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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.

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At least 55 records · Page 3

Photo Protection of Haematococcus pluvialis Algae by Astaxanthin: Unique Properties of Astaxanthin Deduced by EPR, Optical and Electrochemical Studies

The antioxidant astaxanthin is known to accumulate in Haematococcus pluvialis algae under unfavorable environmental conditions for normal cell growth. The accumulated astaxanthin functions as a protective agent against oxidative stress damage, and tolerance to excessive reactive oxygen species (ROS) is greater in astaxanthin-rich cells. The detailed mechanisms of protection have remained elusive, however, our Electron Paramagnetic Resonance (EPR), optical and electrochemical studies on carotenoids suggest that astaxanthin’s efficiency as a protective agent could be related to its ability to form chelate complexes with metals and to be esterified, its inability to aggregate in the ester form, its high oxidation potential and the ability to form proton loss neutral radicals under high illumination in the presence of metal ions. In conclusion, the neutral radical species formed by deprotonation of the radical cations can be very effective quenchers of the excited states of chlorophyll under high irradiation.

59 BASIC BIOLOGICAL SCIENCES↗

Studies of chondrogenesis in rotating systems

A great deal of energy has been exerted over the years researching methods for regenerating and repairing bone and cartilage. Several techniques, especially bone implants and grafts, show great promise for providing a remedy for many skeletal disorders and chondrodystrophies. The bioreactor (rotating-wall vessel, RWV) is a cell culture system that creates a nurturing environment conducive to cell aggregation. Chondrocyte cultures have been studied as implants for repair and replacement of damaged and missing bone and cartilage since 1965 [Chesterman and Smith, J Bone Joint Surg 50B:184-197, 1965]. The ability to use large, tissue-like cartilage aggregates grown in the RWV would be of great clinical significance in treating skeletal disorders. In addition, the RWV may provide a superior method for studying chondrogenesis and chondrogenic mutations. Because the RWV is also reported to simulate many of the conditions of microgravity it is a very useful ground-based tool for studying how cell systems will react to microgravity.

Non-NASA Center↗

Directed assembly of hybrid nanostructures using optically resonant nanotweezers

This represents the final report for this project. Over the course of the project we have made significant progress in photonically driven nano-assembly including: (1) demonstrating the first direct optical tweezer based manipulation of proteins, (2) the ability to apply optical angular torques to microtubuals and other rod-shaped microparticles, (3) direct assembly of hybrid nanostructures comprising of polymeric nanoparticles and carbon nanotubes and, (4) the ability to drive biological reactions (specifically protein aggregation) that are thermodynamically unfavorable by applying localized optical work. These advancements are described in the list of papers provided in section 2.0 of the below. Summary details are provided in prior year annual reports. We have two additional papers which will be submitted shortly based on the work done under this award. An updated publication list will be provided to the program manager when those are accepted. In this report, we report on a new advancement made in the final project year, which uses the nanotweezer technology to perform direct measurements of particle-surface interactions. Briefly, these measurements are important for characterizing the stability and behavior of colloidal and nanoparticle suspensions and current techniques are limited in their ability to measure piconewton scale interaction forces on sub-micrometer particles due to signal detection limits and thermal noise. In this project year we developed a new technique called “Nanophotonic Force Microscopy” which uses the localized region of exponentially decaying, near-field, light to confine small particles close to a surface. From the statistical distribution of the light intensity scattered by the particle the technique maps out the potential well of the trap and directly quantify the repulsive force between the nanoparticle and the surface. The major advantage of the technique is that it can measure forces and energy wells below the thermal noise limit, resolving interaction forces smaller than 1 pN on dielectric particles as small as 100 nm in diameter.

