magnitude enhancement in the frame rate over conventional OSAs.

rf streak camera based ultrafast relativistic electron diffraction.

PubMed

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

2009-01-01

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

Four-dimensional ultrafast electron microscopy of phase transitions

PubMed Central

Grinolds, Michael S.; Lobastov, Vladimir A.; Weissenrieder, Jonas; Zewail, Ahmed H.

2006-01-01

Reported here is direct imaging (and diffraction) by using 4D ultrafast electron microscopy (UEM) with combined spatial and temporal resolutions. In the first phase of UEM, it was possible to obtain snapshot images by using timed, single-electron packets; each packet is free of space–charge effects. Here, we demonstrate the ability to obtain sequences of snapshots (“movies”) with atomic-scale spatial resolution and ultrashort temporal resolution. Specifically, it is shown that ultrafast metal–insulator phase transitions can be studied with these achieved spatial and temporal resolutions. The diffraction (atomic scale) and images (nanometer scale) we obtained manifest the structural phase transition with its characteristic hysteresis, and the time scale involved (100 fs) is now studied by directly monitoring coordinates of the atoms themselves. PMID:17130445

3D microstructuring inside glass by ultrafast laser

NASA Astrophysics Data System (ADS)

Sugioka, Koji; Hanada, Yasutaka; Midorikawa, Katsumi; Kawano, Hiroyuki; Ishikawa, Ikuko S.; Miyawaki, Atsushi

2012-01-01

We demonstrate three-dimensional (3D) microstructuring inside glass by ultrafast laser to fabricate microfluidic chips integrated with some functional microcomponents such as optical attenuators and optical waveguides. The fabricated microchips are applied to understand phenomena and functions of microorganisms and cyanobacteria. Ultrafast laser irradiation followed by thermal treatment and wet etching in dilute hydrofluoric acid solution resulted in fabrication of 3D microfludic structures embedded in a photosensitive glass. The embedded microfludic structures enabled us to easily and efficiently observe Phormidium gliding to the seedling root, which accelerates growth of the vegetable. In addition, integration of optical attenuators and optical waveguides into the microfluidic structures clarified the mechanism of the gliding movement of Phormidium. We termed such integrated microchips nanoaquariums, realizing the highly efficient and functional observation and analysis of various microorganisms.

Real-time visualization of soliton molecules with evolving behavior in an ultrafast fiber laser

NASA Astrophysics Data System (ADS)

Liu, Meng; Li, Heng; Luo, Ai-Ping; Cui, Hu; Xu, Wen-Cheng; Luo, Zhi-Chao

2018-03-01

Ultrafast fiber lasers have been demonstrated to be great platforms for the investigation of soliton dynamics. The soliton molecules, as one of the most fascinating nonlinear phenomena, have been a hot topic in the field of nonlinear optics in recent years. Herein, we experimentally observed the real-time evolving behavior of soliton molecule in an ultrafast fiber laser by using the dispersive Fourier transformation technology. Several types of evolving soliton molecules were obtained in our experiments, such as soliton molecules with monotonically or chaotically evolving phase, flipping and hopping phase. These results would be helpful to the communities interested in soliton nonlinear dynamics as well as ultrafast laser technologies.

Two-Photon Excitation, Fluorescence Microscopy, and Quantitative Measurement of Two-Photon Absorption Cross Sections

NASA Astrophysics Data System (ADS)

DeArmond, Fredrick Michael

As optical microscopy techniques continue to improve, most notably the development of super-resolution optical microscopy which garnered the Nobel Prize in Chemistry in 2014, renewed emphasis has been placed on the development and use of fluorescence microscopy techniques. Of particular note is a renewed interest in multiphoton excitation due to a number of inherent properties of the technique including simplified optical filtering, increased sample penetration, and inherently confocal operation. With this renewed interest in multiphoton fluorescence microscopy, comes an increased demand for robust non-linear fluorescent markers, and characterization of the associated tool set. These factors have led to an experimental setup to allow a systematized approach for identifying and characterizing properties of fluorescent probes in the hopes that the tool set will provide researchers with additional information to guide their efforts in developing novel fluorophores suitable for use in advanced optical microscopy techniques as well as identifying trends for their synthesis. Hardware was setup around a software control system previously developed. Three experimental tool sets were set up, characterized, and applied over the course of this work. These tools include scanning multiphoton fluorescence microscope with single molecule sensitivity, an interferometric autocorrelator for precise determination of the bandwidth and pulse width of the ultrafast Titanium Sapphire excitation source, and a simplified fluorescence microscope for the measurement of two-photon absorption cross sections. Resulting values for two-photon absorption cross sections and two-photon absorption action cross sections for two standardized fluorophores, four commercially available fluorophores, and ten novel fluorophores are presented as well as absorption and emission spectra.

