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At least 55 records · Page 3

Gold Quantum Rods: Modulation of Singlet and Triplet Exciton Populations by the Rod Length

Abstract Gold quantum rods (QRs) of Au60, Au78, Au96, and Au114 (protected by thiolate ligands) exhibit exclusive fluorescence, which is different from the shorter Au42 QR with dual emission (fluorescence + phosphorescence). Herein, we report the excitation wavelength-dependent near-infrared-II photoluminescence (PL) and exciton dynamics of this series of QRs. Interestingly, the fluorescence quantum yield (QY) of the QRs is much higher (2–10×) when the lowest singlet excited state (S1) is excited compared to the excitation of high-lying states (Sn). A metastable intermediate singlet state (denoted S′) is identified by transient absorption spectroscopy when Sn is excited, and this S′ state leads to fast “skybridge” intersystem crossing (ISC), which contributes primarily (>60%) to the total triplet population. With increasing aspect ratio (AR) of QRs (from 6.3 to 18.7), nonradiative processes accelerate, leading to fast decay of the S1 state (hence, less QY) and of the T1 state (barely phosphorescent). A detailed energy flow mechanism is determined for the QRs after photoexcitation, which offers a design principle for manipulation of exciton dynamics toward potential utilization of higher excited states in applications.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Fluorescence from polystyrene - Photochemical processes in polymeric systems, 7

Results are presented for measurements of the fluorescence spectra of polystyrene in dilute solution and in pure solid films. It is determined that a major potential source of experimental error is the concurrent photooxidative degradation in air which may obscure fluorescence emission from monomeric sites in solid films at 25 C. The fluorescence spectra of oriented films are evaluated in terms of the monomer to excimer fluorescence intensity ratio and the excimer 'red shift'. The monomer to excimer fluorescence intensity ratio is determined to be significantly higher in fluid solution than in solid film.

Gupta, M. C.↗

Ca(+) emission in the sunlit ionosphere

In the course of a program of twilight airglow observations, the resonance fluorescence emissions from calcium ions were measured. In particular, twilight sequences were obtained during the period of December 19-22, 1987, which coincided with the Ursids meteorite shower. During this meteorite event the intensities of the Ca(+) emission lines at 3934A increased to the point that the surface brightness profiles could be inverted to volume emission rate profiles. These profiles show evidence for strong spatial redistribution of the Ca(+) over the course of three days. Observations of these emissions during meteor shower periods could provide a valuable tracer for the processes responsible for the transport of ions in the D, E, and F region, allowing the full altitude and latitude extent of the distribution to be determined.

Torr, Marsha R.↗

Very High Spectral Resolution Imaging Spectroscopy: the Fluorescence Explorer (FLEX) Mission

The Fluorescence Explorer (FLEX) mission has been recently selected as the 8th Earth Explorer by the European Space Agency (ESA). It will be the first mission specifically designed to measure from space vegetation fluorescence emission, by making use of very high spectral resolution imaging spectroscopy techniques. Vegetation fluorescence is the best proxy to actual vegetation photosynthesis which can be measurable from space, allowing an improved quantification of vegetation carbon assimilation and vegetation stress conditions, thus having key relevance for global mapping of ecosystems dynamics and aspects related with agricultural production and food security. The FLEX mission carries the FLORIS spectrometer, with a spectral resolution in the range of 0.3 nm, and is designed to fly in tandem with Copernicus Sentinel-3, in order to provide all the necessary spectral / angular information to disentangle emitted fluorescence from reflected radiance, and to allow proper interpretation of the observed fluorescence spatial and temporal dynamics.

Moreno, Jose F.↗

K I 7699 A emission from the Betelgeuse shell

A map of the circumstellar gas shell around Betelgeuse is presented from observations of the fluorescent emission in the K I 7699 A resonance line. The observations obtained at 3 sec and 5 sec from the star indicate approximate spherical symmetry in the 10 km/s expanding shell responsible for the blueshifted sharp cores seen in strong resonance and low excitation lines. Calculations show that the density of neutral K atoms is approximately constant between 3 sec and 5 sec from the star. The emission profiles in the west show a second, higher velocity, component at 5 sec from the star.

