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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 469 records · Page 26
All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

What is the best method to fit time-resolved data? A comparison of the residual minimization and the maximum likelihood techniques as applied to experimental time-correlated, single-photon counting data

The need for measuring fluorescence lifetimes of species in subdiffraction-limited volumes in, for example, stimulated emission depletion (STED) microscopy, entails the dual challenge of probing a small number of fluorophores and fitting the concomitant sparse data set to the appropriate excited-state decay function. This need has stimulated a further investigation into the relative merits of two fitting techniques commonly referred to as “residual minimization” (RM) and “maximum likelihood” (ML). Fluorescence decays of the well-characterized standard, rose bengal in methanol at room temperature (530 ± 10 ps), were acquired in a set of five experiments in which the total number of “photon counts” was approximately 20, 200, 1000, 3000, and 6000 and there were about 2–200 counts at the maxima of the respective decays. Each set of experiments was repeated 50 times to generate the appropriate statistics. Each of the 250 data sets was analyzed by ML and two different RM methods (differing in the weighting of residuals) using in-house routines and compared with a frequently used commercial RM routine. Convolution with a real instrument response function was always included in the fitting. While RM using Pearson’s weighting of residuals can recover the correct mean result with a total number of counts of 1000 or more, ML distinguishes itself by yielding, in all cases, the same mean lifetime within 2% of the accepted value. For 200 total counts and greater, ML always provides a standard deviation of <10% of the mean lifetime, and even at 20 total counts there is only 20% error in the mean lifetime. Here, the robustness of ML advocates its use for sparse data sets such as those acquired in some subdiffraction-limited microscopies, such as STED, and, more importantly, provides greater motivation for exploiting the time-resolved capacities of this technique to acquire and analyze fluorescence lifetime data.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Minimization of Disorder as a Key Design Principle for Natural Sizes of Light Harvesting 2 Complexes

The light harvesting 2 (LH2) complex of purple bacteria has excellent energy conversion efficiency. Clarifying the design principle behind such efficiency at the atomistic level is crucial for understanding its structure–function relationship and can be utilized for the design of artificial light harvesting systems. To this end, we conducted comprehensive computational investigation of the dynamical and statistical nature of electronic excited states of pigment molecules in a natural LH2 complex with 9-fold symmetry and its two non-natural in silico analogues with 6- and 12-fold symmetries. To ensure reliable and efficient all-atomistic molecular dynamics simulations, we combined a well established interpolation approach for the construction of the potential energy surface with a neural network machine learning approach. Outcomes of these calculations clarify that non-natural forms of LH2-type complexes have significantly larger quasistatic disorder than those for the natural one. In addition, non-natural systems have more disruptions of the hydrogen bonding, underscoring its crucial role for reducing the disorder. On the other hand, local environmental dynamics are relatively insensitive to the structural changes although there is moderate enhancement in the anharmonic or interatomic components for the synthetic ones. These findings based on all-atomistic simulations provide direct computational evidence that the structure and sizes of natural LH2 complexes are designed to minimize the energetic disorder. We analyze quantitative implications of these for the energy transferring capability of the LH2 complex.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

High-Temperature Grafting Silylation for Minimizing Leaching of Acid Functionality from Hydrophobic Mesoporous Silicas Used as Catalysts in the Liquid Phase

Ordered-hexagonal silica materials, such as Mobil crystalline material-41 and Santa Barbara amorphous-15, have important applications in heterogeneous catalysis and biomass conversion due to their chemical stability and mesoporous structure. Low-temperature grafting (LG) is one of the most common functionalization methods used to modify the acidity/basicity or hydrophobicity/hydrophilicity of the surface. However, the materials prepared by this method are prone to leaching of functional groups into the reaction medium. The exact nature of the leaching phenomenon has not been fully addressed in the literature. In this contribution, we have investigated this process at the molecular level by combining well-controlled reaction experiments and several characterization techniques (Fourier transform infrared, 1 H– 29 Si cross-polarization magic-angle spinning NMR, X-ray diffraction, thermogravimetric analysis, and N 2 adsorption–desorption). We have found that leaching is originated by the presence of terminal surface silanols, which render the catalysts susceptible to the attack of water and polar compounds. Hence, instead of simple detaching of functional groups, leaching can be better described as a partial dissolution of the surface layers of the silica, which of course also removes the functional groups during this process. Therefore, an effective strategy to minimize leaching is to reduce the density of free silanols via full functionalization of the surface. Here, we propose a novel silylation method, high-temperature grafting, which allows the grafting process to be conducted at high temperatures (180 °C) under solvent-free conditions. By this method, a more complete silylation of surface silanols can be obtained. Consequently, the samples prepared by this high-temperature grafting method show to be highly stable during acid-catalyzed alkylation reaction, conducted under severe conditions (high temperature and in the presence of polar solvents).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Modified Coprecipitation Synthesis of Mesostructure-Controlled Li-Rich Layered Oxides for Minimizing Voltage Degradation