Photon-assisted electron energy loss spectroscopy and ultrafast imaging.

PubMed

Howie, Archie

2009-08-01

A variety of ways is described in which photons can be used not only for ultrafast electron microscopy but also to enormously widen the energy range of spatially-resolved electron spectroscopy. Periodic chains of femtosecond laser pulses are a particularly important and accurately timed source for single-shot imaging and diffraction as well as for several forms of pump-probe microscopy at even higher spatial resolution and sub-picosecond timing. Many exciting new fields are opened up for study by these developments. Ultrafast, single shot diffraction with intense pulses of X-rays supplemented by phase retrieval techniques may eventually offer a challenging alternative and purely photon-based route to dynamic imaging at high spatial resolution.

Excited state intramolecular proton transfer reaction of 4'-N,N-diethylamino-3-hydroxyflavone and solvation dynamics in room temperature ionic liquids studied by optical Kerr gate fluorescence measurement.

PubMed

Kimura, Yoshifumi; Fukuda, Masanori; Suda, Kayo; Terazima, Masahide

2010-09-16

Fluorescence dynamics of 4'-N,N-diethylamino-3-hydroxyflavone (DEAHF) and its methoxy derivative (DEAMF) in various room temperature ionic liquids (RTILs) have been studied mainly by an optical Kerr gate method. DEAMF showed a single band fluorescence whose peak shifted with time by the solvation dynamics. The averaged solvation time determined by the fluorescence peak shift was proportional to the viscosity of the solvent except for tetradecyltrihexylphosphonium bis(trifluoromethanesulfonyl)amide. The solvation times were consistent with reported values determined with different probe molecules. DEAHF showed dual fluorescence due to the normal and tautomer forms produced by the excited state intramolecular proton transfer (ESIPT), and the relative intensities were dependent on the time and the solvent cation or anion species. By using the information of the fluorescence spectrum of DEAMF, the fluorescence spectrum of DEAHF at each delay time after the photoexcitation was decomposed into the normal and the tautomer fluorescence components, respectively. The normal component showed a very fast decay simulated by a biexponential function (2-3 and 20-30 ps) with an additional slower decay component. The tautomer component showed a rise with the time constants corresponding to the faster decay of the normal form with an additional instantaneous rise. The faster dynamics of the normal and tautomer population changes were assigned to the ESIPT process, while the slower decay of the fluorescence was attributed to the population decay from the excited state through the radiative and nonradiative processes. The average ESIPT time was much faster than the averaged solvation time of RTILs. Basically, the ESIPT kinetics in RTILs is similar to those in conventional liquid solvents like acetonitrile (Chou et al. J. Phys. Chem. A 2005, 109, 3777). The faster ESIPT is interpreted in terms of the activation barrierless process from the Franck-Condon state before the solvation of

The use of one- and two- photon induced fluorescence spectroscopy for the optical characterization of carcinogenic aflatoxins

NASA Astrophysics Data System (ADS)

Smeesters, L.; Meulebroeck, W.; Raeymaekers, S.; Thienpont, H.

2014-09-01

Carcinogenic and toxic contaminants in food and feed products are nowadays mostly detected by destructive, time-consuming chemical analyses, like HPLC and LC-MS/MS methods. However, as a consequence of the severe and growing regulations on food products by the European Union, there arose an increased demand for the ultra-fast, high-sensitive and non-destructive detection of contaminants in food and feed products. Therefore, we have investigated fluorescence spectroscopy for the characterization of carcinogenic aflatoxins. With the use of a tunable titanium-sapphire laser in combination with second and third harmonic wavelength generation, both one- and two-photon induced fluorescence excitation wavelengths could be generated using the same setup. We characterized and compared the one- and two-photon induced fluorescence spectra of pure aflatoxin powder, after excitation with 365nm and 730nm respectively. Moreover, we investigated the absolute fluorescence intensity as function of the excitation power density. Afterwards, we applied our characterization setup to the detection of aflatoxins in maize grains. The fluorescence spectra of both healthy and contaminated maize samples were experimentally characterized. In addition to the fluorescence spectrum of the pure aflatoxin, we observed an unwanted influence of the intrinsic fluorescence of the maize. Depending on the excitation wavelength, a varying contrast between the fluorescence spectra of the healthy and contaminated samples was obtained. After a comparison of the measured fluorescence signals, a detection criterion for the optical identification of the contaminated maize samples could be defined. As a result, this illustrates the use of fluorescence spectroscopy as a valuable tool for the non-destructive, real-time and high-sensitive detection of aflatoxins in maize.

