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DOE OSTI2020

Excited Carrier Dynamics in a Dye-Sensitized Niobate Nanosheet Photocatalyst for Visible-Light Hydrogen Evolution

Dye-sensitized photocatalysts that consist of a light-absorbing dye and a wide gap oxide semiconductor have been studied extensively as components of solar energy conversion systems. Although surface modification by a metal and/or metal oxide has a significant impact on the photocatalytic efficiency, the mechanism by which these modifications increase the activity has not been fully understood. Here a dye-sensitized H 2 evolution system was constructed by using Pt-intercalated HCa 2 Nb 3 O 10 nanosheets, Ru(II) complex photosensitizers ([Ru(4,4’-(CH 3 ) 2- bpy) 2 (4,4’-(PO 3 H 2 ) 2- bpy)] 2+ and [Ru(4,4’-(CH 3 ) 2- bpy) 2 (4,4’-(CH 2 PO 3 H 2 ) 2- bpy)] 2+ , abbreviated as RuP 2+ and RuCP 2+ ; bpy = 2,2'-bipyridine), and amorphous Al 2 O 3 as building blocks. In the presence of iodide as the electron donor, the H 2 evolution rate from Pt/HCa 2 Nb 3 O 10 nanosheets sensitized by RuP 2+ was increased by modification of the nanosheets with Al 2 O 3 . On the other hand, Al 2 O 3 had a negative impact on the H 2 evolution rate when RuCP 2+ was employed. These hybrid materials were studied by transient diffuse reflectance spectroscopy and steady-state emission spectroscopy. A detailed analysis of the transient absorption profiles of the adsorbed Ru(II) complexes revealed that there are at least three states of the complexes on the nanosheet surface. The transient bleaching of the ground state absorbance had different lifetime components ranging from a few μs to several hundred μs, which mainly reflect back electron transfer rates from HCa 2 Nb 3 O 10 to the oxidized Ru(II) complexes. Here, the Al 2 O 3 modifier could inhibit not only the back electron transfer events but also electron injection from the excited state photosensitizer. Interestingly, the negative effect of Al 2 O 3 on the electron injection rate was negligible in the case of RuP 2+ , which also had a higher H 2 evolution rate. This work highlights that suppressing fast back electron transfer from Pt/HCa 2 Nb 3 O 10 to the oxidized Ru(II) complex, which occurs on a time scale of a few μs, and maximizing the electron injection efficiency are both necessary for improving dye-sensitized H 2 evolution.

14 SOLAR ENERGY↗

DOE OSTI2021

In vivo evolution of lactic acid hyper-tolerant Clostridium thermocellum

Lactic acid (LA) has several applications in the food, cosmetics and pharmaceutical industries, as well as in the production of biodegradable plastic polymers, namely polylactides. Industrial production of LA is essentially based on microbial fermentation. Recent reports have shown the potential of the cellulolytic bacterium Clostridium thermocellum for direct LA production from inexpensive lignocellulosic biomass. However, C. thermocellum is highly sensitive to acids and does not grow at pH < 6.0. Improvement of LA tolerance of this microorganism is pivotal for its application in cost-efficient production of LA. In the present study, the LA tolerance of C. thermocellum strains LL345 (wild-type fermentation profile) and LL1111 (high LA yield) was increased by adaptive laboratory evolution. At large inoculum size (10 %), the maximum tolerated LA concentration of strain LL1111 was more than doubled, from 15 g/L to 35 g/L, while subcultures evolved from LL345 showed 50–85 % faster growth in medium containing 45 g/L LA. Gene mutations (pyruvate phosphate dikinase, histidine protein kinase/phosphorylase) possibly affecting carbohydrate and/or phosphate metabolism have been detected in most LA-adapted populations. Although improvement of LA tolerance may sometimes also enable higher LA production in microorganisms, C. thermocellum LA-adapted cultures showed a yield of LA, and generally of other organic acids, similar to or lower than parental strains. Based on its improved LA tolerance and LA titer similar to its parent strain (LL1111), mixed adapted culture LL1630 showed the highest performing phenotype and could serve as a framework for improving LA production by further metabolic engineering.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2021

A data-independent acquisition-based global phosphoproteomics system enables deep profiling