36 MATERIALS SCIENCE↗

Spatial variation in microbial processes controlling carbon mineralization within soils and sediments

Soils have a defining role in global carbon cycling, having one of the largest dynamic stocks of C on earth—3300 Pg of C are stored in soils, which is three-times the amount stored in the atmosphere and more than the terrestrial land plants. An important control on soil organic matter (SOM) quantities is the mineralization rate. It is well recognized that the rate and extent of SOM mineralization is affected by climatic factors and mineral-organic matter associations. What remained elusive is to what extent constraints on microbial metabolism induced by the respiratory pathway, and specifically the electron acceptor in respiration, control overall rates of carbon mineralization in soils. Therefore, physical factors limiting oxygen diffusion such as soil texture and aggregate size (soil structure) may therefore be central controls on C mineralization rates. The goal of our research was therefore to determine if variations in microbial metabolic rates induced by anaerobic microsites in soils are a major control on SOM mineralization rates and thus storage. We performed a combination of laboratory experiments and field investigations will be performed to fulfill our research objectives. We used laboratory studies to examine fundamental factors of respiratory constraints (i.e., electron acceptor) on organic matter mineralization rates. We ground our laboratory studies with both manipulation of field samples and in-field measurements. Selection of the field sites is guided by variation in soil texture and structure while having (other environmental/soil factors constant. Our laboratory studies defined redox gradients and variations in microbial metabolism operating at the aggregate-scale (cm-scale) within soils using a novel constructed diffusion reactor. We further examined micro-scale variation in terminal electron accepting processes and resulting C mineralization rates within re-packed soils. A major outcome of our research is the ability to quantitatively place the importance of aggregate-based heterogeneity in microbial redox processes and the resulting lack of oxygen on the rate of carbon mineralization. Collectively, our research shows that anaerobic microsites are prevalent in soils and are important regulators of soil carbon persistence, shifting microbial metabolism to less efficient anaerobic respiration and selectively protecting otherwise bioavailable, reduced organic compounds such as lipids and waxes from decomposition. Further, shifting from anaerobic to aerobic conditions leads to a 10-fold increase in volume-specific mineralization rate, illustrating the sensitivity of anaerobically protected carbon to disturbance. Vulnerability of anaerobically protected carbon to future climate or land use change thus constitutes a yet unrecognized soil carbon-climate feedback that should be incorporated into terrestrial ecosystem models.

54 ENVIRONMENTAL SCIENCES↗

Conjugation- and Aggregation-Directed Design of Covalent Organic Frameworks as White-Light-Emitting Diodes

2D covalent organic frameworks (COFs) have emerged as a promising class of organic luminescent materials due to their structural diversity, which allows the systematic tuning of organic building blocks to optimize emitting properties. However, a significant knowledge gap exists between the design strategy and the fundamental understanding of the key structural parameters that determine their photophysical properties. Here, in this work, we report two highly emissive sp 2 -C-COFs and the direct correlation of the structure (conjugation and aggregation) with their light absorption/emission, charge transfer (CT), and exciton dynamics, the key properties that determine their function as luminescent materials. We show that white light can be obtained by simply coating COFs on an LED strip or mixing the two COFs. Using the combination of time-resolved absorption and emission spectroscopy as well as computational prediction, we show that the planarity, conjugation, orientation of the dipole moment, and interlayer aggregation not only determine the light-harvesting ability of COFs but also control the exciton relaxation pathway and photoluminescent quantum yield.

14 SOLAR ENERGY↗

Adsorption and Catalytic Activity of Gold Nanoparticles in Mesoporous Silica: Effect of Pore Size and Dispersion Salinity

The assembled state of nanoparticles (NPs) within porous matrices plays a governing role in directing their biological, electronic, and catalytic properties. However, the effects of the spatial confinement and environmental factors, such as salinity, on the NP assemblies within the pores are poorly understood. In this study, we use adsorption isotherms, spectrophotometry, and small-angle neutron scattering to develop a better understanding of the effect of spatial confinement on the assembled state and catalytic performance of gold (Au) NPs in propylamine-functionalized SBA-15 and MCM-41 mesoporous silica materials (mSiO 2 ). We carry out a detailed investigation of the effect of pore diameter and ionic strength on the packing and spatial distribution of AuNPs within mSiO 2 to get a comprehensive insight into the structure, functioning, and activity of these NPs. We demonstrate the ability of the adsorbed AuNPs to withstand aggregation under high salinity conditions. We attribute the observed preservation of the adsorbed state of AuNPs to the strong electrostatic attraction between oppositely charged pore walls and AuNPs. The preservation of the structure allows the AuNPs to retain their catalytic activity for a model reaction in high salinity aqueous solution, here, the reduction of p-nitrophenol to p-aminophenol, which otherwise is significantly diminished due to bulk aggregation of the AuNPs. This fundamental study demonstrates the critical role of confinement and dispersion salinity on the adsorption and catalytic performance of NPs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Aliovalent Doping of CeO 2 Improves the Stability of Atomically Dispersed Pt

