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At least 343 records · Page 19

The Limitations of 5f Delocalization and Dispersion

Delocalization in the 5f states of the actinides is an important phenomenon, but poorly quantified. Here, the fundamental limitations of 5f dispersion measurements using angle and momentum resolved variants of photoelectron spectroscopy will be discussed. A novel approach will be suggested, based on a theoretical projection, which should circumvent these limitations: M4,5 X-ray emission spectroscopy. This analysis will utilize the case study of U metal, which can be considered to be the paramount example of 5f dispersion.

36 MATERIALS SCIENCE↗

Fungal elemental profiling unleashed through rapid laser-induced breakdown spectroscopy (LIBS)

Elemental profiling of fungal species as a phenotyping tool is an understudied topic and is typically performed to examine plant tissue or non-biological materials. Traditional analytical techniques such as inductively coupled plasma–optical emission spectroscopy (ICP-OES) and inductively coupled plasma–mass spectrometry (ICP-MS) have been used to identify elemental profiles of fungi; however, these techniques can be cumbersome due to the difficulty of preparing samples. Additionally, the instruments used for these techniques can be expensive to procure and operate. Laser-induced breakdown spectroscopy (LIBS) is an alternative elemental analytical technique—one that is sensitive across the periodic table, easy to use on various sample types, and is cost-effective in both procurement and operation. LIBS has not been used on axenic filamentous fungal isolates grown in substrate media. In this work, as a proof of concept, we used LIBS on two genetically distinct fungal species grown on a nutrient-rich and nutrient-poor substrate media to determine whether robust elemental profiles can be detected and whether differences between the fungal isolates can be identified. This data set contains the raw LIBS spectral data for the summarized results described inRush, et. al. 2024

elemental profiling↗

The determination of aluminum, copper, iron, and lead in glycol formulations by atomic absorption spectroscopy

Initial screening tests and the results obtained in developing procedures to determine Al, Cu, Fe, and Pb in glycol formulations are described. Atomic absorption completion was selected for Cu, Fe and Pb, and after comparison with emission spectroscopy, was selected for Al also. Before completion, carbon, iron, and lead are extracted with diethyl dithio carbamate (DDC) into methyl isobutyl ketone (MIBK). Aluminum was also extracted into MIBK using 8-hydroxyquinoline as a chelating agent. As little as 0.02 mg/l carbon and 0.06 mg/l lead or iron may be determined in glycol formulations. As little as 0.3 mg/l aluminum may be determined.

Source record↗

Optical Diagnostic Characterization of High-Power Hall Thruster Wear and Operation

Optical emission spectroscopy is employed to correlate BN insulator erosion with high-power Hall thruster operation. Specifically, actinometry leveraging excited xenon states is used to normalize the emission spectra of ground state boron as a function of thruster operating condition. Trends in the strength of the boron signal are correlated with thruster power, discharge voltage, and discharge current. In addition, the technique is demonstrated on metallic coupons embedded in the walls of the HiVHAc EM thruster. The OES technique captured the overall trend in the erosion of the coupons which boosts credibility in the method since there are no data to which to calibrate the erosion rates of high-power Hall thrusters. The boron signals are shown to trend linearly with discharge voltage for a fixed discharge current as expected. However, the boron signals of the higher-power NASA 300M and NASA 457Mv2 trend with discharge current and show an unexpectedly weak to inverse dependence on discharge voltage. Electron temperatures measured optically in the near-field plume of the thruster agree well with Langmuir probe data. However, the optical technique used to determine Te showed unacceptable sensitivity to the emission intensities. Near-field, single-frequency imaging of the xenon neutrals is also presented as a function of operating condition for the NASA 457 Mv2.

Williams, George J., Jr.↗

Hyperspectral Imaging and Spectroscopy of Fluorescently Coupled Acyl-CoA: Cholesterol Acyltransferase in Insect Cells

A high-performance hyperspectral imaging module with high throughput of light suitable for low-intensity fluorescence microscopic imaging and subsequent analysis, including single-pixel-defined emission spectroscopy, was tested on Sf21 insect cells expressing green fluorescence associated with recombinant green fluorescent protein linked or not with the membrane protein acyl-CoA:cholesterol acyltransferase. The imager utilized the phenomenon of optical activity as a new technique providing information over a spectral range of 220-1400 nm, and was inserted between the microscope and an 8-bit CCD video-rate camera. The resulting fluorescence image did not introduce observable image aberrations. The images provided parallel acquisition of well resolved concurrent spatial and spectral information such that fluorescence associated with green fluorescent protein alone was demonstrated to be diffuse within the Sf21 insect cell, and that green fluorescence associated with the membrane protein was shown to be specifically concentrated within regions of the cell cytoplasm. Emission spectra analyzed from different regions of the fluorescence image showed blue shift specific for the regions of concentration associated with the membrane protein.