Phosphoproteomics can provide insights into cellular signaling dynamics. To achieve deep and robust quantitative phosphoproteomics profiling for minute amounts of sample, we here develop a global phosphoproteomics strategy based on data-independent acquisition (DIA) mass spectrometry and hybrid spectral libraries derived from data-dependent acquisition (DDA) and DIA data. Benchmarking the method using 166 synthetic phosphopeptides shows high sensitivity (<0.1 ng), accurate site localization and reproducible quantification (~5% median coefficient of variation). As a proof-of-concept, we use lung cancer cell lines and patient-derived tissue to construct a hybrid phosphoproteome spectral library covering 159,524 phosphopeptides (88,107 phosphosites). Based on this library, our single-shot streamlined DIA workflow quantifies 36,350 phosphosites (19,755 class 1) in cell line samples within two hours. Application to drug-resistant cells and patient-derived lung cancer tissues delineates site-specific phosphorylation events associated with resistance and tumor progression, showing that our workflow enables the characterization of phosphorylation signaling with deep coverage, high sensitivity and low between-run missing values.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Parameter Sensitivity Analysis of the SparTen High Performance Sparse Tensor Decomposition Software (Extended Analysis)

Tensor decomposition models play an increasingly important role in modern data science applications. One problem of particular interest is fitting a low-rank Canonical Polyadic (CP) tensor decomposition model when the tensor has sparse structure and the tensor elements are nonnegative count data. SparTen is a high-performance C++ library which computes a low-rank decomposition using different solvers: a first-order quasi-Newton or a second-order damped Newton method, along with the appropriate choice of runtime parameters. Since default parameters in SparTen are tuned to experimental results in prior published work on a single real-world dataset conducted using MATLAB implementations of these methods, it remains unclear if the parameter defaults in SparTen are appropriate for general tensor data. Furthermore, it is unknown how sensitive algorithm convergence is to changes in the input parameter values. This report addresses these unresolved issues with large-scale experimentation on three benchmark tensor data sets. Experiments were conducted on several different CPU architectures and replicated with many initial states to establish generalized profiles of algorithm convergence behavior.

97 MATHEMATICS AND COMPUTING↗

NASA NTRS1982

Interaction of a cumulus cloud ensemble with the large-scale environment. III - Semi-prognostic test of the Arakawa-Schubert cumulus parameterization

The verification of the Arakawa and Schubert (1974) cumulus parameterization is continued using a semiprognostic approach. Observed data from Phase III of GATE are used to provide estimates of the large-scale forcing of a cumulus ensemble at each observation time. Instantaneous values of the precipitation and the warming and drying due to cumulus convection are calculated using the parameterization. The results show that the calculated precipitation agrees very well with estimates from the observed large-scale moisture budget and from radar observations. The calculated vertical profiles of cumulus warming and drying also are quite similar to the observed. It is shown that the closure assumption adopted in the parameterization (the cloud-work function quasi-equilibrium) results in errors of generally less than 10% in the calculated precipitation. The sensitivity of the parameterization to some assumptions of the cloud ensemble model and the solution method for the cloud-base mass flux is investigated.

Lord, S. J.↗

NASA NTRS1989

Recent activities within the Aeroservoelasticity Branch at the NASA Langley Research Center

The objective of research in aeroservoelasticity at the NASA Langley Research Center is to enhance the modeling, analysis, and multidisciplinary design methodologies for obtaining multifunction digital control systems for application to flexible flight vehicles. Recent accomplishments are discussed, and a status report on current activities within the Aeroservoelasticity Branch is presented. In the area of modeling, improvements to the Minimum-State Method of approximating unsteady aerodynamics are shown to provide precise, low-order aeroservoelastic models for design and simulation activities. Analytical methods based on Matched Filter Theory and Random Process Theory to provide efficient and direct predictions of the critical gust profile and the time-correlated gust loads for linear structural design considerations are also discussed. Two research projects leading towards improved design methodology are summarized. The first program is developing an integrated structure/control design capability based on hierarchical problem decomposition, multilevel optimization and analytical sensitivities. The second program provides procedures for obtaining low-order, robust digital control laws for aeroelastic applications. In terms of methodology validation and application the current activities associated with the Active Flexible Wing project are reviewed.

Noll, Thomas E.↗

NASA NTRS1988

Minimum dissipation rates in magnetohydrodynamics

Minimum dissipation rate states are explored for a current-carrying channel of magnetofluid, supported by a dc magnetic field and driven by an applied electric field. The minimization is carried out subject to the constraints of constant axial (toroidal) magnetic flux and constant time-averaged rate of supply of magnetic helicity. The solutions of the resulting Euler-Lagrange equations are sensitive to boundary conditions on the current density j. One set of boundary conditions on j leads to the same consequences as Taylor's 'minimum-energy' theory. A different set leads to significantly different consequences, including a departure from the 'force-free' magnetic profile and a toroidal component of current density that does not reverse at the wall when the toroidal magnetic field reverses.

