Search NASA⌕ Search

SEARCH · Search NASA

Results for “Spectroscopic techniques”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 1,459 records · Page 81
All sourcesNASA NTRSDOE OSTI
DOE OSTI2014

{sup 1}H NMR spectroscopic studies establish that heparanase is a retaining glycosidase

Highlights: •{sup 1}H and {sup 13}C NMR chemical shifts of fondaparinux were fully assigned by 1D and 2D NMR techniques. •Hydrolysis of fondaparinux by heparanase was monitored by {sup 1}H NMR spectroscopy. •Heparanase is established to be a retaining glycosidase. -- Abstract: Heparanase is an endo-β-glucuronidase that cleaves heparan sulfate side chains of proteoglycans in basement membranes and the extracellular matrix (ECM). Heparanase is implicated in several diverse pathological processes associated with ECM degradation such as metastasis, inflammation and angiogenesis and is thus an important target for anti-cancer and anti-inflammatory drug discovery. Heparanase has been classed as belonging to the clan A glycoside hydrolase family 79 based on sequence analysis, secondary structure predictions and mutagenic analysis, and thus it has been inferred that it is a retaining glycosidase. However, there has been no direct experimental evidence to support this conclusion. Herein we describe {sup 1}H NMR spectroscopic studies of the hydrolysis of the pentasaccharide substrate fondaparinux by heparanase, and provide conclusive evidence that heparanase hydrolyses its substrate with retention of configuration and is thus established as a retaining glycosidase. Knowledge of the mechanism of hydrolysis may have implications for future design of inhibitors for this important drug target.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2015

Contributed Review: Quantum cascade laser based photoacoustic detection of explosives

Detecting trace explosives and explosive-related compounds has recently become a topic of utmost importance for increasing public security around the world. A wide variety of detection methods and an even wider range of physical chemistry issues are involved in this very challenging area. Optical sensing methods, in particular mid-infrared spectrometry techniques, have a great potential to become a more desirable tools for the detection of explosives. The small size, simplicity, high output power, long-term reliability make external cavity quantum cascade lasers (EC-QCLs) the promising spectroscopic sources for developing analytical instrumentation. This work reviews the current technical progress in EC-QCL-based photoacoustic spectroscopy for explosives detection. The potential for both close-contact and standoff configurations using this technique is completely presented over the course of approximately the last one decade.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
NASA NTRS2004

Vibrational Spectroscopy at Cryogenic Temperatures: From the Laboratory to the Ends of the Universe

Polycyclic aromatic compounds (PAC) have been the subject of astrophysical interest for nearly two decades. Indeed, there is now evidence that these compounds are among the most abundant interstellar molecules, comprising perhaps 10 - 30% of all the carbon in our galaxy. Ranging in size from as few as 20 to as many as hundreds or thousands of carbon atoms, these molecules are enormous by interstellar standards and impact a wide range of astrophysical phenomena including: the near- and mid-infrared emission spectrum of a wide range of astronomical objects; the ultraviolet/visible/near-infrared absorption of the diffuse medium that permeates our galaxy; and the heating and cooling mechanisms of interstellar clouds. Nevertheless, until recently a lack of laboratory spectroscopic data on PAC under astrophysically relevant conditions (i.e. isolated, ionized molecules; ionized molecular clusters, etc.) has hindered critical evaluation and extension of this model. Fortunately, the last decade has seen an explosion of experimental and theoretical techniques aimed specifically at addressing these issues. Here, we begin with a brief review of the evidence for the existence and abundance of interstellar PAC. From there, we move on to an overview of the general spectroscopic characteristics of the range of isolated, neutral and ionized PAC that we have studied over the last decade. Finally, we will conclude with a consideration of the astrophysical implications and applications of interstellar PAC. Our discussion will revolve primarily around the observed interstellar infrared emission spectra and the ability of the laboratory spectra of varying combinations of PAC to accommodate both the global appearance and the region-to-region variability of this emission. Careful models based on sound laboratory spectroscopic data such as these now have the potential to provide insight into the structure, abundance, and ionization state of the interstellar PAC population. That, in turn, will provide direct insight into the processes of carbon nucleation, growth and evolution as matter is processed through the interstellar medium.