Bernat, A. P.↗

Laboratory studies of UV emissions of H2 by electron impact - The Werner- and Lyman-band systems

The vacuum ultraviolet electron-impact-induced fluorescence emissions of H2 were studied for the Lyman and Werner band systems in the range of 120-170 nm, using an optical system containing a photomultiplier and a spectrometer, over an energy range from threshold to 400 eV. The emission cross sections for the Lyman and Werner transitions at 100 eV are determined. The cross-section ratio is in excellent agreement with theoretical calculations and experimental data for the optical oscillator strengths. The cross-section for cascading to the B state is stated as a percentage of the total emission cross section at both 100 and 300 eV, increasing substantially at 20 eV. The vibrational population distribution of the B state is found to be a function of electron-impact energy as the importance of cascading relative to direct excitation changes with electron-impact energy.

Ajello, J. M.↗

Mechanism of the Non‐Kasha Fluorescence in Pyrene

The high-energy shoulder in the gas-phase fluorescence emission spectrum of pyrene is a well-known example of non-Kasha emission. Here, we comparatively assess two approaches, vibronic perturbation theory and nonadiabatic dynamics, in their ability to predict and explain the gas-phase fluorescence spectrum of pyrene. While both methods qualitatively capture the non-Kasha emission, they differ in their computational requirements, accuracy, and physical interpretation. Vibronic perturbation theory and nonadiabatic dynamics are complementary and can be combined in a two-step approach to non-Kasha fluorescence.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High-pressure ruby and diamond fluorescence - Observations at 0.21 to 0.55 terapascal

A diamond-anvil, high-pressure apparatus was used to extend the upper pressure limit of static laboratory experiments. Shifts of the R1 strong fluorescent line of ruby were observed that correspond to static pressures of 0.21 to 0.55 terapascal (2.1 to 5.5 megabars) at 25 C. Sensitive spectroscopic techniques in the pressure range 0.15 to 0.28 terapascal were used to observe ruby and diamond fluorescence separately; these two fluorescent emissions overlap strongly at high pressures. At pressures greater than approximately 0.28 terapascal, the diamond fluorescence diminished and the ruby fluorescence reappeared strongly. Pressure was determined by extrapolation of the calibrated shift of the ruby R1 line.

Xu, J. A.↗

Characterization of marine macroalgae by fluorescence signatures

The feasibility of distinguishing macroalgal classes by their fluorescence signatures was investigated using narrow-waveband light to excite groups of accessory pigments in brown, red, and green macroalgae and measuring fluorescence emission at 685 nm. Results obtained on 20 marine macroalgae field-collected samples showed that fluorescence excitation signatures were relatively uniform within phylogenetic classes but were substantially different for different classes. It is suggested that it may be possible to characterize the type and the abundance of subtidal macroalgae from low-flying aircraft using existing laser-induced fluorescence methodology.

Topinka, J. A.↗

Distinct Secondary Structures of the Leucine-Rich Repeat Proteoglycans Decorin and Biglycan: Glycosylation-Dependent Conformational Stability

Biglycan and decorin, closely related small leucine-rich repeat proteoglycans, have been overexpressed in eukaryotic cers and two major glycoforms isolated under native conditions: a proteoglycan substituted with glycosaminoglycan chains; and a core protein form secreted devoid of glycosaminoglycans. A comparative biophysical study of these glycoforms has revealed that the overall secondary structures of biglycan and decorin are different. Far-UV Circular Dichroism (CD) spectroscopy of decorin and biglycan proteoglycans indicates that, although they are predominantly Beta-sheet, biglycan has a significantly higher content of alpha-helical structure. Decorin proteoglycan and core protein are very similar, whereas the biglycan core protein exhibits closer similarity to the decorin glycoforms than to. the biglycan proteoglycan form. However, enzymatic removal of the chondroitin sulfate chains from biglycan proteoglycan does not induce a shift to the core protein structure, suggesting that the fmal form is influenced by polysaccharide addition only during biosynthesis. Fluorescence emission spectroscopy demonstrated that the single tryptophan residue, which is at a conserved position at the C-terminal domain of both biglycan and decorin, is found in similar microenvironments. This indicates that at least in this specific domain, the different glycoforms do exhibit apparent conservation of structure. Exposure of decorin and biglycan to 10 M urea resulted in an increase in fluorescent intensity, which indicates that the emission from tryptophan in the native state is quenched. Comparison of urea-induced protein unfolding curves provided further evidence that decorin and biglycan assume different structures in solution. Decorin proteoglycan and core protein unfold in a manner similar to a classic two-state model, in which there is a steep transition to an unfolded state between 1-2 M urea. The biglycan core protein also shows a similar steep transition. However, biglycan proteoglycan shows a broad unfolding transition between 1-6 M urea, probably indicating the presence of stable unfolding intermediates.

