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The fluorescence and fluorescence excitation spectra of the perylene cation isolated in neon and argon matrices are reported. This is the first report of the fluorescence spectrum of a polycyclic aromatic hydrocarbon ion in any phase.
A flow-visualization technique, known as the fluorescent-oil film method, has been developed which appears to be generally simpler and to require less experience and development of technique than previously published methods. The method is especially adapted to use in the large high-powered wind tunnels which require considerable time to reach the desired test conditions. The method consists of smearing a film of fluorescent oil over a surface and observing where the thickness is affected by the shearing action of the boundary layer. These films are detected and identified, and their relative thicknesses are determined by use of ultraviolet light. Examples are given of the use of this technique. Other methods that show promise in the study of boundary-layer conditions are described. These methods include the use of a temperature-sensitive fluorescent paint and the use of a radiometer that is sensitive to the heat radiation from a surface. Some attention is also given to methods that can be used with a spray apparatus in front of the test model.
Green fluorescent protein (GFP) from jellyfish Aequorea Victoria has become a popular marker for e.g. mutagenesis work. Its fluorescent property, which originates from a chromophore located in the center of the molecule, makes it widely applicable as a research too]. GFP clones have been produced with a variety of spectral properties, such as blue and yellow emitting species. The protein is a single chain of molecular weight 27 kDa and its structure has been determined at 1.9 Angstrom resolution. The combination of GFP's fluorescent property, the knowledge of its several crystallization conditions, and its increasing use in biophysical and biochemical studies, all led us to consider it as a model material for macromolecular crystal growth studies. Initial preparations of GFP were from E.coli with yields of approximately 5 mg/L of culture media. Current yields are now in the 50 - 120 mg/L range, and we hope to further increase this by expression of the GFP gene in the Pichia system. The results of these efforts and of preliminary crystal growth studies will be presented.
Vegetational changes are primary indicators of the present and future ecological status of the globe. These are changes which not only impact upon the primary productivity, but the total of the biogeochemical processes occurring on the planet. The impacts of global climatic and other environmental changes on vegetation must be monitored by some means in order to develop models which will allow us to predict long term effects. Large scale monitoring is now possible only with remote sensing systems, primarily passive reflectance, obtained by the use of satellite and aircraft platforms. However, passive reflectance techniques at this time are limited in their ability to detect subtle changes in the concentration and oxidation states of the many compounds involved in the light reactions of photosynthesis. Knowledge of these changes we consider to be fundamental in the remote assessment of both the rate and efficiency of photosynthesis and also the early detection of stress damage. The above factors pointed to the desirability of a sensing technique with the sensitivity and specificity necessary for detecting and quantifying those biological entities involved in photosynthesis. Another optical technique for vegetation monitoring is fluorescence. Previously, the lack of adequate excitation light sources and detector technologies have limited the use of fluorescence on intact plant leaves in the field. It is only recently with the advent of lasers with short pulse duration and advanced detector technologies that fluorescence measurements in the remote mode have become possible in the presence of ambient light.
Sodium fluorescence induced by a narrow bandwidth tunable laser has been used to measure temperature, pressure, axial velocity and species concentrations in wind tunnels, rocket engine exhausts and the upper atmosphere. Optical pumping of the ground states of the sodium, however, can radically alter the shape of the laser induced fluorescence excitation spectrum, complicating such measurements. Here a straightforward extension of rate equations originally proposed to account for the features of the pumped spectrum is to make temperature measurements from spectra taken in pumped vapor. Also determined from the spectrum is the relative fluorescence cycle number, which has application to measurement of diffusion rate and transverse flow velocity. The accuracy of both the temperature and cycle-number measurements is comparable with that of temperature measurements made in the absence of pumping.
Sodium fluorescence induced by a narrow-bandwidth tunable laser has been used to measure temperature, pressure, axial velocity, and species concentrations in wind tunnels, rocket engine exhausts, and the upper atmosphere. Optical pumping of the ground states of the sodium, however, can radically alter the shape of the laser-induced fluorescence excitation spectrum, complicating such measurements. Here a straightforward extension of rate equations originally proposed to account for the features of the pumped spectrum is used to make temperature measurements from spectra taken in pumped vapor. Also determined from the spectrum is the relative fluorescence cycle number, which has application to measurement of diffusion rate and transverse flow velocity, The accuracy of both the temperature and the cycle-number measurements is comparable with that of temperature measurements made in the absence of pumping.