Hudgins, Douglas M.↗
DOE OSTI2015

Ab initio calculations of the electronic structure of the low-lying states for the ultracold LiYb molecule

Ab initio techniques have been applied to investigate the electronic structure of the LiYb molecule. The potential energy curves have been computed in the Born–Oppenheimer approximation for the ground and 29 low-lying doublet and quartet excited electronic states. Complete active space self-consistent field, multi-reference configuration interaction, and Rayleigh Schrödinger perturbation theory to second order calculations have been utilized to investigate these states. The spectroscopic constants, ω{sub e}, R{sub e}, B{sub e}, …, and the static dipole moment, μ, have been investigated by using the two different techniques of calculation with five different types of basis. The eigenvalues, E{sub v}, the rotational constant, B{sub v}, the centrifugal distortion constant, D{sub v}, and the abscissas of the turning points, R{sub min} and R{sub max}, have been calculated by using the canonical functions approach. The comparison between the values of the present work, calculated by different techniques, and those available in the literature for several electronic states shows a very good agreement. Twenty-one new electronic states have been studied here for the first time.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2024

Gradient Technique Theory: Tracing Magnetic Field and Obtaining Magnetic Field Strength

Abstract The gradient technique is a promising tool with theoretical foundations based on the fundamental properties of MHD turbulence and turbulent reconnection. Its various incarnations use spectroscopic, synchrotron, and intensity data to trace the magnetic field and measure the media magnetization in terms of Alfvén Mach number. We provide an analytical theory of gradient measurements and quantify the effects of averaging gradients along the line of sight and over the plane of the sky. We derive analytical expressions that relate the properties of gradient distribution with the Alfvén Mach number M A . We show that these measurements can be combined with measures of sonic Mach number or line broadening to obtain the magnetic field strength. The corresponding technique has advantages to the Davis–Chandrasekhar–Fermi way of obtaining the magnetic field strength.

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRS1987

Spectrometry: Report of panel

Spectroscopic measurements are required to define the spectral background and provide the detailed spectral information that is essential for the design of species-specific systems and the analysis of data obtained from them. This function of spectroscopic measurements is expected to be an important part of any tropospheric remote-sensing program, and both emission and absorption spectroscopy are relevant in this context. The data from such observations are of value to tropospheric science in their own right, during the initial phases while species-specific techniques and instruments are under development. In addition, there are a number of unresolved problems in tropospheric radiative transfer and spectroscopy which presently limit the accuracy and reliability of all remote sensing methods. Only through a supporting program of spectroscopic measurements can progress be made in improving the understanding of these aspects of radiative transfer and ultimately reaching the desired confidence in the accuracy to species-specific monitoring techniques.

Farmer, C. Barney↗
DOE OSTI2011

Infrared Spectroscopic Study For Structural Investigation Of Lithium Lead Silicate Glasses

Lithium lead silicate glasses with composition 30Li{sub 2}O{center_dot}(70-x)PbO{center_dot}xSiO{sub 2}(where, x = 10, 20, 30, 40, 50 mol %)(LPS glasses) were prepared by normal melt quench technique at 1373 K for half an hour in air to understand their structure. Compositional dependence of density, molar volume and glass transition temperature of these glasses indicates more compactness of the glass structure with increasing SiO{sub 2} content. Fourier transform infrared (FTIR) spectroscopic data obtained for these glasses was used to investigate the changes induced in the local structure of samples as the ratio between PbO and SiO{sub 2} content changes from 6.0 to 0.4. The observed absorption band around 450-510 cm{sup -1} in IR spectra of these glasses indicates the presence of network forming PbO{sub 4} tetrahedral units in glass structure. The increase in intensity with increasing SiO{sub 2} content (upto x = 30 mol %) suggests superposition of Pb-O and Si-O bond vibrations in absorption band around 450-510 cm{sup -1}. The values of optical basicity in these glasses were found to be dependent directly on PbO/SiO{sub 2} ratio.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Estimating Internal Stress of an Alteration Layer Formed on Corroded Boroaluminosilicate Glass through Spectroscopic Ellipsometry Analysis