In this work, modified carbonate coprecipitation synthesis without addition of chelating agent is introduced to obtain mesostructure-controlled Li-rich layered oxides. The designed mesostructure for target material Li 1.2 Ni 0.2 Mn 0.6 O 2 has uniformly dispersed spherical secondary particles with size around 3 μm. These micrometer-sized particles consist of self-assembled crystallites with size of ~150 nm. This unique design not only decreases the surface area compared with the sample with dispersive particles, but also increases overall structural mechanical stability compared with the sample with larger dense secondary particles as observed by transmission X-ray microscope. As a result, the voltage decay and capacity loss during long-term cycling have been minimized to a large extent. Our findings clearly demonstrate that mesostructure design of Li-rich layered oxides play a key role in optimizing this class of cathode materials. Surprisingly, the voltage fading issue can be partially mitigated by such an approach.

25 ENERGY STORAGE↗
DOE OSTI2020

Si Microwire-Array Photocathodes Decorated with Cu Allow CO 2 Reduction with Minimal Parasitic Absorption of Sunlight

High loadings of Cu were integrated on the light-facing side of Si microwire arrays used under simulated sunlight for the photoelectrochemical reduction of CO 2 (aq) to hydrocarbons in 0.10 M KHCO 3 (aq). Radial-junction n + p-Si microwire arrays decorated with Cu exhibited absolute photocurrent densities comparable to an uncovered Si surface. Moreover, with respect to a Cu foil electrode, the positive shift in the onset potential for hydrocarbon formation at n + p-Si/Cu microwire arrays was equal to or greater than the photovoltage of the semiconductor alone. Selective electrodeposition of Cu on the tips and sidewalls of Si microwires was responsible for the minimal parasitic reflection and absorption exhibited by the catalyst, such that light-limited, absolute current densities >25 mA·cm –2 were sustained for 48 h under simulated sunlight. Photoelectrodes prepared from semiconductors with low diode quality factors and electrocatalysts with large Tafel slopes are shown to benefit from increased microstructured surface area. Si microwire arrays are thus suitable for photoelectrochemical reactions requiring high loadings of metallic and reflective electrocatalysts.

25 ENERGY STORAGE↗
DOE OSTI2018

Hydrogen Evolution with Minimal Parasitic Light Absorption by Dense Co–P Catalyst Films on Structured p-Si Photocathodes

Planar and three-dimensionally structured p-Si devices, consisting of an electrodeposited Co–P catalyst on arrays of Si microwires or Si micropyramids, were used as photocathodes for solar-driven hydrogen evolution in 0.50 M H 2 SO 4 (aq) to assess the effects of electrode structuring on parasitic absorption by the catalyst. Without the use of an emitter layer, p-Si/Co–P microwire arrays produced a photocurrent density of -10 mA cm –2 at potentials that were 130 mV more positive than those of optimized planar p-Si/Co–P devices. Champion p-Si/Co–P microwire array devices exhibited ideal regenerative cell solar-to-hydrogen efficiencies of >2.5% and were primarily limited by the photovoltage of the p-Si/Co–P junction. Therefore, the vertical sidewalls of the Si microwire photoelectrodes minimized effects due to parasitic absorption at high loadings of catalyst for device structures with or without emitters.