Malak, H.↗

Fungal elemental profiling unleashed through rapid laser-induced breakdown spectroscopy (LIBS)

ABSTRACT Elemental profiling of fungal species as a phenotyping tool is an understudied topic and is typically performed to examine plant tissue or non-biological materials. Traditional analytical techniques such as inductively coupled plasma–optical emission spectroscopy (ICP-OES) and inductively coupled plasma–mass spectrometry (ICP-MS) have been used to identify elemental profiles of fungi; however, these techniques can be cumbersome due to the difficulty of preparing samples. Additionally, the instruments used for these techniques can be expensive to procure and operate. Laser-induced breakdown spectroscopy (LIBS) is an alternative elemental analytical technique—one that is sensitive across the periodic table, easy to use on various sample types, and is cost-effective in both procurement and operation. LIBS has not been used on axenic filamentous fungal isolates grown in substrate media. In this work, as a proof of concept, we used LIBS on two genetically distinct fungal species grown on a nutrient-rich and nutrient-poor substrate media to determine whether robust elemental profiles can be detected and whether differences between the fungal isolates can be identified. Our results demonstrate a distinct correlation between fungal species and their elemental profile, regardless of the substrate media, as the same strains shared a similar uptake of carbon, zinc, phosphorus, manganese, and magnesium, which could play a vital role in their survival and propagation. Independently, each fungal species exhibited a unique elemental profile. This work demonstrates a unique and valuable approach to rapidly phenotype fungi through optical spectroscopy, and this approach can be critical in understanding these fungi's behavior and interactions with the environment. IMPORTANCE Historically, ionomics, the elemental profiling of an organism or materials, has been used to understand the elemental composition in waste materials to identify and recycle heavy metals or rare earth elements, identify the soil composition in space exploration on the moon or Mars, or understand human disorders or disease. To our knowledge, ionomic profiling of microbes, particularly fungi, has not been investigated to answer applied and fundamental biological questions. The reason is that current ionomic analytical techniques can be laborious in sample preparation, fail to measure all potential elements accurately, are cost-prohibitive, or provide inconsistent results across replications. In our previous efforts, we explored whether laser-induced breakdown spectroscopy (LIBS) could be used in determining the elemental profiles of poplar tissue, which was successful. In this proof-of-concept endeavor, we undertook a transdisciplinary effort between applied and fundamental mycology and elemental analytical techniques to address the biological question of how LIBS can used for fungi grown axenically in a nutrient-rich and nutrient-poor environment.

59 BASIC BIOLOGICAL SCIENCES↗

Spectroscopic Signature of Metal-hydroxo and Peroxo Species in K-edge X-ray Absorption Spectra

Metal-dioxygen species are important intermediates formed during dioxygen activations by metalloenzymes in various biological processes, by catalysts in fuel cells, and prior to O 2 evolution by photosystem II. In this work, we focus on manganese-porphyrin complexes using tetramesitylporphyrin ligand (TMP) to explore changes in Mn K-edge X-ray absorption spectroscopy (XAS) associated with the formation of Mn-hydroxide and Mn–O 2 peroxide species. With limited spectroscopic characterization of these compounds, Mn K β X-ray emission spectroscopy (XES), XAS, density functional theory (DFT), and time-dependent DFT (TD-DFT) analysis will enhance our understanding of their complex electronic structure. We show that the shape of the pre-edge in the K-edge Mn X-ray absorption near-edge structure (XANES) can serve as a spectroscopic signature of the Mn III -peroxo formation and thus can be used to track the presence of the side-on peroxide as an intermediate in time-resolved or in situ experiments. In conclusion, our results will help to further summarize the spectroscopic fingerprints for peroxo and hydroxo species, addressing the challenge of identifying the reactive metal species in catalytic reactions.