Fluorescence lifetimes of anthracycline drugs in phospholipid bilayers determined by frequency-domain fluorometry

NASA Astrophysics Data System (ADS)

Burke, Thomas G.; Malak, Henryk M.; Doroshow, James H.

1990-05-01

Time-resolved fluorescence intensity decay data from anthracycline anticancer drugs present in model membranes were obtained using a gigahertz frequency-domain fluorometer [Lakowicz et al. (1986) Rev. Sci. Instrum. 57, 2499-2506]. Exciting light of 290 nm, modulated at multiple frequencies from 8 MHz to 400 MHz, was used to study the interactions of Adriamycin, daunomycin and related antibiotics with small unilamellar vesicles composed of dimyristoylphosphatidylcholine (DMPC) at 28°C. Fluorescence decay data for drug molecules free in solution as well as bound to membranes were best fit by exponentials requiring two terms rather than by single exponential decays. For example, one-component analysis of the decay data for Adriamycin free in phosphate buffered saline (PBS) solution resulted in a reduced x2 value of 140 ((tau) = 0.88 ns), while a two-component fit resulted in a substantially smaller reduced x2 value of 2.6 ((tau)1 = 1.13 ns, (alpha)1 = 0.60, (tau)2 = 0.30 ns). Upon association with membranes, each of the anthracyclines studied displayed a larger r1 value while the r2 value remained the same or increased (for example, DMPC-bound Adriamycin showed r1 = 1.68 ns , a1 = 0 . 64 , r2 = 0 . 33 ns) . Analyses of the fluorescence emission decays of anthracyclines were also made assuming each decay is composed of a single Lorentzian distribution of lifetimes. Data taken on Adriamycin in PBS, when fit using one continuous component, displayed (tau), (alpha), w, and reduced x2 values of 0.68 ns, 1, 0.60 ns, and 9.1, respectively. The distribution became quite broad upon drug association with membrane (DMPCbound Adriamycin: (tau) = 0.75 ns, (alpha) = 1, w = 2.24 ns, x2 = 13). For each anthracycline studied, continuous component fits showed significant broadening in the distributions upon drug association with membrane. Relatively large shifts in lifetime values were observed for the carminomycin and 4-demethoxydaunomycin analogues upon binding model lipid membranes

The Ultrafast Wolff Rearrangement in the Gas Phase

NASA Astrophysics Data System (ADS)

Steinbacher, Andreas; Roeding, Sebastian; Brixner, Tobias; Nuernberger, Patrick

The Wolff rearrangement of gas-phase 5-diazo Meldrum's acid is disclosed with femtosecond ion spectroscopy. Distinct differences are found for 267 nm and 200 nm excitation, the latter leading to even two ultrafast rearrangement reactions.

Fluorescence detection and photodynamic activity of endogenous protoporphyrin in human skin

NASA Astrophysics Data System (ADS)

Koenig, Karsten; Rueck, Angelika C.; Schneckenburger, Herbert

1992-07-01

Human skin shows a strong autofluorescence in the red spectral region with main peaks around 600, 620, and 640 nm caused by the porphyrin production of the gram positive lipophile skin bacterium Propionibacterium acnes. Irradiation of these bacteria reduces the integral fluorescence intensity and induces the formation of photoproducts with fluorescence bands around 670 nm and decay times of about 1 and 5 ns. The photoproduct formation is connected with an increased absorption in the red spectral region. The endogenous fluorescent porphyrins act as photosensitizers. Photodestruction of Propionibacteria acnes by visible light appears therefore to be a promising therapy. The photodynamic activity of the photoproducts was lower than that of protoporphyrin IX.

Characterization of wave phenomena in the relaxation of flash-induced chlorophyll fluorescence yield in cyanobacteria.