Krishnan, Priya↗

Molecular Hydrogen in the Quiescent Disk of SW UMa

The FUSE observation has been reduced and a paper has been submitted to ApJ. The analysis has been slow because of the very noisy quality of the data, but we have derived line profile information for O VI and limits to the continuum brightness which place an interesting limit on the white dwarf temperature. The primary results are that a narrow O VI emission component seems to arise from the accretion flow onto the white dwarf itself, in agreement with cooling flow models for the X-ray spectra of low accretion rate dwarf novae. The broad component of the O VI lines is weaker than the observed C IV emission, suggesting that the UV line emission from the disk comes from photoionized plasma. A secondary result is that there is no H-2 fluorescent emission. The upper limits indicate that if molecular gas is present in the disk, it is shielded from Ly alpha photons by a layer of atomic hydrogen on the disk surface. We also derive an upper limit to the continuum level is below that observed by IUE. The limits are compatible with the lower end of the WD temperature range derived from IUE measurements, and they appear to agree with unpublished analysis of HST spectra. The grant has provided partial support for a data aide (Matt Povich) and a postdoc (Alex Lobel). It purchased a computer for M. Menou.

Raymond, John C.↗

Ultraviolet emission of the Vela supernova remnant and the Cygnus Loop

Ultraviolet emission spectra of several filaments in the Vela supernova remnant and the Cygnus Loop are compared with theoretical models of radiative shocks. Shock velocities range from 85 to 130 km/s. Little or no grain depletion is apparent. Several of the observed filaments deviate from the steady-flow models in the sense that much of the photoionization-recombination zone is absent. It is shown that resonance line scattering within the emitting region can account for the weakness of the C II 1335 and C IV 1550 lines. Evaporation fronts, which are basic to the McKee and Ostriker picture of supernova remnant evolution, do not contribute significantly to the observed emission. Some discrepancies in UV emission predicted by different sets of shock models are traced to differing atomic rates used in the calculations. A fluorescent emission line of H2 may be observable in some supernova remnants.

Raymond, J. C.↗

Optical spectroscopy of a highly fluorescent aggregate of bacteriochlorophyll c

Bacteriochlorophyll (BChl) c and a similar model compound, Mg-methyl bacteriopheophorbide d, form several types of aggregates in nonpolar solvents. One of these aggregates is highly fluorescent, with a quantum yield higher than that of the monomer. This aggregate is also unusual in that it shows a rise time in its fluorescence emission decay at certain wavelengths, which is ascribed to a change in conformation of the aggregate. An analysis of fluorescence depolarization data is consistent with either a linear aggregate of four or five monomers or preferably a cyclic arrangement of three dimers.

NASA Discipline Exobiology↗

Spatially Resolved Galactic Wind in Lensed Galaxy RCSGA 032727-132609

We probe the spatial distribution of outflowing gas along four lines of sight separated by up to 6 kpc in a gravitationally lensed star-forming galaxy at z = 1.70. Using Mg II and Fe II emission and absorption as tracers, we find that the clumps of star formation are driving galactic outflows with velocities of − 170 to − 250 km/s. The velocities of Mg II emission are redshifted with respect to the systemic velocities of the galaxy, consistent with being backscattered. By contrast, the Fe II fluorescent emission lines are either slightly blueshifted or at the systemic velocity of the galaxy. Taken together, the velocity structure of the Mg II and Fe II emission is consistent with arising through scattering in galactic winds. Assuming a thin shell geometry for the outflowing gas, the estimated masses carried out by these outflows are large (approx 30-50 M/yr), with mass loading factors several times the star formation rate. Almost 20 per cent to 50 per cent of the blueshifted absorption probably escapes the gravitational potential of the galaxy. In this galaxy, the outflow is 'locally sourced', that is, the properties of the outflow in each line of sight are dominated by the properties of the nearest clump of star formation; the wind is not global to the galaxy. The mass outflow rates and the momentum flux carried out by outflows in individual star-forming knots of this object are comparable to that of starburst galaxies in the local Universe.