Aqueous corrosion of glass may result in the formation of an alteration layer in the glass surface of which chemical composition and network structure are different from those of the bulk glass. Since corrosion occurs far below the glass-transition temperature, the alteration layer cannot fully relax to the new structure with the lowest possible energy. Molecular dynamics simulations suggested that such a network will contain highly strained chemical bonds, which can be manifested as a stress in the alteration layer. Common techniques to measure stress in thin films or surface layers were found inadequate for thick monolithic glass samples corroded in water. Here, we explored the use of spectroscopic ellipsometry to test the presence of internal stress in the alteration layer formed by aqueous corrosion of glass. Furthermore, a procedure for analyses of spectroscopic ellipsometry data to determine birefringence in the alteration layer was developed. Findings with the established fitting procedure suggested that a stress builds up in the corroded surface layer of a boroaluminosilicate glass if there is a change in relative humidity, pH, or electrolyte concentration of the environment to which the glass surface is exposed. A similar process may occur in other types of glass, and it may affect the surface properties of corroded glass objects.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2012

PHOTOMETRIC REDSHIFTS AND QUASAR PROBABILITIES FROM A SINGLE, DATA-DRIVEN GENERATIVE MODEL

We describe a technique for simultaneously classifying and estimating the redshift of quasars. It can separate quasars from stars in arbitrary redshift ranges, estimate full posterior distribution functions for the redshift, and naturally incorporate flux uncertainties, missing data, and multi-wavelength photometry. We build models of quasars in flux-redshift space by applying the extreme deconvolution technique to estimate the underlying density. By integrating this density over redshift, one can obtain quasar flux densities in different redshift ranges. This approach allows for efficient, consistent, and fast classification and photometric redshift estimation. This is achieved by combining the speed obtained by choosing simple analytical forms as the basis of our density model with the flexibility of non-parametric models through the use of many simple components with many parameters. We show that this technique is competitive with the best photometric quasar classification techniques-which are limited to fixed, broad redshift ranges and high signal-to-noise ratio data-and with the best photometric redshift techniques when applied to broadband optical data. We demonstrate that the inclusion of UV and NIR data significantly improves photometric quasar-star separation and essentially resolves all of the redshift degeneracies for quasars inherent to the ugriz filter system, even when included data have a low signal-to-noise ratio. For quasars spectroscopically confirmed by the SDSS 84% and 97% of the objects with Galaxy Evolution Explorer UV and UKIDSS NIR data have photometric redshifts within 0.1 and 0.3, respectively, of the spectroscopic redshift; this amounts to about a factor of three improvement over ugriz-only photometric redshifts. Our code to calculate quasar probabilities and redshift probability distributions is publicly available.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2014

Surface modification of sol–gel synthesized TiO{sub 2} nanoparticles induced by La-doping

The influence of La-doping in the range of 0.5–6.0 mol% on structural and morphological properties of TiO{sub 2} nanopowders synthesized by sol–gel routine has been investigated by XRPD, AFM, EDS and BET measurements, as well as Raman spectroscopy. The XRPD and Raman measurements have revealed the anatase phase as dominant in all nanopowders, with crystallite size decreasing from ∼ 15 nm in pure TiO{sub 2} to ∼ 12 nm in La-doped samples. The BET data suggest that all samples are fully mesoporous, with mean pore diameters in the range of ∼ 6–8 nm. The specific surface area and the complexity of pore structure are greater in doped samples than in pure TiO{sub 2} sample. The spectroscopic ellipsometry has apparently shown that the band gap has been gradually increased with the increase of La content. The STM and STS techniques have been used successfully to evaluate the surface morphology and electronic properties of La-doped nanopowders. All investigated properties have been related to photocatalytic activity, tested in degradation of a metoprolol tartrate salt (0.05 mM), and induced by UV-radiation. All doped samples showed increased photocatalytic activity compared to pure TiO{sub 2}, among which the 0.65 mol% La-doped sample appeared to be the most efficient. - Highlights: • Effects of La-doping on structural, morphological and electronic properties of TiO{sub 2} nanopowders. • Surface morphology and electronic properties of La-doped nanopowders evaluated by STM/STS. • Spectroscopic ellipsometry shown gradual increase of bandgap with the increase of La content. • Photocatalytic activity of samples was tested in degradation of MET under UV light.