Atomically dispersed supported catalysts hold considerable promise as catalytic materials. The ability to employ and stabilize them against aggregation in complex process environments remains a key challenge to the elusive goal of 100% atom utilization in catalysis. In this work, using a Gd-doped ceria support for atomically dispersed surface Pt atoms, we establish how the combined effects of aliovalent doping and oxygen vacancy generation provide dynamic mechanisms that serve to enhance the stability of supported single atom configurations. Using correlated, in situ X-ray absorption, photoelectron and vibrational spectroscopies for analysis of the samples on the two types of support (with and without Gd doping), we establish that the Pt atoms locate proximal to Gd dopants, forming a speciation that serves to enhance the thermal stability of Pt atoms against aggregation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Experimentally Validated Computational Modeling of Creep and Creep-Cracking for Nuclear Concrete Structures

In a Nuclear Power Plant, one of the most important components is the concrete nuclear reactor cavity, which serves both a structural and protective function as the biological radiation shield. Given that creep has been identified as a major knowledge gap in the assessment of nuclear structures (NUREG/CR-7153), this work helps to further the understanding of creep behavior of massive concrete containment structures for decades to enable safe and long-term operation of these facilities. This project has developed a robust, experimentally validated model to predict creep in nuclear concrete structures for up 60 years using short-term creep data thereby enabling a longer service life of critical facilities and early detection of structural failure. The work presented in this report is a pairing of computational and experimental methods. For the first time, the time temperature superposition (TTS) principle was successfully used to generate a uniaxial creep compliance master curve to predict mortar creep response for up to 22,500 days (nearly 60 years) at a reference temperature of 20°C. These data were used as input into finite element analysis (FEA) codes that use highly realistic random, 3D concrete microstructures from reconstructed coarse limestone aggregates. Finite element analysis performed provides the ability to quickly upscale mortar viscoelastic behavior to long-term concrete creep/relaxation data. A master creep compliance curve, constructed from the TTS principle, spanning 27 years, was used to validate two and a half decades of simulated concrete creep. Concurrently, three different simulated wall specimens were designed to mimic the behavior of post-tensioned concrete nuclear containment facility vessel walls over time as a result of concrete creep. The specimens were designed with different thicknesses, transverse and longitudinal reinforcement ratios, and level of post-tensioning stress. Each specimen contained various instrumentation to measure internal concrete temperature, concrete strain, and post-tensioning strain hourly for over 3 years. The concrete creep model developed in this project, based on the FEA concrete simulations, was applied to simulate the structural-scale experiments of prestressed concrete walls conducted in this project using the Grizzly code. These models can represent the effects of reinforcing and prestressing. Although there are some discrepancies with the experimental data, the model can predict the overall trends of the creep response in these experiments. One of these experimental models was also applied to an extended time to demonstrate how the findings from this study can be used to predict the behavior of actual structures of interest that have been in service for extended periods of time.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

SCUC-DER Integration Report: Integrating Distributed Energy Resources (DER) Using Advanced Unit Commitment Models and DER Aggregation Methodologies