14 SOLAR ENERGY↗
DOE OSTI2019

Determining and Minimizing Resistance for Ion Transport at the Polymer/Ceramic Electrolyte Interface

In this work, we report methods to quantify and minimize the interfacial resistance for Li ion transport, R interface , between a model polymer electrolyte, poly(ethylene oxide) + LiCF 3 SO 3 (PE), and a model Li + -conducting ceramic electrolyte, LICGC from Ohara Corporation. By constructing a PE–ceramic–PE trilayer cell, we found R interface to be very large, 1.2 kΩ·cm 2 at 30 °C, accounting for 66% of the total trilayer cell resistance. When dimethyl carbonate, a loose-binding solvent of Li + , was introduced into the trilayer, R interface decreased to essentially zero. As a result, a composite electrolyte with carbonate plasticizers wherein 40 vol % ceramic particles were dispersed in the polymer showed extraordinary room-temperature conductivity of approximately 10 –4 S/cm, 3 orders of magnitude higher than that of the dry composite electrolyte. Here, this discovery can be used as guidance in designing composite electrolytes to achieve synergistic effects.

36 MATERIALS SCIENCE↗
DOE OSTI2020

A Preorganized Electric Field Leads to Minimal Geometrical Reorientation in the Catalytic Reaction of Ketosteroid Isomerase

Electrostatic interactions play a pivotal role in enzymatic catalysis and are increasingly modeled explicitly in computational enzyme design; nevertheless, they are challenging to measure experimentally. Using vibrational Stark effect (VSE) spectroscopy, we have measured electric fields inside the active site of the enzyme ketosteroid isomerase (KSI). These studies have shown that these fields can be unusually large, but it has been unclear to what extent they specifically stabilize the transition state (TS) relative to a ground state (GS). In the following, we use crystallography and computational modeling to show that KSI’s intrinsic electric field is nearly perfectly oriented to stabilize the geometry of its reaction’s TS. Moreover, we find that this electric field adjusts the orientation of its substrate in the ground state so that the substrate needs to only undergo minimal structural changes upon activation to its TS. This work provides evidence that the active site electric field in KSI is preorganized to facilitate catalysis and provides a template for how electrostatic preorganization can be measured in enzymatic systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Increased Crystal Field Drives Intermediate Coupling and Minimizes Decoherence in Tetravalent Praseodymium Qubits

Crystal field (CF) control of rare-earth (RE) ions has been employed to minimize decoherence in qubits and to enhance the effective barrier of single-molecule magnets. The CF approach has been focused on the effects of symmetry on dynamic magnetic properties. Herein, the magnitude of the CF is increased via control of the RE oxidation state. The enhanced 4f metal-ligand covalency in Pr 4+ gives rise to CF energy scales that compete with the spin-orbit coupling of Pr 4+ and thereby shifts the paradigm from the ionic ζ SOC >> V CF limit, used to describe trivalent RE-ion, to an intermediate coupling (IC) regime. We examine Pr 4+ -doped perovskite oxide lattices (BaSnO 3 and BaZrO 3 ). These systems are defined by IC which quenches orbital angular momentum. Therefore, the single-ion spin-orbit coupled states in Pr 4+ can be chemically tuned. We demonstrate a relatively large hyperfine interaction of A iso = 1800 MHz for Pr 4+ , coherent manipulation of the spin with Q M = 2Ω R $T$ m reaching up to ~400 for 0.1Pr:BSO at $T$ = 5 K, and significant improvement of the temperature at which $T$ m is limited by $T$ 1 ($T$* = 60 K) compared to other RE ion qubits.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Biosynthesis of Minimal C-Phycocyanin Chromophore Assemblies in E. coli Provides a Platform to Dissect Protein-Mediated Tuning of Exciton Transfer

Cyanobacteria are arguably among the most evolutionarily successful organisms on Earth, inhabiting a wide range of ocean, freshwater, soil, and even desert environments on every continent. The cyanobacterial phycobilisome consists of stacks of disk-like light-collecting moieties, allophycocyanin (APC) and phycocyanin (CPC), with covalently bound phycocyanobilin (PCB) pigments. The ways in which the energies of the specific chromophores in these complexes are tuned by the protein to achieve its highly efficient and directional energy transfer are not fully understood, as complex combinations of decay pathways are occurring simultaneously and competitively through this elaborate light-harvesting system. This makes it difficult to extract information about isolated protein-pigment interactions. We provide herein a description of a useful new experimental platform in which we have recombinantly expressed a fully functioning CPC complex and selectively created minimal chromophore sets to study their individual contributions to the overall CPC spectra. Structural and computational analysis of this protein system have provided a greater understanding of how the protein environment serves to alter the photophysics of each of these chromophores. Introduction of a quencher into various positions within CPC confirmed the ability of the protein environment to tune the directionality of energy transport in this assembly. Further mutational analysis suggested the roles of key amino acids surrounding the chromophores, showcasing the utility of heterologous expression techniques for understanding the effects of structure on EET mechanisms in the phycobilisome.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Deciphering minimal antigenic epitopes associated with Burkholderia pseudomallei and Burkholderia mallei lipopolysaccharide O-antigens