PubMed

Deák, Zsuzsanna; Sass, László; Kiss, Eva; Vass, Imre

2014-09-01

Fluorescence yield relaxation following a light pulse was studied in various cyanobacteria under aerobic and microaerobic conditions. In Synechocystis PCC 6803 fluorescence yield decays in a monotonous fashion under aerobic conditions. However, under microaerobic conditions the decay exhibits a wave feature showing a dip at 30-50 ms after the flash followed by a transient rise, reaching maximum at ~1s, before decaying back to the initial level. The wave phenomenon can also be observed under aerobic conditions in cells preilluminated with continuous light. Illumination preconditions cells for the wave phenomenon transiently: for few seconds in Synechocystis PCC 6803, but up to one hour in Thermosynechocystis elongatus BP-1. The wave is eliminated by inhibition of plastoquinone binding either to the QB site of Photosystem-II or the Qo site of cytochrome b6f complex by 3-(3',4'-dichlorophenyl)-1,1-dimethylurea or 2,5-dibromo-3-methyl-6-isopropyl-p-benzoquinone, respectively. The wave is also absent in mutants, which lack either Photosystem-I or the NAD(P)H-quinone oxidoreductase (NDH-1) complex. Monitoring the redox state of the plastoquinone pool revealed that the dip of the fluorescence wave corresponds to transient oxidation, whereas the following rise to re-reduction of the plastoquinone pool. It is concluded that the unusual wave feature of fluorescence yield relaxation reflects transient oxidation of highly reduced plastoquinone pool by Photosystem-I followed by its re-reduction from stromal components via the NDH-1 complex, which is transmitted back to the fluorescence yield modulator primary quinone electron acceptor via charge equilibria. Potential applications of the wave phenomenon in studying photosynthetic and respiratory electron transport are discussed. This article is part of a special issue entitled: photosynthesis research for sustainability: keys to produce clean energy. Copyright © 2014 Elsevier B.V. All rights reserved.

Cooperative bi-exponential decay of dye emission coupled via plasmons.

PubMed

Lyvers, David P; Moazzezi, Mojtaba; de Silva, Vashista C; Brown, Dean P; Urbas, Augustine M; Rostovtsev, Yuri V; Drachev, Vladimir P

2018-06-22

Bi-exponential decay of dye fluorescence near the surface of plasmonic metamaterials and core-shell nanoparticles is shown to be an intrinsic property of the coupled system. Indeed, the Dicke, cooperative states involve two groups of transitions: super-radiant, from the most excited to the ground states and sub-radiant, which cannot reach the ground state. The relaxation in the sub-radiant system occurs mainly due to the interaction with the plasmon modes. Our theory shows that the relaxation leads to the population of the sub-radiant states by dephasing the super-radiant Dicke states giving rise to the bi-exponential decay in agreement with the experiments. We use a set of metamaterial samples consisting of gratings of paired silver nanostrips coated with Rh800 dye molecules, having resonances in the same spectral range. The bi-exponential decay is demonstrated for Au\\SiO 2 \\ATTO655 core-shell nanoparticles as well, which persists even when averaging over a broad range of the coupling parameter.

Ultrafast X-Ray Spectroscopy of Conical Intersections

NASA Astrophysics Data System (ADS)

Neville, Simon P.; Chergui, Majed; Stolow, Albert; Schuurman, Michael S.

2018-06-01

Ongoing developments in ultrafast x-ray sources offer powerful new means of probing the complex nonadiabatically coupled structural and electronic dynamics of photoexcited molecules. These non-Born-Oppenheimer effects are governed by general electronic degeneracies termed conical intersections, which play a key role, analogous to that of a transition state, in the electronic-nuclear dynamics of excited molecules. Using high-level ab initio quantum dynamics simulations, we studied time-resolved x-ray absorption (TRXAS) and photoelectron spectroscopy (TRXPS) of the prototypical unsaturated organic chromophore, ethylene, following excitation to its S2(π π*) state. The TRXAS, in particular, is highly sensitive to all aspects of the ensuing dynamics. These x-ray spectroscopies provide a clear signature of the wave packet dynamics near conical intersections, related to charge localization effects driven by the nuclear dynamics. Given the ubiquity of charge localization in excited state dynamics, we believe that ultrafast x-ray spectroscopies offer a unique and powerful route to the direct observation of dynamics around conical intersections.