This report documents work performed through the NASA Graduate Student Researchers Program, Grant No. NGT3-52316. Research performed included investigation of two-line fluorescence imaging of OH for temperature measurement and an investigation of negative flame speeds for modeling of premixed turbulent flames. The laboratory work and initial analysis of the fluorescence imaging was performed at NASA Glen Research Center with follow up analysis at Vanderbilt University. The negative flame speed investigation was performed using an opposed jet flow simulation program at Vanderbilt University. The fluorescence imaging work is presented first followed by the negative flame speed investigation.
We report spatially resolved laser-saturated fluorescence measurements of NO concentration in a pre-heated, lean-direct injection (LDI) spray flame at atmospheric pressure. The spray is produced by a hollow-cone, pressure-atomized nozzle supplied with liquid heptane. NO is excited via the Q2(26.5) transition of the gamma(0,0) band. Detection is performed in a 2-nm region centered on the gamma(0,1) band. Because of the relatively close spectral spacing between the excitation (226 nm) and detection wavelengths (236 nm), the gamma(0,1) band of NO cannot be isolated from the spectral wings of the Mie scattering signal produced by the spray. To account for the resulting superposition of the fluorescence and scattering signals, a background subtraction method has been developed that utilizes a nearby non-resonant wavelength. Excitation scans have been performed to locate the optimum off-line wavelength. Detection scans have been performed at problematic locations in the flame to determine possible fluorescence interferences from UHCs and PAHs at both the on-line and off-line excitation wavelengths. Quantitative radial NO profiles are presented and analyzed so as to better understand the operation of lean-direct injectors for gas turbine combustors.
The excited state charge transfer for a series of highly fluorescent dyes containing thiophenylimidazole moiety was investigated. These systems follow the Twisted Intramolecular Charge Transfer (TICT) model. Dual fluorescence was observed for each substituted dye. X-ray structures analysis reveals a twisted ground state geometry for the donor substituted aryl on the 4 and 5 position at the imidazole ring. The excited state charge transfer was modeled by a linear solvation energy relationship using Taft's pi and Dimroth's E(sub T)(30) as solvent parameters. There is linear relation between the energy of the fluorescence transition and solvent polarity. The degree of stabilization of the excited state charge transfer was found to be consistent with the intramolecular molecular charge transfer. Excited dipole moment was studied by utilizing the solvatochromic shift method.
We performed multispectral in-situ fluorescence measurement of colored dissolved organic matter and chlorophyll in surface water of the West Florida Shelf using West Labs Spectral absorption and Fluorescence Instrument (SAFIre). Continuous measurements underway allowed us to simultaneously map the dispersion of riverine organic material and chlorophyll on the shelf. By using two fluorescence emission ratios we were able to differentiate between riverine and marine CDOM. Our data also showed unusually high concentrations of CDOM offshore. These were attributed to an intrusion of the Mississippi River Plume. We performed limited comparisons between in-situ chlorophyll concentrations measured with SAFIre and chlorophyll values obtained from SeaWiFS satellite data using OC4 and MODIS algorithm. Our results show that, although both algorithms overestimated chlorophyll, MODIS performed better than OC4, particularly in areas with high CDOM concentrations. Analysis of the relationship between chlorophyll and CDOM concentrations within the study area showed regional variability causes by differences in river source.
A new method for generating photogrammetric targets by projecting an array of laser beams onto a membrane doped with fluorescent laser dye has recently been developed. In this paper we review this new fluorescence based technique, then proceed to show how it can be used for dynamic measurements, and how a short pulsed (10 ns) laser allows the measurement of vibration modes at frequencies several times the sampling frequency. In addition, we present experimental results showing the determination of fundamental and harmonic vibration modes of a drum style dye-doped polymer membrane tautly mounted on a 12-inch circular hoop and excited with 30 Hz and 62 Hz sinusoidal acoustic waves. The projected laser dot pattern was generated by passing the beam from a pulsed Nd:YAG laser though a diffractive optical element, and the resulting fluorescence was imaged with three digital video cameras, all of which were synchronized with a pulse and delay generator. Although the video cameras are capable of 240 Hz frame rates, the laser s output was limited to 30 Hz and below. Consequently, aliasing techniques were used to allow the measurement of vibration modes up to 186 Hz with a Nyquist limit of less than 15 Hz.
