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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 865 records · Page 48
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Cell-Free-Based Thermophilic Biocatalyst for the Synthesis of Amino Acids from One-Carbon Feedstocks

Bioproduction from one-carbon compounds, such as formate, is an attractive prospect due to reduced energy requirements and the possibility for using CO 2 as a sustainable feedstock. Formate-fixing pathways engineered using Escherichia coli lysate-based cell-free expression (CFE) biocatalysts have the potential to route 100% of feedstock carbon toward chemical synthesis but are undermined by siphoning of in-pathway metabolites and cofactors by the CFE background metabolism. To address this limitation, we engineer a CFE-based thermophilic multienzyme biocatalyst for the synthesis of serine and glycine from formate, bicarbonate, and ammonia. After expression of the thermophilic formate-to-serine pathway in a one-pot reaction, the mesophilic E. coli CFE background machinery is removed by simple heat denaturation, eliminating the siphoning of cofactors, inpathway metabolites, and products. After bioprocess optimization, including pathway gene expression duration and chemical synthesis temperature, we achieve near stoichiometric conversion of formate and bicarbonate to serine and glycine, reaching 97% of stoichiometric yield. The use of a moderately thermophilic biocatalyst allowed chemical synthesis to take place at mesophilic temperatures, enabling the balance of optimal enzyme activity with minimal metabolite/cofactor thermal degradation. In a fed-batch experiment, the biocatalyst shows sustained chemical synthesis rates for 8 h, paving the way toward a continuous bioprocess. Finally, a sensitivity analysis of cofactor usage revealed that the most expensive cofactors, THF and NADPH, can be reduced by 5-fold without significantly lowering product yields. To the best of our knowledge, this is the first instance of expressing a thermophilic pathway in an E. coli lysate-based CFE system to generate a thermophilic biocatalyst for use at mesophilic temperatures. The CFEbased thermophilic formate-to-serine biocatalyst triples the combined serine and glycine yield previously obtained by a CFE-based mesophilic formate-to-serine biocatalyst (30%), and quadruple the yield obtained by a purified enzyme system (22%). Ultimately, this work opens the door to using E. coli lysate-based CFE for thermophilic biocatalyst generation to achieve high chemical synthesis yields.

bacteria↗
DOE OSTI2025

Solvent Screening for Separation Processes Using Machine Learning and High-Throughput Technologies

As the chemical industry shifts toward sustainable practices, there is a growing initiative to replace conventional fossil-derived solvents with environmentally friendly alternatives such as ionic liquids (ILs) and deep eutectic solvents (DESs). Artificial intelligence (AI) plays a key role in the discovery and design of novel solvents and the development of green processes. This review explores the latest advancements in AI-assisted solvent screening with a specific focus on machine learning (ML) models for physicochemical property prediction and separation process design. Additionally, this paper highlights recent progress in the development of automated high-throughput (HT) platforms for solvent screening. Finally, this paper discusses the challenges and prospects of ML-driven HT strategies for green solvent design and optimization. To this end, this review provides key insights to advance solvent screening strategies for future chemical and separation processes.

Artificial intelligence↗
DOE OSTI2022

Pressure-Driven Changes in the Electronic Bonding Environment of GeO 2 Glass above Megabar Pressures

Noncrystalline oxides under pressure undergo gradual structural modifications, highlighted by the formation of a dense noncrystalline network topology. The nature of the densified networks and their electronic structures at high pressures may account for the mechanical hardening and the anomalous changes in electromagnetic properties. Despite its importance, direct probing of the electronic structures in amorphous oxides under compression above the Mbar pressure (>100 GPa) is currently lacking. Here, we report the observation of pressure-driven changes in electronic configurations and their delocalization around oxygen in glasses using inelastic X-ray scattering spectroscopy (IXS). In particular, the first O K-edge IXS spectra for compressed GeO 2 glass up to 148 GPa, the highest pressure ever reached in an experimental study of GeO 2 glass, reveal that the glass densification results from a progressive increase of oxygen proximity. While the triply coordinated oxygen [3] O is dominant below ~50 GPa, the IXS spectra resolve multiple edge features that are unique to topologically disordered [4] O upon densification above 55 GPa. Topological compaction in GeO 2 glass above 100 GPa results in pronounced electronic delocalization, revealing the contribution from Ge d-orbitals to oxide densification. Strong correlations between the glass density and the electronic configurations beyond the Mbar conditions highlight the electronic origins of densification of heavy-metal-bearing oxide glasses. Furthermore, current experimental breakthroughs shed light on the direct probing of the electronic density of states in high-Z oxides above 1 Mbar, offering prospects for studies on the pressure-driven changes in magnetism, superconductivity, and electronic transport properties in heavy-metal-bearing oxides under compression.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Ligand Desorption and Fragmentation in Oleate-Capped CdSe Nanocrystals under High-Intensity Photoexcitation