Extended X-ray absorption fine structure↗

Balloon-borne cryogenic spectrometer for measurement of lower stratospheric trace constituents

A liquid-nitrogen cooled, multidetector Fourier transform spectrometer has been constructed to measure minor stratospheric constituents via high resolution, earth-limb emission spectroscopy from a balloon-borne platform. Cryogenic cooling, combined with the use of extrinsic silicon photoconductor detectors cooled to liquid-helium temperature, allows the detection of weak emission features of gaseous species. The spectrometer has two basic scan modes: the first mode records the continuous spectrum from 650-2100/cm with 0.2/cm resolution; the second simultaneously records four preselected narrow intervals (about 175/cm bandpass each) with 0.02/cm resolution, unapodized. Filtering of the interferogram signal is done by real-time, digital signal processing. The most important feature of this flat mirror Michelson system, with respect to remote balloon-borne operation, is the dynamic alignment system which maintains the relative parallelism of the two flat reflectors of the interferometer. Species identified to date in data obtained during a Nov. 6, 1984, flight include: CO2, O3, H2O, CH4, HNO3, N2O, NO2, NO, CCl3F (Freon-11) and CF2Cl2 (Freon-12).

Brasunas, J. C.↗

Influence of liquid conductance on the temporal evolution of self-organization patterns in atmospheric pressure DC glow discharges

Abstract Self-Organized Patterns (SOPs) at plasma-liquid interface in atmospheric pressure plasma discharges refer to the formation of intricate and puzzling structures due to the interplay of electrodynamic and hydrodynamic processes. Studies conducted to date have shown that this phenomenon results in the formation of distinctive patterns such as circular ring, star, gear, dots, spikes, etc., and primarily depends on working gas, electrolyte type, gap distance, current, conductivity, etc. However, an adequate understanding of how these patterns change from one type to another is still not available. This study aims to elucidate the influence of initial liquid conductance ( σ i ) on the temporal evolution of SOPs in liquid-anode discharges. The discharge was generated in a pin-to-liquid anode configuration at a constant helium (He) flow rate of 500 sccm and DC applied voltage of 6 kV at a gap distance of 12 mm. Through the gradual increment of σ i from 1.8 μ S to 4820 μ S, we observe that the trend in the evolution of SOPS takes place as solid discs, spikes, dots, rings, double rings, and stars. The continuous formation of reactive species onto the liquid anode in all conductive solutions results in a decrease in pH, an increase in bulk liquid temperature, and an increase in total dissolved solutes, and these have been confirmed through experimental measurements. Observations using optical emission spectroscopy show that the electrons at the plasma-liquid interface participate in the reduction of cations followed by their excitation & ionization due to which electron density as well as emissions from excited species (mainly hydroxyl radicals & excited nitrogen) decrease with time. Our investigation provides experimental evidence on the presence of cations at the plasma-liquid interface required for SOP formation.

Physics↗

Auger spectroscopy analysis of lubrication with zinc dialkyldithiophosphate of several metal combinations in sliding contact

Sliding friction experiments were conducted with aluminum and other riders rubbing on disks of various elemental metals in the presence of a thin film of zinc dialkyldithiophosphate (ZDP). Auger emission spectroscopy was used to in situ monitor the changes in surface chemistry with rubbing under various loads. The metal disks examined included iron, titanium, rhodium, tungsten, molybdenum, and copper. For equivalent films of ZDP the film is a more effective lubricant for some metals than it is for others. The important active element in the compound varies with the metal lubricated and is a function of metal chemistry. The zinc in the ZDP is susceptible to electron beam induced desorption.