Burkholderia pseudomallei (Bp) and Burkholderia mallei (Bm), the etiologic agents of melioidosis and glanders, respectively, cause severe disease in both humans and animals. Studies have highlighted the importance of Bp and Bm lipopolysaccharides (LPS) as vaccine candidates. Here we describe the synthesis of seven oligosaccharides as the minimal structures featuring all of the reported acetylation/methylation patterns associated with Bp and Bm LPS O-antigens (OAgs). Our approach is based on the conversion of an L-rhamnose into a 6-deoxy-L-talose residue at a late stage of the synthetic sequence. Using biochemical and biophysical methods, we demonstrate the binding of several Bp and Bm LPS-specific monoclonal antibodies with terminal OAg residues. Mice immunized with terminal disaccharide–CRM197 constructs produced high-titer antibody responses that crossreacted with Bm-like OAgs. Collectively, these studies serve as foundation for the development of novel therapeutics, diagnostics, and vaccine candidates to combat diseases caused by Bp and Bm.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Minimally disruptive optical control of protein tyrosine phosphatase 1B

Protein tyrosine phosphatases regulate a myriad of essential subcellular signaling events, yet they remain difficult to study in their native biophysical context. Here we develop a minimally disruptive optical approach to control protein tyrosine phosphatase 1B (PTP1B)—an important regulator of receptor tyrosine kinases and a therapeutic target for the treatment of diabetes, obesity, and cancer—and we use that approach to probe the intracellular function of this enzyme. Our conservative architecture for photocontrol, which consists of a protein-based light switch fused to an allosteric regulatory element, preserves the native structure, activity, and subcellular localization of PTP1B, affords changes in activity that match those elicited by post-translational modifications inside the cell, and permits experimental analyses of the molecular basis of optical modulation. Findings indicate, most strikingly, that small changes in the activity of PTP1B can cause large shifts in the phosphorylation states of its regulatory targets.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Design of COVID-19 staged alert systems to ensure healthcare capacity with minimal closures

Community mitigation strategies to combat COVID-19, ranging from healthy hygiene to shelter-in-place orders, exact substantial socioeconomic costs. Judicious implementation and relaxation of restrictions amplify their public health benefits while reducing costs. We derive optimal strategies for toggling between mitigation stages using daily COVID-19 hospital admissions. With public compliance, the policy triggers ensure adequate intensive care unit capacity with high probability while minimizing the duration of strict mitigation measures. In comparison, we show that other sensible COVID-19 staging policies, including France’s ICU-based thresholds and a widely adopted indicator for reopening schools and businesses, require overly restrictive measures or trigger strict stages too late to avert catastrophic surges. As proof-of-concept, we describe the optimization and maintenance of the staged alert system that has guided COVID-19 policy in a large US city (Austin, Texas) since May 2020. As cities worldwide face future pandemic waves, our findings provide a robust strategy for tracking COVID-19 hospital admissions as an early indicator of hospital surges and enacting staged measures to ensure integrity of the health system, safety of the health workforce, and public confidence.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2021

Minimizing hydrogen vacancies to enable highly efficient hybrid perovskites

Defect-induced non-radiative losses are currently limiting the performance of hybrid perovskite devices. Experimental reports have indicated the existence of point defects that act as detrimental non-radiative recombination centres under iodine-poor synthesis conditions. However, the microscopic nature of these defects is still unknown. Here we demonstrate that hydrogen vacancies can be present in high densities under iodine-poor conditions in the prototypical hybrid perovskite MAPbI 3 (MA = CH 3 NH 3 ). They act as very efficient non-radiative recombination centres with an exceptionally high carrier capture coefficient of 10 –4 cm 3 s –1 . By contrast, the hydrogen vacancies in FAPbI 3 [FA = CH(NH 2 ) 2 ] are much more difficult to form and have a capture coefficient that is three orders of magnitude lower. Our study unveils the critical but overlooked role of hydrogenvacancies in hybrid perovskites and rationalizes why FA is essential for realizing high efficiency in hybrid perovskite solar cells. Furthermore, minimizing the incorporation of hydrogen vacancies is key to enabling the best performance of hybrid perovskites.