36 MATERIALS SCIENCE↗
DOE OSTI2012

IMPROVING CORRELATION FUNCTION FITTING WITH RIDGE REGRESSION: APPLICATION TO CROSS-CORRELATION RECONSTRUCTION

Cross-correlation techniques provide a promising avenue for calibrating photometric redshifts and determining redshift distributions using spectroscopy which is systematically incomplete (e.g., current deep spectroscopic surveys fail to obtain secure redshifts for 30%-50% or more of the galaxies targeted). In this paper, we improve on the redshift distribution reconstruction methods from our previous work by incorporating full covariance information into our correlation function fits. Correlation function measurements are strongly covariant between angular or spatial bins, and accounting for this in fitting can yield substantial reduction in errors. However, frequently the covariance matrices used in these calculations are determined from a relatively small set (dozens rather than hundreds) of subsamples or mock catalogs, resulting in noisy covariance matrices whose inversion is ill-conditioned and numerically unstable. We present here a method of conditioning the covariance matrix known as ridge regression which results in a more well behaved inversion than other techniques common in large-scale structure studies. We demonstrate that ridge regression significantly improves the determination of correlation function parameters. We then apply these improved techniques to the problem of reconstructing redshift distributions. By incorporating full covariance information, applying ridge regression, and changing the weighting of fields in obtaining average correlation functions, we obtain reductions in the mean redshift distribution reconstruction error of as much as {approx}40% compared to previous methods. We provide a description of POWERFIT, an IDL code for performing power-law fits to correlation functions with ridge regression conditioning that we are making publicly available.

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRS2001

Ambient formaldehyde detection with a laser spectrometer based on difference-frequency generation in PPLN

A laser spectrometer based on difference-frequency generation in periodically poled LiNbO3 (PPLN) has been used to quantify atmospheric formaldehyde with a detection limit of 0.32 parts per billion in a given volume (ppbV) using specifically developed data-processing techniques. With state-of-the-art fiber-coupled diode-laser pump sources at 1083 nm and 1561 nm, difference-frequency radiation has been generated in the 3.53-micrometers (2832-cm-1) spectral region. Formaldehyde in ambient air in the 1- to 10-ppb V range has been detected continuously for nine and five days at two separate field sites in the Greater Houston area operated by the Texas Natural Resource Conservation Commission (TNRCC) and the Houston Regional Monitoring Corporation (HRM). The acquired spectroscopic data are compared with results obtained by a well-established wet-chemical o-(2,3,4,5,6-pentafluorobenzyl) hydroxylamine (PFBHA) technique.

NASA Discipline Life Sciences Technologies↗
DOE OSTI2018

Spectroscopic Imaging of Molecular Functions at Surfaces

The focus of this project is on understanding the nature of intramolecular chemical bonds and intermolecular interactions using a unique technique developed in 2014 under DOE support: the inelastic tunneling probe (itProbe) with the scanning tunneling microscope (STM). By operating the STM at ~0.6 K, high energy resolution of ~0.6 meV is achieved, in combination with the inherent atomic scale spatial resolution of the STM. High energy and spatial resolutions of inelastic electron tunneling spectroscopy (IETS) with the STM enables itProbe to monitor energy shifts in the carbon monoxide (CO) hindered translational vibration as the CO-tip is scanned over an adsorbed molecule. Images are obtained that relate to the two-dimensional slices of the potential energy surface for different heights above the substrate, rendering a tomography of the molecule. Comparison of experimental results to density functional theory (DFT) calculations relates itProbe images to the potential energy surface of the CO-tip probing the potential of the adsorbed molecule. Results from this project provide information on the electronic, vibrational, and structural properties of single molecules, as well as how these properties relate to the reactivity, chemical sensing, self-assembly, and other chemical interactions of higher complexity. This research leads to new insights into the fundamental principles of chemistry that can be applied to the understanding of a broad range of phenomena, such as surface chemistry and catalysis, environmental processes and energy generation, electronic processing and electron transport through molecules as in molecular electronics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