New subarcsecond far-UV observations of T Tau with Hubble Space Telescope STIS show spatially resolved structure in the 2in. x 2in. area around the star. The structures are apparent in multiline emission of fluorescent H2 pumped by Ly(alpha). One emission structure follows the cavity walls observed around T Tau N in scattered light in the optical. A temperature of greater than or = l000 K is required to have a high enough population in the H2 to produce the observed fluorescent lines; in the cool environment of the T Tau system, shock heating is required to achieve this temperature at distances of a few tens of AU. Fluorescent H2 along the cavity wall represent the best evidence to date for the action of low-density, wide opening angle outflows driving cavities into the molecular medium at scales less than or = 100 AU. A southern region of emission consists of two arcs, with shape and orientation similar to the arcs of H2 2.12 microns and forbidden-line emission crossing the outflow associated with the embedded system T Tau S. This region is located near the centroid of forbidden-line emission at the blueshifted lobe of the north-south outflow.
Tryptophan fluorescence of reaction centers isolated from Rhodobacter sphaeroides, both stationary and time-resolved, was studied. Fluorescence kinetics were found to fit best a sum of four discrete exponential components. Half of the initial amplitude was due to a component with a lifetime of congruent to 60 ps, belonging to Trp residues, capable of efficient transfer of excitation energy to bacteriochlorophyll molecules of the reaction center. The three other components seem to be emitted by Trp ground-state conformers, unable to participate in such a transfer. Under the influence of intense actinic light, photooxidizing the reaction centers, the yield of stationary fluorescence diminished by congruent to 1.5 times, while the number of the kinetic components and their life times remained practically unchanged. Possible implications of the observed effects for the primary photosynthesis events are considered.
This grant has supported the acquisition, reduction and analysis of data targeting the structure and excitation of molecular hydrogen in the reflection nebula IC 63 and in particular the fluorescent emission seen in the UV. In addition to manpower for analyzing the FUSE data, the grant supported the (attempted) acquisition of supporting ground-based data. We proposed for and received observing time for two sets of ground based, data; narrow band imaging ([S II], [O III) at KPNO (July 2002; Observer: Burgh) and imaging spectro-photometry of several of the near-infrared rotation-vibration lines of H2 at the IRTF (October 2003; Observer: Andersson). Unfortunately, both of these runs were failures, primarily because of bad weather, and did not result in any useful data. We combined the FUSE observations with rocket borne observations of the star responsible for exciting the H2 fluorescence in IC 63: gamma Cas, and with archival HUT observations of IC 63, covering the long-wavelength part of the molecular hydrogen fluorescence.
A portable x-ray fluorescence spectrometer has a portable sensor unit containing a battery, a high voltage power supply, an x-ray tube which produces a beam x-ray radiation directed toward a target sample, and a detector for fluorescent x-rays produced by the sample. If a silicon-lithium detector is used, the sensor unit also contains either a thermoelectric or thermochemical cooler, or a small dewar flask containing liquid nitrogen to cool the detector. A pulse height analyzer (PHA) generates a spectrum of data for each sample consisting of the number of fluorescent x-rays detected as a function of their energy level. The PHA can also store spectrum data for a number of samples in the field. A processing unit can be attached to the pulse height analyzer to upload and analyze the stored spectrum data for each sample. The processing unit provides a graphic display of the spectrum data for each sample, and provides qualitative and/or quantitative analysis of the elemental composition of the sample by comparing the peaks in the sample spectrum against known x-ray energies for various chemical elements. An optional filtration enclosure can be used to filter particles from a sample suspension, either in the form of a natural suspension or a chemically created precipitate. The sensor unit is then temporarily attached to the filtration unit to analyze the particles collected by the filter medium.