Montgomery, David↗

NASA NTRS1989

Recent activities within the aeroservoelasticity branch at the NASA Langley Research Center

Noll, Thomas↗

NASA NTRS2009

Assimilating EOS-Aura OMI and MLS Data in GEOS-5

Data assimilation is a potentially powerful method of extracting the maximum amount of information from observed data by combining their information with models. in this application, we will use stratospheric ozone profiles retrieved from EOS MLS and total column amounts retrieved from OMI' along with the GEOS-5 GCM, that includes a representation of ozone chemistry and transport. The presentation will discuss how well we can derive tropospheric ozone column information in this system, including its sensitivity to model errors and some assumptions made in the assimilation system. We discuss also ozone structures in the tropopause region and their sensitivity to model resolution and other fact=ors. An important issue we examine is how much more information we obtain from ozone assimilation than from model studies using state of the art chemistry models - answering such questions helps determine how useful ozone assimilation really is, given our present capabilities in chemical modeling.

Pawson, Steven↗

NASA NTRS2012

Human Settlements in the South-Central U.S., Viewed at Night from the International Space Station

A recent innovation of astronauts observing Earth from the International Space Station (ISS) is documenting human footprints by photographing city lights at night time. One of the earliest night-time images from the ISS was the US-Mexico border at El Paso-Ciudad Juarez. The colors, patterns and density of city lights document the differences in the cultural settlement patterns across the border region, as well as within the urban areas themselves. City lights help outline the most populated areas in settlements around the world, and can be used to explore relative population densities, changing patterns of urban/suburban development, transportation networks, spatial relationship to geographic features, and more. The data also provides insight into parameters such as surface roughness for input into local and regional climate modeling and studies of light pollution. The ground resolution of night-time astronaut photography from the ISS is typically an order of magnitude greater than current Defense Meteorological Satellite Program (DMSP) data, and therefore can serve as a "zoom lens" for selected urban areas. Current handheld digital cameras in use on the ISS, optimized for greater light sensitivity, provide opportunities to obtain new detailed imagery of atmospheric phenomena such as airglow, aurora, and noctilucent clouds in addition to documenting urban patterns. ISS astronauts have taken advantage of increasingly sensitive digital cameras to document the world at night in unprecedented detail. In addition, the capability to obtain time-lapse imagery from fixed cameras has been exploited to produce dynamic videos of both changing surface patterns around the world and atmospheric phenomena. We will profile some spectacular images of human settlements over the South-Central U.S., and contrast with other images from around the world. More data can be viewed at http://eol.jsc.nasa.gov/Videos/CrewEarthObservationsVideos/. US-Mexico border is obvious by the different lighting pattern. Not surprisingly, the densely illuminated city of Juarez indicates a higher population; El Paso's smaller population is spread out over a larger area.

Dawson, Melissa↗

NASA NTRS2015

Characterization of Encapsulated Corrosion Inhibitors Containing Microparticles for Environmentally Friendly Smart Coatings

This poster presents the results obtained from experiments designed to evaluate the release properties, as well as the corrosion inhibition effectiveness, of several encapsulated corrosion inhibitors. Microencapsulation has been used in the development of environmentally friendly multifunctional smart coatings. This technique enables the incorporation of autonomous corrosion detection, inhibition and self-healing functionalities into many commercially available coating systems. Select environmentally friendly corrosion inhibitors were encapsulated in organic and inorganic pH-sensitive microparticles and their release in basic solutions was studied. The release rate results showed that the encapsulation can be tailored from fast, for immediate corrosion protection, to slow, which will provide continued long-term corrosion protection. The incorporation of several corrosion inhibitor release profiles into a coating provides effective corrosion protection properties. To investigate the corrosion inhibition efficiency of the encapsulated inhibitors, electrochemical techniques were used to obtain corrosion potential, polarization curve and polarization resistance data. These measurements were performed using the free as well as the encapsulated inhibitors singly or in combinations. Results from these electrochemical tests will be compared to those obtained from weight loss and other accelerated corrosion experiments.