Direct Imaging of Frenkel Exciton Transport by Ultrafast Microscopy.

PubMed

Zhu, Tong; Wan, Yan; Huang, Libai

2017-07-18

Long-range transport of Frenkel excitons is crucial for achieving efficient molecular-based solar energy harvesting. Understanding of exciton transport mechanisms is important for designing materials for solar energy applications. One major bottleneck in unraveling of exciton transport mechanisms is the lack of direct measurements to provide information in both spatial and temporal domains, imposed by the combination of fast energy transfer (typically ≤1 ps) and short exciton diffusion lengths (typically ≤100 nm). This challenge requires developing experimental tools to directly characterize excitation energy transport, and thus facilitate the elucidation of mechanisms. To address this challenge, we have employed ultrafast transient absorption microscopy (TAM) as a means to directly image exciton transport with ∼200 fs time resolution and ∼50 nm spatial precision. By mapping population in spatial and temporal domains, such approach has unraveled otherwise obscured information and provided important parameters for testing exciton transport models. In this Account, we discuss the recent progress in imaging Frenkel exciton migration in molecular crystals and aggregates by ultrafast microscopy. First, we establish the validity of the TAM methods by imaging singlet and triplet exciton transport in a series of polyacene single crystals that undergo singlet fission. A new singlet-mediated triplet transport pathway has been revealed by TAM, resulting from the equilibrium between triplet and singlet exciton populations. Such enhancement of triplet exciton transport enables triplet excitons to migrate as singlet excitons and leads to orders of magnitude faster apparent triplet exciton diffusion rate in the picosecond and nanosecond time scales, favorable for solar cell applications. Next we discuss how information obtained by ultrafast microscopy can evaluate coherent effects in exciton transport. We use tubular molecular aggregates that could support large exciton

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

PubMed

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

2016-10-01

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

Time-Domain Fluorescence Lifetime Imaging Techniques Suitable for Solid-State Imaging Sensor Arrays

PubMed Central

Li, David Day-Uei; Ameer-Beg, Simon; Arlt, Jochen; Tyndall, David; Walker, Richard; Matthews, Daniel R.; Visitkul, Viput; Richardson, Justin; Henderson, Robert K.

2012-01-01

We have successfully demonstrated video-rate CMOS single-photon avalanche diode (SPAD)-based cameras for fluorescence lifetime imaging microscopy (FLIM) by applying innovative FLIM algorithms. We also review and compare several time-domain techniques and solid-state FLIM systems, and adapt the proposed algorithms for massive CMOS SPAD-based arrays and hardware implementations. The theoretical error equations are derived and their performances are demonstrated on the data obtained from 0.13 μm CMOS SPAD arrays and the multiple-decay data obtained from scanning PMT systems. In vivo two photon fluorescence lifetime imaging data of FITC-albumin labeled vasculature of a P22 rat carcinosarcoma (BD9 rat window chamber) are used to test how different algorithms perform on bi-decay data. The proposed techniques are capable of producing lifetime images with enough contrast. PMID:22778606

Ultrafast Brain MRI: Clinical Deployment and Comparison to Conventional Brain MRI at 3T.

PubMed

Prakkamakul, Supada; Witzel, Thomas; Huang, Susie; Boulter, Daniel; Borja, Maria J; Schaefer, Pamela; Rosen, Bruce; Heberlein, Keith; Ratai, Eva; Gonzalez, Gilberto; Rapalino, Otto

2016-09-01

To compare an ultrafast brain magnetic resonance imaging (MRI) protocol to the conventional protocol in motion-prone inpatient clinical settings. This retrospective study was HIPAA compliant and approved by the Institutional Review Board with waived inform consent. Fifty-nine inpatients (30 males, 29 females; mean age 55.1, range 23-93 years)who underwent 3-Tesla brain MRI using ultrafast and conventional protocols, both including five sequences, were included in the study. The total scan time for five ultrafast sequences was 4 minutes 59 seconds. The ideal conventional acquisition time was 10 minutes 32 seconds but the actual acquisition took 15-20 minutes. The average scan times for ultrafast localizers, T1-weighted, T2-weighted, fluid-attenuated inversion recovery (FLAIR), diffusion-weighted, T2*-weighted sequences were 14, 41, 62, 96, 80, 6 seconds, respectively. Two blinded neuroradiologists independently assessed three aspects: (1) image quality, (2) gray-white matter (GM-WM) differentiation, and (3) diagnostic concordance for the detection of six clinically relevant imaging findings. Wilcoxon signed-rank test was used to compare image quality and GM-WM scores. Interobserver reproducibility was calculated. The ultrafast T1-weighted sequence demonstrated significantly better image quality (P = .005) and GM-WM differentiation (P < .001) compared to the conventional sequence. There was high agreement (>85%) between both protocols for the detection of mass-like lesion, hemorrhage, diffusion restriction, WM FLAIR hyperintensities, subarachnoid FLAIR hyperintensities, and hydrocephalus. The ultrafast protocol achieved at least comparable image quality and high diagnostic concordance compared to the conventional protocol. This fast protocol can be a viable option to replace the conventional protocol in motion-prone inpatient clinical settings. Copyright © 2016 by the American Society of Neuroimaging.