Stereoscopic time-resolved visualization of three-dimensional structures in a hypersonic flow has been performed for the first time. Nitric Oxide (NO) was seeded into hypersonic boundary layer flows that were designed to transition from laminar to turbulent. A thick laser sheet illuminated and excited the NO, causing spatially-varying fluorescence. Two cameras in a stereoscopic configuration were used to image the fluorescence. The images were processed in a computer visualization environment to provide stereoscopic image pairs. Two methods were used to display these image pairs: a cross-eyed viewing method which can be viewed by naked eyes, and red/blue anaglyphs, which require viewing through red/blue glasses. The images visualized three-dimensional information that would be lost if conventional planar laser-induced fluorescence imaging had been used. Two model configurations were studied in NASA Langley Research Center's 31-Inch Mach 10 Air Wind tunnel. One model was a 10 degree half-angle wedge containing a small protuberance to force the flow to transition. The other model was a 1/3-scale, truncated Hyper-X forebody model with blowing through a series of holes to force the boundary layer flow to transition to turbulence. In the former case, low flowrates of pure NO seeded and marked the boundary layer fluid. In the latter, a trace concentration of NO was seeded into the injected N2 gas. The three-dimensional visualizations have an effective time resolution of about 500 ns, which is fast enough to freeze this hypersonic flow. The 512x512 resolution of the resulting images is much higher than high-speed laser-sheet scanning systems with similar time response, which typically measure 10-20 planes.
Nitric-oxide planar laser-induced fluorescence (NO PLIF) was used to perform velocity measurements in hypersonic flows by generating multiple tagged lines which fluoresce as they convect downstream. For each laser pulse, a single interline, progressive scan intensified CCD camera was used to obtain separate images of the initial undelayed and delayed NO molecules that had been tagged by the laser. The CCD configuration allowed for sub-microsecond acquisition of both images, resulting in sub-microsecond temporal resolution as well as sub-mm spatial resolution (0.5-mm x 0.7-mm). Determination of axial velocity was made by application of a cross-correlation analysis of the horizontal shift of individual tagged lines. Quantification of systematic errors, the contribution of gating/exposure duration errors, and influence of collision rate on fluorescence to temporal uncertainty were made. Quantification of the spatial uncertainty depended upon the analysis technique and signal-to-noise of the acquired profiles. This investigation focused on two hypersonic flow experiments: (1) a reaction control system (RCS) jet on an Orion Crew Exploration Vehicle (CEV) wind tunnel model and (2) a 10-degree half-angle wedge containing a 2-mm tall, 4-mm wide cylindrical boundary layer trip. The experiments were performed at the NASA Langley Research Center's 31-inch Mach 10 wind tunnel.
Surface-enhanced x-ray fluorescence (SEn-XRF) spectroscopy is a form of surface- enhanced spectroscopy that was conceived as a means of obtaining greater sensitivity in x-ray fluorescence (XRF) spectroscopy. As such, SEn-XRF spectroscopy joins the ranks of such other, longer-wavelength surface-enhanced spectroscopies as those based on surface-enhanced Raman scattering (SERS), surface-enhanced resonance Raman scattering (SERRS), and surfaceenhanced infrared Raman absorption (SEIRA), which have been described in previous NASA Tech Briefs articles. XRF spectroscopy has been used in analytical chemistry for determining the elemental compositions of small samples. XRF spectroscopy is rapid and quantitative and has been applied to a variety of metal and mineralogical samples. The main drawback of XRF spectroscopy as practiced heretofore is that sensitivity has not been as high as required for some applications. In SEn-XRF as in the other surface-enhanced spectroscopies, one exploits several interacting near-field phenomena, occurring on nanotextured surfaces, that give rise to local concentrations of incident far-field illumination. In this case, the far-field illumination comes from an x-ray source. Depending on the chemical composition and the geometry of a given nanotextured surface, these phenomena could include the lightning-rod effect (concentration of electric fields at the sharpest points on needlelike surface features), surface plasmon resonances, and grazing incidence geometric effects. In the far field, the observable effect of these phenomena is an increase in the intensity of the spectrum of interest - in this case, the x-ray fluorescence spectrum of chemical elements of interest that may be present within a surface layer at distances no more than a few nanometers from the surface.