Distributed energy resources (DERs) are continuing to grow due to regulatory, policy, and market shifts, and it needs to be ensured that small DERs are given a level playing field with traditional resources. Legacy market processes such as unit-commitment problems were designed for a power grid consisting largely of centralized power plants. In contrast, DERs consist of many small devices with distinct operating characteristics that may or may not be connected at the transmission interconnection points, limiting their visibility to the independent system operators (ISOs) who operate wholesale electricity markets. This report details the development and initial results from a simulation platform that integrates state-of-the-art security-constrained unit commitment software, detailed feeder models, and a DER aggregator model to quantify potential DER integration issues. Quantitative results to date illustrate potential infeasible scheduling solutions from SCUC when the DERA includes aggregations of energy-limited energy storage resources. Likewise, if aggregations are not penalized for dispatch deviations, they may have incentives to deviate from the SCUC-determined resource schedules. Assumptions about the amount of aggregated demand response resources (DRRs) and the ability of DERAs to follow profit incentives have an important impact – DRRs have significant flexibility and can typically feasibly meet their SCUC schedule, but on the other hand, their profit incentives can cause unscheduled increases in load before and after DRR dispatch. Computation time results on the SCUC solver and simulation platform only show a modest increase in SCUC solution time as the number of DERAs is increased, but results to date only reflect the RTS-GMLC test system; results may show more significant solver slowdown in larger transmission systems. The largest contribution to simulation time is attributed to the DERA offer generation method, which is suggested for future improvements.

24 POWER TRANSMISSION AND DISTRIBUTION↗

A Brief Review of Chaotropic vs. Kosmotropic Salts on the Degree of Saturation of Membrane Fatty Acids: Implications for Preservation of Environmental Biomarkers

Water activity is well known to have a significant impact on habitability, due to the presence of salts. However, salt composition is also important for habitability, as it can impact microbial activity and biomolecular interactions since certain salts are known to disrupt hydrogen bonding. Chaotropic agents disrupt hydrogen bonding in aqueous solutions leading to increased entropy (chaos) whereas kosmotropic agents are compounds that promote hydrogen bonding (order). The Hofmeister series (Fig. 1) shows the ordering of ions in terms of their ability to stabilize and induce precipitation or aggregation of proteins.

M B Wilhelm↗

Structure-based inhibitors of amyloid beta core suggest a common interface with tau

Alzheimer’s disease (AD) pathology is characterized by plaques of amyloid beta (Aβ) and neurofibrillary tangles of tau. Aβ aggregation is thought to occur at early stages of the disease, and ultimately gives way to the formation of tau tangles which track with cognitive decline in humans. Here, we report the crystal structure of an Aβ core segment determined by MicroED and in it, note characteristics of both fibrillar and oligomeric structure. Using this structure, we designed peptide-based inhibitors that reduce Aβ aggregation and toxicity of already-aggregated species. Unexpectedly, we also found that these inhibitors reduce the efficiency of Aβ-mediated tau aggregation, and moreover reduce aggregation and self-seeding of tau fibrils. The ability of these inhibitors to interfere with both Aβ and tau seeds suggests these fibrils share a common epitope, and supports the hypothesis that cross-seeding is one mechanism by which amyloid is linked to tau aggregation and could promote cognitive decline.

59 BASIC BIOLOGICAL SCIENCES↗

X-ray CT characterization and fracture simulation of ASR damage of glass particles in alkaline solution and mortar

The alkali-silica reaction (ASR) damage in reactive aggregates affects the long-term durability of the concrete infrastructure. The generated ASR gel can expand by imbibing water from the pore solution and the resulting expansion pressure causes the aggregate fracture. This study aims to simulate the development of ASR damage in glass particles of two types of samples (glass in alkali solution and glass mortars). The dynamic micro X-ray CT technique was conducted to monitor the crack propagation in glass aggregates at different reaction stages (up to 64 hrs). The Boundary Element Method (BEM) and Displacement Discontinuity Method (DDM) were used to efficiently simulate the crack propagation within irregular glass particles under gel expansion pressures. The aggregate boundaries were built with the BEM elements and the initial cracks were meshed with the DDM elements. The estimated expansion pressure was applied to the initial crack surfaces. The discontinuous displacements and stresses were calculated along the crack path and crack tip. The mixed-mode Stress Intensity Factors (SIFs) were calculated based on plane stress conditions. The maximum circumferential stress criteria was used to simulate the propagation of cracks along a specific angle. The simulation results include the simulated crack path and the combined SIFs changing with the increments. With the estimate expansion pressure, the glass particle damages were simulated within conditions of alkali solution and confined motar samples. The predicted crack propagation path was compared with the X-ray CT imaging data. The comparison results demonstrate the DDM has the ability to predicting the ASR damage propagation inside aggregates.