Coatings↗

NASA NTRS2017

CLASP2: The Chromospheric LAyer Spectro-Polarimeter

A major remaining challenge for heliophysicsis to decipher the magnetic structure of the chromosphere, due to its "large role in defining how energy is transported into the corona and solar wind" (NASA's Heliophysics Roadmap). Recent observational advances enabled by the Interface Region Imaging Spectrometer (IRIS) have revolutionized our view of the critical role this highly dynamic interface between the photosphere and corona plays in energizing and structuring the outer solar atmosphere. Despite these advances, a major impediment to better understanding the solar atmosphere is our lack of empirical knowledge regarding the direction and strength of the magnetic field in the upper chromosphere. Such measurements are crucial to address several major unresolved issues in solar physics: for example, to constrain the energy flux carried by the Alfven waves propagating through the chromosphere (De Pontieuet al., 2014), and to determine the height at which the plasma Beta = 1 transition occurs, which has important consequences for the braiding of magnetic fields (Cirtainet al., 2013; Guerreiroet al., 2014), for propagation and mode conversion of waves (Tian et al., 2014a; Straus et al., 2008) and for non-linear force-free extrapolation methods that are key to determining what drives instabilities such as flares or coronal mass ejections (e.g.,De Rosa et al., 2009). The most reliable method used to determine the solar magnetic field vector is the observation and interpretation of polarization signals in spectral lines, associated with the Zeeman and Hanle effects. Magnetically sensitive ultraviolet spectral lines formed in the upper chromosphere and transition region provide a powerful tool with which to probe this key boundary region (e.g., Trujillo Bueno, 2014). Probing the magnetic nature of the chromosphere requires measurement of the Stokes I, Q, U and V profiles of the relevant spectral lines (of which Q, U and V encode the magnetic field information).

Chromosphere↗

NASA NTRS2017

CLASP2: The Chromospheric LAyer Spectro-Polarimeter

A major remaining challenge for heliophysicsis to decipher the magnetic structure of the chromosphere, due to its 'large role in defining how energy is transported into the corona and solar wind' (NASA's Heliophysics Roadmap). Recent observational advances enabled by the Interface Region Imaging Spectrometer (IRIS) have revolutionized our view of the critical role this highly dynamic interface between the photosphere and corona plays in energizing and structuring the outer solar atmosphere. Despite these advances, a major impediment to better understanding the solar atmosphere is our lack of empirical knowledge regarding the direction and strength of the magnetic field in the upper chromosphere. Such measurements are crucial to address several major unresolved issues in solar physics: for example, to constrain the energy flux carried by the Alfven waves propagating through the chromosphere (De Pontieuet al., 2014), and to determine the height at which the plasma β = 1 transition occurs, which has important consequences for the braiding of magnetic fields (Cirtainet al., 2013; Guerreiroet al., 2014), for propagation and mode conversion of waves (Tian et al., 2014a; Straus et al., 2008) and for non-linear force-free extrapolation methods that are key to determining what drives instabilities such as flares or coronal mass ejections (e.g., De Rosa et al., 2009). The most reliable method used to determine the solar magnetic field vector is the observation and interpretation of polarization signals in spectral lines, associated with the Zeeman and Hanle effects. Magnetically sensitive ultraviolet spectral lines formed in the upper chromosphere and transition region provide a powerful tool with which to probe this key boundary region (e.g., Trujillo Bueno, 2014). Probing the magnetic nature of the chromosphere requires measurement of the Stokes I, Q, U and V profiles of the relevant spectral lines (of which Q, U and V encode the magnetic field information).

Solar; Chromosphere; Polarization↗

NASA NTRS2007

Materials-of-Construction Radiation Sensitivity for a Fission Surface Power Convertor

A fission reactor combined with a free-piston Stirling convertor is one of many credible approaches for producing electrical power in space applications. This study assumes dual-opposed free-piston Stirling engines/linear alternators that will operate nominally at 825 K hot-end and 425 K cold-end temperatures. The baseline design options, temperature profiles, and materials of construction discussed here are based on historical designs as well as modern convertors operating at lower power levels. This notional design indicates convertors primarily made of metallic components that experience minimal change in mechanical properties for fast neutron fluences less than 10(sup 20) neutrons per square centimeter. However, these radiation effects can impact the magnetic and electrical properties of metals at much lower fluences than are crucial for mechanical property integrity. Moreover, a variety of polymeric materials are also used in common free-piston Stirling designs for bonding, seals, lubrication, insulation and others. Polymers can be affected adversely by radiation doses as low as 10(sup 5) - 10(sup 10) rad. Additionally, the absorbing dose rate, radiation hardness, and the resulting effect (either hardening or softening) varies depending on the nature of the particular polymer. The classes of polymers currently used in convertor fabrication are discussed along possible substitution options. Thus, the materials of construction of prototypic Stirling convertor engines have been considered and the component materials susceptible to damage at the lowest neutron fluences have been identified.