14 SOLAR ENERGY↗
DOE OSTI2018

Minimal East Antarctic Ice Sheet retreat onto land during the past eight million years

We report the East Antarctic Ice Sheet (EAIS) is the largest potential contributor to sea-level rise. However, efforts to predict the future evolution of the EAIS are hindered by uncertainty in how it responded to past warm periods, for example, during the Pliocene epoch (5.3 to 2.6 million years ago), when atmospheric carbon dioxide concentrations were last higher than 400 parts per million. Geological evidence indicates that some marine-based portions of the EAIS and the West Antarctic Ice Sheet retreated during parts of the Pliocene, but it remains unclear whether ice grounded above sea level also experienced retreat. This uncertainty persists because global sea-level estimates for the Pliocene have large uncertainties and cannot be used to rule out substantial terrestrial ice loss, and also because direct geological evidence bearing on past ice retreat on land is lacking. Here we show that land-based sectors of the EAIS that drain into the Ross Sea have been stable throughout the past eight million years. We base this conclusion on the extremely low concentrations of cosmogenic 10 Be and 26 Al isotopes found in quartz sand extracted from a land-proximal marine sediment core. This sediment had been eroded from the continent, and its low levels of cosmogenic nuclides indicate that it experienced only minimal exposure to cosmic radiation, suggesting that the sediment source regions were covered in ice. These findings indicate that atmospheric warming during the past eight million years was insufficient to cause widespread or long-lasting meltback of the EAIS margin onto land. We suggest that variations in Antarctic ice volume in response to the range of global temperatures experienced over this period—up to 2–3 degrees Celsius above preindustrial temperatures, corresponding to future scenarios involving carbon dioxide concentrations of between 400 and 500 parts per million—were instead driven mostly by the retreat of marine ice margins, in agreement with the latest models.

58 GEOSCIENCES↗
DOE OSTI2023

Grassland carbon-water cycling is minimally impacted by a photovoltaic array

Agrivoltaic systems, whereby photovoltaic arrays are co-located with crop or forage production, can alleviate the tension between expanding solar development and loss of agricultural land. However, the ecological ramifications of these arrays are poorly known. We used field measurements and a plant hydraulic model to quantify carbon-water cycling in a semi-arid C 3 perennial grassland growing beneath a single-axis tracking solar array in Colorado, USA. Although the agrivoltaic array reduced light availability by 38%, net photosynthesis and aboveground net primary productivity were reduced by only 6–7% while evapotranspiration decreased by 1.3%. The minimal changes in carbon-water cycling occurred largely because plant photosynthetic traits underneath the panels changed to take advantage of the dynamic shading environment. Our results indicate that agrivoltaic systems can serve as a scalable way to expand solar energy production while maintaining ecosystem function in managed grasslands, especially in climates where water is more limiting than light.

14 SOLAR ENERGY↗
DOE OSTI2014

Towards ultra-thin plasmonic silicon wafer solar cells with minimized efficiency loss

The cost-effectiveness of market-dominating silicon wafer solar cells plays a key role in determining the competiveness of solar energy with other exhaustible energy sources. Reducing the silicon wafer thickness at a minimized efficiency loss represents a mainstream trend in increasing the cost-effectiveness of wafer-based solar cells. In this paper we demonstrate that, using the advanced light trapping strategy with a properly designed nanoparticle architecture, the wafer thickness can be dramatically reduced to only around 1/10 of the current thickness (180 mm) without any solar cell efficiency loss at 18.2%. Nanoparticle integrated ultra-thin solar cells with only 3% of the current wafer thickness can potentially achieve 15.3% efficiency combining the absorption enhancement with the benefit of thinner wafer induced open circuit voltage increase. This represents a 97% material saving with only 15% relative efficiency loss. These results demonstrate the feasibility and prospect of achieving high-efficiency ultra-thin silicon wafer cells with plasmonic light trapping.

14 SOLAR ENERGY↗