CONSTRAINING SOLAR FLARE DIFFERENTIAL EMISSION MEASURES WITH EVE AND RHESSI

Deriving a well-constrained differential emission measure (DEM) distribution for solar flares has historically been difficult, primarily because no single instrument is sensitive to the full range of coronal temperatures observed in flares, from ≲2 to ≳50 MK. We present a new technique, combining extreme ultraviolet (EUV) spectra from the EUV Variability Experiment (EVE) onboard the Solar Dynamics Observatory with X-ray spectra from the Reuven Ramaty High Energy Solar Spectroscopic Imager (RHESSI), to derive, for the first time, a self-consistent, well-constrained DEM for jointly observed solar flares. EVE is sensitive to ∼2-25 MK thermal plasma emission, and RHESSI to ≳10 MK; together, the two instruments cover the full range of flare coronal plasma temperatures. We have validated the new technique on artificial test data, and apply it to two X-class flares from solar cycle 24 to determine the flare DEM and its temporal evolution; the constraints on the thermal emission derived from the EVE data also constrain the low energy cutoff of the non-thermal electrons, a crucial parameter for flare energetics. The DEM analysis can also be used to predict the soft X-ray flux in the poorly observed ∼0.4-5 nm range, with important applications for geospace science.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2023

Enhancing CO 2 Transport Across a PEEK‐Ionene Membrane and Water‐Lean Solvent Interface

Abstract Efficient direct air capture (DAC) of CO 2 will require strategies to deal with the relatively low concentration in the atmosphere. One such strategy is to employ the combination of a CO 2 ‐selective membrane coupled with a CO 2 capture solvent acting as a draw solution. Here, the interactions between a leading water‐lean carbon‐capture solvent, a polyether ether ketone (PEEK)‐ionene membrane, CO 2 , and combinations were probed using advanced NMR techniques coupled with advanced simulations. We identify the speciation and dynamics of the solvent, membrane, and CO 2 , presenting spectroscopic evidence of CO 2 diffusion through benzylic regions within the PEEK‐ionene membrane, not spaces in the ionic lattice as expected. Our results demonstrate that water‐lean capture solvents provide a thermodynamic and kinetic funnel to draw CO 2 from the air through the membrane and into the bulk solvent, thus enhancing the performance of the membrane. The reaction between the carbon‐capture solvent and CO 2 produces carbamic acid, disrupting interactions between the imidazolium (Im + ) cations and the bistriflimide anions within the PEEK‐ionene membrane, thereby creating structural changes through which CO 2 can diffuse more readily. Consequently, this restructuring results in CO 2 diffusion at the interface that is faster than CO 2 diffusion in the bulk carbon‐capture solvent.

Walter, Eric D.↗
DOE OSTI2020

Spectroscopic characterization of a new Re(i) tricarbonyl complex with a thiosemicarbazone derivative: towards sensing and electrocatalytic applications