Buckley, D. H.↗

Molecular Iodine Interactions with Fe, Ni, Cr, and Stainless Steel Alloys

The adsorption behavior of molecular iodine is important for understanding the spread of radioiodine in a nuclear accident. Prior experiments indicate that, in addition to the interaction with Fe, molecular iodine [i.e., I 2(g) ] also interacts with the next most abundant components of austenitic stainless steel (i.e., Ni, and Cr) at room temperature. Here, we investigate iodine adsorption on Fe, Ni, and Cr while focusing on understanding the variables affecting adsorption as well as the iodine compounds that are formed during adsorption. Scanning electron microscopy and energy-dispersive X-ray spectroscopy were used to characterize the surfaces of exposed metal particles and aid in the understanding of the morphology and chemistry of iodine interactions with the substrates. Inductively coupled plasma optical emission spectroscopy was used to detect low levels of metal iodides and X-ray photoelectron spectroscopy was used to confirm the formation of the metal iodides. The role of environmental factors (e.g., humidity and oxygen content) for iodine adsorption on metal substrates is addressed. The individual metals demonstrated formation of metal iodides for Fe and Ni particles from interaction with I 2(g) . The formation of metal iodides may indicate the affinity of iodine for the respective metal. In this study, the iodine affinities ranked Fe > Ni > Cr as determined by the quantity of chemisorbed iodine. This trend is also supported by the distributions and proportions of metals in the corrosion product of the stainless steels. The exposures without oxygen and humidity indicate the potential of a multistep iodine adsorption process where iodine first attacks the oxide layer and then chemisorbs to the exposed metal.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Optical Emission Characterization of High-Power Hall Thruster Wear

Optical emission spectroscopy is employed to correlate BN insulator erosion with high-power operation of the NASA 300M Hall-effect thruster. Actinometry leveraging excited xenon states is used to normalize the emission spectra of ground state boron as a function of thruster operating condition. Trends in the strength of the boron signal are correlated with thruster power, discharge voltage, discharge current and magnetic field strength. The boron signals are shown to trend with discharge current and show weak dependence on discharge voltage. The trends are consistent with data previously collected on the NASA 300M and NASA 457M thrusters but are different from conventional wisdom.

WIlliams, George J.↗

Telescope-optical system performance analysis for the Cryogenic Limb Array Etalon Spectrometer (CLAES) on the Upper Atmospheric Research Satellite

A first-order performance analysis of the CLAES telescope-optical system is presented. The experiment involves the passive measurement of earth-limb radiance over a 10-60 km tangent altitude range, and is based on a solid Fabry-Perot spectrometer which provides spectral resolution of 0.25/cm for atmospheric emission spectroscopy over the 3.5-12 micron IR range. The optical system is required to provide a high degree of off-axis rejection and stray-light control, primarily to suppress intense emission from the earth surface. The astigmatism and other geometric aberrations are corrected by a secondary mirror which produces an excellent image of the primary one, allowing for location of a diffraction control or Lyot stop. The off-axis scattering performance of the telescope is examined in terms of the mirror scatter coefficient and point source rejection ratio. A mirror bidirectional reflectance distribution function of 0.0001 at 1 deg with a 1/theta-squared roll-off between 1 and 0.2 deg is realizable based on recent measurements. This results in an off-axis radiance term that is generally small in comparison with the system-limiting NER.

Roche, A. E.↗

Hyperspectral Infrared Imaging of Flames Using a Spectrally Scanning Fabry-Perot Filter

The temperatures and compositions of gases in and around flames can be diagnosed using infrared emission spectroscopy to observe molecular band shapes and intensities. We have combined this approach with a low-order scanning Fabry-Perot filter and an infrared camera to obtain spectrally scanned infrared emission images of a laboratory flame and exhaust plume from 3.7 to 5.0 micrometers, at a spectral resolution of 0.043 micrometers, and a spatial resolution of 1 mm. The scanning filter or AIRIS (Adaptive Infrared Imaging Spectroradiometer) is a Fabry-Perot etalon operating in low order (mirror spacing = wavelength) such that the central spot, containing a monochromatic image of the scene, is viewed by the detector array. The detection system is a 128 x 128 liquid-nitrogen-cooled InSb focal plane array. The field of view is controlled by a 50 mm focal length multielement lens and an V4.8 aperture, resulting in an image 6.4 x 6.4 cm in extent at the flame and a depth of field of approximately 4 cm. Hyperspectral images above a laboratory CH4/air flame show primarily the strong emission from CO2 at 4.3 micrometers, and weaker emissions from CO and H2O. We discuss techniques to analyze the spectra, and plans to use this instrument in microgravity flame spread experiments.