Bordoloi, Rongmon↗

A Quantum Band Model of the nu3 Fundamental of Methanol (CH3OH) and Its Application to Fluorcescence Spectra of Comets

Methanol (CH3OH) radiates efficiently at infrared wavelengths, dominating the C-H stretching region in comets, yet inadequate quantum-mechanical models have imposed limits on the practical use of its emission spectra. Accordingly, we constructed a new line-by-line model for the 3 fundamental band of methanol at 2844 / cm (3.52 micron) and applied it to interpret cometary fluorescence spectra. The new model permits accurate synthesis of line-by-line spectra for a wide range of rotational temperatures, ranging from 10 K to more than 400 K.We validated the model by comparing simulations of CH3OH fluorescent emission with measured spectra of three comets (C/2001 A2 LINEAR, C/2004 Q2 Machholz and 8P/Tuttle) acquired with high-resolution infrared spectrometers at high-altitude sites. The new model accurately describes the complex emission spectrum of the nu3 band, providing distinct rotational temperatures and production rates at greatly improved confidence levels compared with results derived from earlier fluorescence models. The new model reconciles production rates measured at infrared and radio wavelengths in C/2001 A2 (LINEAR). Methanol can now be quantified with unprecedented precision and accuracy in astrophysical sources through high-dispersion spectroscopy at infrared wavelengths

Villanueva, Geronimo L.↗

Study of the Many Fluorescent Lines and the Absorption Variability in GX 301-2 with XMM-Newton

We present an in-depth study of the High Mass X-ray Binary (HMXB) GX 301-2 during its pre-periastron flare using data from the XMM-Newton satellite. The energy spectrum shows a power law continuum absorbed by a large equivalent hydrogen column on the order of 10(exp 24)/ sq cm and a prominent Fe K-alpha fluorescent emission line. Besides the Fe K-alpha line, evidence for Fe K-Beta, Ni K-alpha, Ni K-Beta, S K-alpha, Ar K-alpha, Ca K-alpha, and Cr K-alpha fluorescent lines is found. The observed line strengths are consistent with fluorescence in a cold absorber. This is the first time that Cr K-alpha is seen in emission in the X-ray spectrum of a HMXB. In addition to the modulation by the strong pulse period of approx 685 sec the source is highly variable and shows different states of activity. We perform time-resolved as well as pulse-to-pulse resolved spectroscopy to investigate differences between these states of activity. We find that fluorescent line fluxes are strongly variable and generally follow the overall flux. The N-H value is variable by a factor of 2, but not correlated to continuum normalization. We find an interval of low flux in the light curve in which the pulsations cease almost completely, without any indication of an increasing absorption column. We investigate this dip in detail and argue that it is most likely that during the dip the accretion ceased and the afterglow of the fluorescent iron accounted for the main portion of the X-ray flux. A similar dip was found earlier in RXTE data, and we compare our findings to these results.

Fuerst, F.↗

Outer layers of a carbon star: The view from the Hubble Space Telescope

To advance our understanding of the relationship between stellar chromospheres and mass loss, which is a common property of carbon stars and other asymptotic giant branch stars, we have obtained ultraviolet spectra of the nearby N-type carbon star UU Aur using the Hubble Space Telescope (HST). In this paper we describe the HST observations, identify spectral features in both absorption and emission, and attempt to infer the velocity field in the chromosphere, upper troposphere, and circumstellar envelope from spectral line shifts. A mechanism for producing fluoresced emission to explain a previously unobserved emission line is proposed. Some related ground-based observations are also described.

Johnson, H. R.↗

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

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

Garcia, Christopher S.↗