This work describes the preparation of a new thiosemicarbazone derivative, (Z)- N -ethyl-2-(6-oxo-1,10-phenanthrolin-5(6 H )-ylidene)hydrazinecarbothioamide (phet) and its respective Re( I ) tricarbonyl chloro complex, fac -[ReCl(CO) 3 (phet)]. The spectroscopic, photophysical and electrochemical properties of the new complex were fully investigated through steady state and time-resolved techniques along with computational calculations. In fac -[ReCl(CO) 3 (phet)], the new ligand is coordinated to the metal center through the pyridyl rings of the phenanthroline moiety. The unbound electron pairs in the S atom of the bending thiosemicarbazone group induce new low energy lying electronic transitions. Consequently, enhanced visible light absorption up to 550 nm is observed in acetonitrile due to the overlap between MLCT Re→phet and IL phet(n→π*) transitions. The absorption bands and emission quantum yields of fac -[ReCl(CO) 3 (phet)] are sensitive to proton concentration due to an acid-basic equilibrium in the N atoms of the thiosemicarbazone. Proton dissociation constants of 10.0 ± 0.1 and 11.4 ± 0.2 were determined respectively for the ground and excited states of the new complex. Spectral changes could also be observed in the presence of Zn 2+ cations which can be further explored for sensing applications. The electrochemical behavior of the new complex was studied in detail, revealing up to four one electron reduction processes in the range from 0 to -2.4 V vs. Fc + /Fc. With support of DFT calculations, the first three processes are ascribed to the reduction of the coordinated phet ligand followed by the Re I/0 reduction and consequent Cl - release. Furthermore, the new complex was able to act as an electrocatalyst for CO 2 reduction into CO ( E onset = -1.92 V vs. Fc + /Fc), with a turnover frequency of 2.81 s -1 and turnover number of 24 ± 1 in anhydrous acetonitrile, being the first Re( I ) tricarbonyl complex with a thiosemicarbazone derivative described for this goal. The detailed characterization carried out here can drive the development of new Re( I )-thiosemicarbazone derivatives for different applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Structural and optical studies of hydrothermally synthesized MoS{sub 2} nanostructures

Transition-metal dichalcogenides like molybdenum disulphide have intrigued intensive interest as two-dimensional (2D) materials beyond extensively studied graphene due to their unique electronic and optical properties. Here we report the hydrothermal synthesis of MoS{sub 2} nanostructures without the addition of any surfactants. The structural and optical properties of the synthesized samples were characterized by various techniques, including X-ray diffraction (XRD), UV-Vis absorption, photoluminescence (PL), and Raman analysis. XRD and Raman spectroscopic studies confirm the formation of hexagonal phase and well ordered stacking of S-Mo-S layers. The increased lattice parameters of MoS{sub 2} samples are due to the stress or strain induced bending and folding of the layers. The synthesized MoS{sub 2} nanostructures shows a large optical absorption in 300-700 nm region and strong luminescence at 640 nm. In addition, the optical results demonstrates the quantum confinement in layered d-electron material MoS{sub 2} that can lead to engineer its various properties for electronic and optoelectronic applications.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2018

ProtoDESI: First On-Sky Technology Demonstration for the Dark Energy Spectroscopic Instrument

The Dark Energy Spectroscopic Instrument (DESI) is under construction to measure the expansion history of the universe using the baryon acoustic oscillations technique. The spectra of 35 million galaxies and quasars over 14,000 square degrees will be measured during a 5-year survey. A new prime focus corrector for the Mayall telescope at Kitt Peak National Observatory will deliver light to 5,000 individually targeted fiber-fed robotic positioners. The fibers in turn feed ten broadband multi-object spectrographs. We describe the ProtoDESI experiment, that was installed and commissioned on the 4-m Mayall telescope from 2016 August 14 to September 30. ProtoDESI was an on-sky technology demonstration with the goal to reduce technical risks associated with aligning optical fibers with targets using robotic fiber positioners and maintaining the stability required to operate DESI. The ProtoDESI prime focus instrument, consisting of three fiber positioners, illuminated fiducials, and a guide camera, was installed behind the existing Mosaic corrector on the Mayall telescope. A fiber view camera was mounted in the Cassegrain cage of the telescope and provided feedback metrology for positioning the fibers. ProtoDESI also provided a platform for early integration of hardware with the DESI Instrument Control System that controls the subsystems, provides communication with the Telescope Control System, and collects instrument telemetry data. In conclusion, lacking a spectrograph, ProtoDESI monitored the output of the fibers using a fiber photometry camera mounted on the prime focus instrument. ProtoDESI was successful in acquiring targets with the robotically positioned fibers and demonstrated that the DESI guiding requirements can be met.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