36 MATERIALS SCIENCE↗

Monolayer Vanadium‐Doped Tungsten Disulfide: A Room‐Temperature Dilute Magnetic Semiconductor

Abstract Dilute magnetic semiconductors (DMS), achieved through substitutional doping of spin‐polarized transition metals into semiconducting systems, enable experimental modulation of spin dynamics in ways that hold great promise for novel magneto–electric or magneto–optical devices, especially for two‐dimensional (2D) systems such as transition metal dichalcogenides that accentuate interactions and activate valley degrees of freedom. Practical applications of 2D magnetism will likely require room‐temperature operation, air stability, and (for magnetic semiconductors) the ability to achieve optimal doping levels without dopant aggregation. Here, room‐temperature ferromagnetic order obtained in semiconducting vanadium‐doped tungsten disulfide monolayers produced by a reliable single‐step film sulfidation method across an exceptionally wide range of vanadium concentrations, up to 12 at% with minimal dopant aggregation, is described. These monolayers develop p‐type transport as a function of vanadium incorporation and rapidly reach ambipolarity. Ferromagnetism peaks at an intermediate vanadium concentration of ~2 at% and decreases for higher concentrations, which is consistent with quenching due to orbital hybridization at closer vanadium–vanadium spacings, as supported by transmission electron microscopy, magnetometry, and first‐principles calculations. Room‐temperature 2D‐DMS provide a new component to expand the functional scope of van der Waals heterostructures and bring semiconducting magnetic 2D heterostructures into the realm of practical application.

36 MATERIALS SCIENCE↗

A method for processing the Confidential Carload Waybill Sample for railroad freight analysis

Freight transportation research is often constrained by the availability of appropriate data. Within the context of freight rail research, use of traditional freight datasets present some critical challenges. Aggregating freight data to geographic areas diminishes the ability to perform nuanced analysis. More challenging, the complexity of railroad operations limits the usability of publicly available freight flow data which do not account for which rail company is economically and legally responsible for the movement of the goods or for the contractual arrangements between infrastructure owners and carriers. Finally, detailed data are usually privately owned and not readily-accessible for analysis outside the individual rail companies. As part of their regulatory authority, the Surface Transportation Board has developed the Confidential Carload Waybill Sample, a stratified sample representing 1% to 3% of all rail traffic in the United States for a particular year. While the sample is rich with data, it is limited in spatial information as well as in its implementation in geospatial analysis. This paper introduces a methodology for geospatially enabling the Confidential Carload Waybill Sample which can then be used to generate rail routes based on a topological representation of the U.S. railroad network. As a result, this methodology is applied using two case studies, a freight diversion analysis and transporting hazardous materials.

42 ENGINEERING↗

Mycobacterium tuberculosis SatS is a chaperone for the SecA2 protein export pathway

The SecA2 protein export system is critical for the virulence of Mycobacterium tuberculosis. However, the mechanism of this export pathway remains unclear. Through a screen for suppressors of a secA2 mutant, we identified a new player in the mycobacterial SecA2 pathway that we named SatS for SecA2 (two) Suppressor. In M. tuberculosis, SatS is required for the export of a subset of SecA2 substrates and for growth in macrophages. We further identify a role for SatS as a protein export chaperone. SatS exhibits multiple properties of a chaperone, including the ability to bind to and protect substrates from aggregation. Our structural studies of SatS reveal a distinct combination of a new fold and hydrophobic grooves resembling preprotein-binding sites of the SecB chaperone. These results are significant in better defining a molecular pathway for M. tuberculosis pathogenesis and in expanding our appreciation of the diversity among chaperones and protein export systems.