Bowman, Cheryl L.↗

DOE OSTI2022

Measuring the thermal and ionization state of the low- z IGM using likelihood free inference

ABSTRACT We present a new approach to measure the power-law temperature density relationship $T=T_0 (\rho/ \bar{\rho })^{\gamma -1}$ and the UV background photoionization rate $\Gamma _{{{{\rm H\, {\small I}}}}{}}$ of the intergalactic medium (IGM) based on the Voigt profile decomposition of the Ly α forest into a set of discrete absorption lines with Doppler parameter b and the neutral hydrogen column density $N_{\rm H\, {\small I}}$. Previous work demonstrated that the shape of the $b-N_{{{{\rm H\, {\small I}}}}{}}$ distribution is sensitive to the IGM thermal parameters T0 and γ, whereas our new inference algorithm also takes into account the normalization of the distribution, i.e. the line-density dN/dz, and we demonstrate that precise constraints can also be obtained on $\Gamma _{{{{\rm H\, {\small I}}}}{}}$. We use density-estimation likelihood-free inference (DELFI) to emulate the dependence of the $b-N_{{{{\rm H\, {\small I}}}}{}}$ distribution on IGM parameters trained on an ensemble of 624 nyx hydrodynamical simulations at z = 0.1, which we combine with a Gaussian process emulator of the normalization. To demonstrate the efficacy of this approach, we generate hundreds of realizations of realistic mock HST/COS data sets, each comprising 34 quasar sightlines, and forward model the noise and resolution to match the real data. We use this large ensemble of mocks to extensively test our inference and empirically demonstrate that our posterior distributions are robust. Our analysis shows that by applying our new approach to existing Ly α forest spectra at z ≃ 0.1, one can measure the thermal and ionization state of the IGM with very high precision ($\sigma _{\log T_0} \sim 0.08$ dex, σγ ∼ 0.06, and $\sigma _{\log \Gamma _{{{{\rm H\, {\small I}}}}{}}} \sim 0.07$ dex).

79 ASTRONOMY AND ASTROPHYSICS↗

NASA NTRS1975

Description of CASCOMP Comprehensive Airship Sizing and Performance Computer Program, Volume 2

The computer program CASCOMP, which may be used in comparative design studies of lighter than air vehicles by rapidly providing airship size and mission performance data, was prepared and documented. The program can be used to define design requirements such as weight breakdown, required propulsive power, and physical dimensions of airships which are designed to meet specified mission requirements. The program is also useful in sensitivity studies involving both design trade-offs and performance trade-offs. The input to the program primarily consists of a series of single point values such as hull overall fineness ratio, number of engines, airship hull and empennage drag coefficients, description of the mission profile, and weights of fixed equipment, fixed useful load and payload. In order to minimize computation time, the program makes ample use of optional computation paths.

Davis, J.↗

NASA NTRS1977

Features of a separating turbulent boundary layer in the vicinity of separation

Laser anemometer measurements using a directionally sensitive system were obtained for a nominally two-dimensional separating turbulent boundary layer produced by an adverse pressure gradient. An airfoil-type flow was generated in which the flow was accelerated and then decelerated until separation. The results include the skin friction, mean velocity profiles, turbulent shear stresses and intensities, spectra, dissipation rate, turbulent/non-turbulent interfacial intermittency, and eddy speeds.

Simpson, R. L.↗

NASA NTRS1981

Atmospheric studies related to aerospace activities and remote sensing technology

Parallel investigations were conducted relating to: the sensitivity of 1-D photochemical model simulated column ozone perturbations due to a projected fleet of 1000 aircraft cruising 7 hours per day at altitudes of 15-16 and 18-19 km to uncertainties in kinetic rate constant data determining modeled OH concentrations and eddy diffusivity profile parameterization and a comparison of the inherent strengths and weaknesses of Eulerian and Langrangian averaging processes in the development of multidimensional models and investigation of approaches to applying the Generalized Lagrangian Mean (GLM) formalism to zonal-mean models. The role of multiple scattering and Earth curvature in the evaluation of diurnally dependent photodissociation rates and trace species variations was examined.

Sze, N. D.↗