Fusion of Ultraviolet-Visible and Infrared Transient Absorption Spectroscopy Data to Model Ultrafast Photoisomerization.

PubMed

Debus, Bruno; Orio, Maylis; Rehault, Julien; Burdzinski, Gotard; Ruckebusch, Cyril; Sliwa, Michel

2017-08-03

Ultrafast photoisomerization reactions generally start at a higher excited state with excess of internal vibrational energy and occur via conical intersections. This leads to ultrafast dynamics which are difficult to investigate with a single transient absorption spectroscopy technique, be it in the ultraviolet-visible (UV-vis) or infrared (IR) domain. On one hand, the information available in the UV-vis domain is limited as only slight spectral changes are observed for different isomers. On the other hand, the interpretation of vibrational spectra is strongly hindered by intramolecular relaxation and vibrational cooling. These limitations can be circumvented by fusing UV-vis and IR transient absorption spectroscopy data in a multiset multivariate curve resolution analysis. We apply this approach to describe the spectrodynamics of the ultrafast cis-trans photoisomerization around the C-N double bond observed for aromatic Schiff bases. Twisted intermediate states could be elucidated, and isomerization was shown to occur through a continuous complete rotation. More broadly, data fusion can be used to rationalize a vast range of ultrafast photoisomerization processes of interest in photochemistry.

Ultrafast terahertz electrodynamics of photonic and electronic nanostructures

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

Luo, Liang

This thesis summarizes my work on using ultrafast laser pulses to study Terahertz (THz) electrodynamics of photonic and electronic nanostructures and microstructures. Ultrafast timeresolved (optical, NIR, MIR, THz) pump-probe spectroscopy setup has been successfully built, which enables me to perform a series of relevant experiments. Firstly, a novel high e ciency and compact THz wave emitter based on split-ring-resonators has been developed and characterized. The emitter can be pumped at any wavelength by tailoring the magnetic resonance and could generate gapless THz waves covering the entire THz band. Secondly, two kinds of new photonic structures for THz wave manipulation havemore » been successfully designed and characterized. One is based on the 1D and 2D photo-imprinted di ractive elements. The other is based on the photoexcited double-split-ring-resonator metamaterials. Both structures are exible and can modulate THz waves with large tunability. Thirdly, the dark excitons in semiconducting singlewalled carbon nanotubes are studied by optical pump and THz probe spectroscopy, which provides the rst insights into the THz responses of nonequilibrium excitonic correlations and dynamics from the dark ground states in carbon nanotubes. Next, several on-going projects are brie y presented such as the study of ultrafast THz dynamics of Dirac fermions in topological insulator Bi 2Se 3 with Mid-infrared excitation. Finally, the thesis ends with a summary of the completed experiments and an outlook of the future plan.« less

Light-induced pyroelectric effect as an effective approach for ultrafast ultraviolet nanosensing

NASA Astrophysics Data System (ADS)

Wang, Zhaona; Yu, Ruomeng; Pan, Caofeng; Li, Zhaoling; Yang, Jin; Yi, Fang; Wang, Zhong Lin

2015-09-01

Zinc oxide is potentially a useful material for ultraviolet detectors; however, a relatively long response time hinders practical implementation. Here by designing and fabricating a self-powered ZnO/perovskite-heterostructured ultraviolet photodetector, the pyroelectric effect, induced in wurtzite ZnO nanowires on ultraviolet illumination, has been utilized as an effective approach for high-performance photon sensing. The response time is improved from 5.4 s to 53 μs at the rising edge, and 8.9 s to 63 μs at the falling edge, with an enhancement of five orders in magnitudes. The specific detectivity and the responsivity are both enhanced by 322%. This work provides a novel design to achieve ultrafast ultraviolet sensing at room temperature via light-self-induced pyroelectric effect. The newly designed ultrafast self-powered ultraviolet nanosensors may find promising applications in ultrafast optics, nonlinear optics, optothermal detections, computational memories and biocompatible optoelectronic probes.