Miller, Brittany K.↗

Modeling Electrolysis-based H2 Production for Grid Service Assessment

Hydrogen is a promising clean and renewable source of energy. Its high energy density offers a unique and effective means to store energy. The integration of hydrogen production devices with the power grid could lead to a cleaner and more reliable grid operation at reasonable costs. In this work, the capability of Proton Exchange Membrane (PEM) electrolyzers to perform grid services is assessed using a battery equivalent model approach. The Battery Equivalent Model (BEM) has been developed to represent the physics and operation of a fleet of PEM electrolyzers. The BEM model has been designed to be modular and readily incorporated into grid planning studies. This application of PEM electrolyzers can be integrated with other power generation and consumption devices, aggregating capabilities of each device to enhance the ability of the integrated system to provide grid services and improves grid stability. The developed model is evaluated using ancillary support services including peak management, frequency regulation, voltage regulation, artificial inertia, spinning reserve, and wholesale market price response using a representative price and power system profiles. The BEM model has also been evaluated to provide frequency regulation service that conforms to the IEEE 1547-2018 standard. Metrics such as energy efficiency, charging efficiency, hydrogen production rate, and service efficacy have been incorporated into the model to quantify the performance of the fleet while responding to grid services. Results show the electrolyzer fleet's effectiveness in quickly adjusting its real power consumption based on grid service requests. The energy efficiency of the fleet is maintained relatively high – in the range of 78% and 90% during the service operation. These results demonstrate the ability of PEM electrolyzers to effectively provide fast dispatch capability through storing off-peak hour energy while regulating power consumption during peak hours. The BEM model can assist in quantifying the stability and variability impacts from integration of PEM electrolyzers with intermittent renewable resources in grid integration studies.

08 HYDROGEN↗

Layer-by-Layer-Processed Organic Solar Cells with 18.02% Efficiency Enabled by Regulating the Aggregation of Bottom Polymers

The fabrication of organic solar cells (OSCs) by a layer-by-layer (LBL) method has attracted growing attention in recent years. As already known, the pre-aggregates of conjugated polymers in solution have a profound impact on their microstructure morphology in films. Herein, by simply controlling the solution temperature and annealing processes, the pre-aggregation behavior of D18 polymer in solution can be fine-tuned and the microstructure of D18 bottom layer is well manipulated. The optimized D18 bottom layer can effectively regulate L8-BO upper-layer-forming suitable networks for efficient charge transportation. In addition, a vertical phase separation with a special D/D:A/A structure (P-i-N-type component distribution) is also formed. As a result, compared to the 16.43% power conversion efficiency (PCE) of the bulk heterojunction devices, such control enables bilayer OSC devices based on the polymer D18 and L8-BO to deliver an enhanced PCE of 18.02% with simultaneously improved short-circuit current density, open-circuit voltage, and fill factor. Importantly, it is also demonstrated in these results that the LBL deposition process utilizing the pre-aggregation of polymer and its fiber-network-forming ability is a very promising approach to improve charge dynamics, suppress carrier recombination, and fabricate highly efficient OSCs.

14 SOLAR ENERGY↗

Anomalous Anisotropic Nanoparticle Aggregation in Cu 2 (OH) 3 Br Gels

Aerogels are of interest for their ability to uniformly incorporate nanoscale features into macroscopic assemblies, which enabled applications that require low density, high surface area, and/or bicontinuous networks. The structure of the nanoporous network is intrinsically linked to the macroscopic properties of aerogels. Hence, control of this structure is of paramount importance. Small-angle X-ray scattering (SAXS) is used here to monitor nanoparticle aggregation in situ in Cu 2 (OH) 3 Br aerogels formed via epoxide-assisted gelation. Anomalous anisotropic aggregation is observed in the absence of templating agents and is attributed to the molecular structure of the inorganic nanoparticles themselves. This is a fundamental departure from the models currently used to describe traditional inorganic sol–gel chemistry where nanoparticles are believed to undergo isotropic diffusion- and/or kinetically limited aggregation. Time-resolved SAXS indicates that Cu 2 (OH) 3 Br nanoparticles nucleate rapidly from solution to form unbranched chain-like aggregates rather than branched mass-fractal aggregates. Sizes of primary particles (~1.5 nm) and the chain-like structure of their aggregates are independent of particle concentration (gel density), while rates of particle aggregation, gelation time, and aggregate size are strongly dependent upon particle concentration, which implies that the chemistry of particle formation and the physics of particle aggregation are independent processes. Because the conditions necessary for creating anisotropic structures are not unique to Cu 2 (OH) 3 Br, these results could provide insight into the structure and gelation mechanisms of other inorganic aerogels.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