Rawlins, W. T.↗

Four dimensional reconstruction and analysis of plume images

A number of methods have been investigated and are under current investigation for monitoring the health of the Space Shuttle Main Engine (SSME). Plume emission analysis has recently emerged as a potential technique for correlating the emission characteristics with the health of an engine. In order to correlate the visual and spectral signatures of the plume emission with the characteristic health monitoring features of the engine, the plume emission data must be acquired, stored, and analyzed in a manner similar to flame emission spectroscopy. The characteristic visual and spectral signatures of the elements vaporized in exhaust plume along with the features related to their temperature, pressure, and velocity can be analyzed once the images of plume emission are effectively acquired, digitized, and stored on a computer. Since the emission image varies with respect to time at a specified planar location, four dimensional visual and spectral analysis need to be performed on the plume emission data. In order to achieve this objective, feasibility research was conducted to digitize, store, analyze, and visualize the images of a subsonic jet in a cross flow. The jet structure was made visible using a direct injection flow visualization technique. The results of time-history based three dimensional reconstruction of the cross sectional images corresponding to a specific planar location of the jet structure are presented. The experimental set-up to acquire such data is described and three dimensional displays of time-history based reconstructions of the jet structure are discussed.

Dhawan, Atam P.↗

Measurements of constituents of interest in the photochemistry of the ozone layer using infrared techniques

Infrared solar spectra and infrared atmospheric emission spectra were obtained from the ground, from aircraft and from balloons. The initial detection of most stratospheric molecules was achieved by the solar spectral technique because better resolution helps remove interference from other molecules. Because the sun is an intense source of radiation, the resolution which can be obtained with good signal-to-noise, is greater than with atmospheric emission spectroscopy. Data are generally taken using a method that enhances the number of molecules in the optical path i.e. at large solar zenith angles for solar spectra and at low elevation angles for atmospheric emission spectra. The search for molecules which are predicted to be present but which, the detection of a molecule known to be present from other measurement techniques but observed for the first time in infrared solar spectra, and some further data on the variability of HNO3 are discussed.

Murcray, D. G.↗

Finite field of view effects on inversion of limb thermal emission observations

It is pointed out that the technique of thermal emission spectroscopy provides an effective means for remote sounding of stratospheric temperature structure and constituent distributions. One procedure for measuring the stratospheric infrared spectrum involves the conduction of observations along ray paths tangent to the stratospheric limb. Thermal emission limb tangent observations have certain advantages compared to other types of observations. The techniques for determining temperature and trace gas distributions from limb thermal emission radiances are based on the assumption that the bulk of opacity lies near the tangent point. Ideally, the field of view (FOV) of the observing instrument should be very small. The effect of a finite FOV is to reduce the spatial resolution of the retrieved temperature and constituent profiles. The present investigation is concerned with the effects of the FOV on the inversion of infrared thermal emission measurements for balloon platforms. Attention is given to a convenient method for determining the weighting functions.

Abbas, M. M.↗

Millisecond timescale reactions observed via X-ray spectroscopy in a 3D microfabricated fused silica mixer

Determination of electronic structures during chemical reactions remains challenging in studies which involve reactions in the millisecond timescale, toxic chemicals, and/or anaerobic conditions. Here, a three-dimensionally (3D) microfabricated microfluidic mixer platform that is compatible with time-resolved X-ray absorption and emission spectroscopy (XAS and XES, respectively) is presented. This platform, to initiate reactions and study their progression, mixes a high flow rate (0.50–1.5 ml min –1 ) sheath stream with a low-flow-rate (5–90 µl min –1 ) sample stream within a monolithic fused silica chip. The chip geometry enables hydro­dynamic focusing of the sample stream in 3D and sample widths as small as 5 µm. The chip is also connected to a polyimide capillary downstream to enable sample stream deceleration, expansion, and X-ray detection. In this capillary, sample widths of 50 µm are demonstrated. Further, convection–diffusion-reaction models of the mixer are presented. The models are experimentally validated using confocal epifluorescence microscopy and XAS/XES measurements of a ferricyanide and ascorbic acid reaction. The models additionally enable prediction of the residence time and residence time uncertainty of reactive species as well as mixing times. Residence times (from initiation of mixing to the point of X-ray detection) during sample stream expansion as small as 2.1 ± 0.3 ms are also demonstrated. Importantly, an exploration of the mixer operational space reveals a theoretical minimum mixing time of 0.91 ms. The proposed platform is applicable to the determination of the electronic structure of conventionally inaccessible reaction intermediates.

3D microfabrication↗