Four-Dimensional Ultrafast Electron Microscopy: Insights into an Emerging Technique.

PubMed

Adhikari, Aniruddha; Eliason, Jeffrey K; Sun, Jingya; Bose, Riya; Flannigan, David J; Mohammed, Omar F

2017-01-11

Four-dimensional ultrafast electron microscopy (4D-UEM) is a novel analytical technique that aims to fulfill the long-held dream of researchers to investigate materials at extremely short spatial and temporal resolutions by integrating the excellent spatial resolution of electron microscopes with the temporal resolution of ultrafast femtosecond laser-based spectroscopy. The ingenious use of pulsed photoelectrons to probe surfaces and volumes of materials enables time-resolved snapshots of the dynamics to be captured in a way hitherto impossible by other conventional techniques. The flexibility of 4D-UEM lies in the fact that it can be used in both the scanning (S-UEM) and transmission (UEM) modes depending upon the type of electron microscope involved. While UEM can be employed to monitor elementary structural changes and phase transitions in samples using real-space mapping, diffraction, electron energy-loss spectroscopy, and tomography, S-UEM is well suited to map ultrafast dynamical events on materials surfaces in space and time. This review provides an overview of the unique features that distinguish these techniques and also illustrates the applications of both S-UEM and UEM to a multitude of problems relevant to materials science and chemistry.

Ultrafast Surface-Enhanced Raman Probing of the Role of Hot Electrons in Plasmon-Driven Chemistry.

PubMed

Brandt, Nathaniel C; Keller, Emily L; Frontiera, Renee R

2016-08-18

Hot electrons generated through plasmonic excitations in metal nanostructures show great promise for efficiently driving chemical reactions with light. However, the lifetime, yield, and mechanism of action of plasmon-generated hot electrons involved in a given photocatalytic process are not well understood. Here, we develop ultrafast surface-enhanced Raman scattering (SERS) as a direct probe of plasmon-molecule interactions in the plasmon-catalyzed dimerization of 4-nitrobenzenethiol to p,p'-dimercaptoazobenzene. Ultrafast SERS probing of these molecular reporters in plasmonic hot spots reveals transient Fano resonances, which we attribute to near-field coupling of Stokes-shifted photons to hot electron-driven metal photoluminescence. Surprisingly, we find that hot spots that yield more photoluminescence are much more likely to drive the reaction, which indirectly proves that plasmon-generated hot electrons induce the photochemistry. These ultrafast SERS results provide insight into the relative reactivity of different plasmonic hot spot environments and quantify the ultrafast lifetime of hot electrons involved in plasmon-driven chemistry.

Double-Wall Carbon Nanotubes for Wide-Band, Ultrafast Pulse Generation

PubMed Central

2014-01-01

We demonstrate wide-band ultrafast optical pulse generation at 1, 1.5, and 2 μm using a single-polymer composite saturable absorber based on double-wall carbon nanotubes (DWNTs). The freestanding optical quality polymer composite is prepared from nanotubes dispersed in water with poly(vinyl alcohol) as the host matrix. The composite is then integrated into ytterbium-, erbium-, and thulium-doped fiber laser cavities. Using this single DWNT–polymer composite, we achieve 4.85 ps, 532 fs, and 1.6 ps mode-locked pulses at 1066, 1559, and 1883 nm, respectively, highlighting the potential of DWNTs for wide-band ultrafast photonics. PMID:24735347

Ultrafast electron transport across nano gaps in nanowire circuits

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

Potma, Eric O.

In this Program we aim for a closer look at electron transfer through single molecules. To achieve this, we use ultrafast laser pulses to time stamp an electron tunneling event in a molecule that is connected between two metallic electrodes, while reading out the electron current. A key aspect of this project is the use of metallic substrates with plasmonic activity to efficiently manipulate the tunneling probability. The first Phase of this program is concerned with developing highly sensitive tools for the ultrafast optical manipulation of tethered molecules through the evanescent surface field of plasmonic substrates. The second Phase ofmore » the program aims to use these tools for exercising control over the electron tunneling probability.« less

10-fs-level synchronization of photocathode laser with RF-oscillator for ultrafast electron and X-ray sources

PubMed Central

Yang, Heewon; Han, Byungheon; Shin, Junho; Hou, Dong; Chung, Hayun; Baek, In Hyung; Jeong, Young Uk; Kim, Jungwon

2017-01-01

Ultrafast electron-based coherent radiation sources, such as free-electron lasers (FELs), ultrafast electron diffraction (UED) and Thomson-scattering sources, are becoming more important sources in today’s ultrafast science. Photocathode laser is an indispensable common subsystem in these sources that generates ultrafast electron pulses. To fully exploit the potentials of these sources, especially for pump-probe experiments, it is important to achieve high-precision synchronization between the photocathode laser and radio-frequency (RF) sources that manipulate electron pulses. So far, most of precision laser-RF synchronization has been achieved by using specially designed low-noise Er-fibre lasers at telecommunication wavelength. Here we show a modular method that achieves long-term (>1 day) stable 10-fs-level synchronization between a commercial 79.33-MHz Ti:sapphire laser oscillator and an S-band (2.856-GHz) RF oscillator. This is an important first step toward a photocathode laser-based femtosecond RF timing and synchronization system that is suitable for various small- to mid-scale ultrafast X-ray and electron sources. PMID:28067288

10-fs-level synchronization of photocathode laser with RF-oscillator for ultrafast electron and X-ray sources

NASA Astrophysics Data System (ADS)

Yang, Heewon; Han, Byungheon; Shin, Junho; Hou, Dong; Chung, Hayun; Baek, In Hyung; Jeong, Young Uk; Kim, Jungwon

2017-01-01

Ultrafast electron-based coherent radiation sources, such as free-electron lasers (FELs), ultrafast electron diffraction (UED) and Thomson-scattering sources, are becoming more important sources in today’s ultrafast science. Photocathode laser is an indispensable common subsystem in these sources that generates ultrafast electron pulses. To fully exploit the potentials of these sources, especially for pump-probe experiments, it is important to achieve high-precision synchronization between the photocathode laser and radio-frequency (RF) sources that manipulate electron pulses. So far, most of precision laser-RF synchronization has been achieved by using specially designed low-noise Er-fibre lasers at telecommunication wavelength. Here we show a modular method that achieves long-term (>1 day) stable 10-fs-level synchronization between a commercial 79.33-MHz Ti:sapphire laser oscillator and an S-band (2.856-GHz) RF oscillator. This is an important first step toward a photocathode laser-based femtosecond RF timing and synchronization system that is suitable for various small- to mid-scale ultrafast X-ray and electron sources.

10-fs-level synchronization of photocathode laser with RF-oscillator for ultrafast electron and X-ray sources.

PubMed

Yang, Heewon; Han, Byungheon; Shin, Junho; Hou, Dong; Chung, Hayun; Baek, In Hyung; Jeong, Young Uk; Kim, Jungwon

2017-01-09

Ultrafast electron-based coherent radiation sources, such as free-electron lasers (FELs), ultrafast electron diffraction (UED) and Thomson-scattering sources, are becoming more important sources in today's ultrafast science. Photocathode laser is an indispensable common subsystem in these sources that generates ultrafast electron pulses. To fully exploit the potentials of these sources, especially for pump-probe experiments, it is important to achieve high-precision synchronization between the photocathode laser and radio-frequency (RF) sources that manipulate electron pulses. So far, most of precision laser-RF synchronization has been achieved by using specially designed low-noise Er-fibre lasers at telecommunication wavelength. Here we show a modular method that achieves long-term (>1 day) stable 10-fs-level synchronization between a commercial 79.33-MHz Ti:sapphire laser oscillator and an S-band (2.856-GHz) RF oscillator. This is an important first step toward a photocathode laser-based femtosecond RF timing and synchronization system that is suitable for various small- to mid-scale ultrafast X-ray and electron sources.

Monitoring of photoluminescence decay by alkali and alkaline earth metal cations using a photoluminescent bolaamphiphile self-assembly as an optical probe.

PubMed

Kim, Sunhyung; Kwak, Jinyoung; Lee, Sang-Yup

2014-05-01