Semiconductor nanocrystals (NCs) offer prospective use as active optical elements in photovoltaics, light-emitting diodes, lasers, and photocatalysts due to their tunable optical absorption and emission properties, high stability, and scalable solution processing, as well as compatibility with additive manufacturing routes. Over the course of experiments, during device fabrication, or while in use commercially, these materials are often subjected to intense or prolonged electronic excitation and high carrier densities. The influence of such conditions on ligand integrity and binding remains underexplored. Here, in this study, we expose CdSe NCs to laser excitation and monitor changes in oleate that is covalently attached to the NC surface using nuclear magnetic resonance as a function of time and laser intensity. Higher photon doses cause increased rates of ligand loss from the particles, with upward of 50% total ligand desorption measured for the longest, most intense excitation. Surprisingly, for a range of excitation intensities, fragmentation of the oleate is detected and occurs concomitantly with formation of aldehydes, terminal alkenes, H 2 , and water. After illumination, NC size, shape, and bandgap remain constant although low-energy absorption features (Urbach tails) develop in some samples, indicating formation of substantial trap states. The observed reaction chemistry, which here occurs with low photon to chemical conversion efficiency, suggests that ligand reactivity may require examination for improved NC dispersion stability but can also be manipulated to yield desired photocatalytically accessed chemical species.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Entropy-Tailored Fast-Charging Sodium Layered Cathodes

O3-type layered transition metal (TM) oxides are widely used as cathode materials for Na-ion batteries due to their high energy density potential, enabled by the state of charge (SoC)-dependent transition from octahedral (O-type) to prismatic (P-type) structures during Na-ion (de)sodiation. However, the O–P transition is often criticized for compromising the Na-ion mobility and limiting the cycle life. Herein, we reveal the intrinsic correlation between O–P transitions, oxygen behaviors, and Na-ion kinetics. We demonstrate that a compositionally versatile, entropy-tailored approach can promote preferred transitions (characterized by large lattice parameter deviations in the O-type region and rapid O–P biphasic reactions), enhancing Na-ion migration, as revealed by in situ high-energy synchrotron X-ray diffraction (HEXRD). Additionally, irreversible oxygen loss at high SoC is effectively mitigated, while TM migration and surface reconstruction are greatly suppressed, further accelerating Na-ion transport and stabilizing the structure, as confirmed by X-ray absorption spectroscopy (XAS) and theoretical analyses. The result is an exceptionally high rate capability of 88.7 mAh g –1 at 20 C (2.4 A g –1 ) with a superior normalized retention of 72.6%, accompanied by a prolonged lifetime with 74.3% retention after 1000 cycles. In conclusion, this work advances the understanding of the chemistry–property relationships in O3-type layered cathodes and broadens the prospects for fabricating high-power-density electrodes.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Permanent Nanobubbles in Water: Liquefied Hollow Carbon Spheres Break the Limiting Diffusion Current of Oxygen Reduction Reaction

Porous liquids have traditionally been designed with sterically hindered solvents. Alternatively, recent efforts rely on dispersing microporous frameworks in simpler solvents like water. Here we report a unique strategy to construct macroporous water by selectively incorporating hydrophilicity on the surfaces of hydrophobic hollow carbon spheres (HCS). Specifically, we show that the stable dispersion surface ionized HCS in water while retaining the inherent porosity. The electrocatalytic conversion of small gas molecules in aqueous electrolytes is limited by the concentration and diffusion rates of gas molecules in water. In this case, macroporous water exhibited 6 times gas uptake compared to nonporous (pure) water. Furthermore, by leveraging the high gas capacity and enhanced diffusion kinetics, the limiting diffusion current of oxygen reduction reaction (ORR) in macroporous water is 2 times that in nonporous water, offering promising prospects for sustainable energy conversion technologies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Can the Hock Process Be Used to Produce Phenol from Polystyrene?

Polystyrene (PS) is a widely used thermoplastic polymer, but its very low recycling rate has motivated consideration of chemical conversion strategies to convert waste PS into value-added products. Oxidation methods have been widely studied, but they typically generate benzoic acid, a product with a relatively low market demand. Phenol is a higher volume chemical that would be an appealing target, but no methods currently exist for the conversion of PS into phenol. The repeat unit in PS closely resembles cumene, the primary feedstock used to produce phenol through the Hock process. Here, we investigate prospects for adapting the Hock process to PS, generating hydroperoxides through the autoxidation of benzylic C–H bonds followed by the acid-promoted rearrangement of the hydroperoxides to afford phenol and a partially oxygenated polymer. Experimental and computational studies of dimeric and trimeric PS model compounds show that neighboring phenyl rings impose conformational constraints that raise the barrier to hydrogen-atom transfer from the tertiary benzylic C–H bond. These effects are also evident with PS and contribute to lower yields of phenol when PS is subjected to Hock process conditions. Furthermore, these results provide valuable insights that have important implications for other efforts that seek to adapt small-molecule reactivity to polymeric feedstocks.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Long-Range Resonant Charge Transport through Open-Shell Donor–Acceptor Macromolecules

A grand challenge in molecular electronics is the development of molecular materials that can facilitate efficient longrange charge transport. Research spanning more than two decades has been fueled by the prospects of creating a new generation of miniaturized electronic technologies based on molecules whose synthetic tunability offers tailored electronic properties and functions unattainable with conventional electronic materials. However, current design paradigms produce molecules that exhibit off-resonant transport under low bias, which limits the conductance of molecular materials to unsatisfactorily low levels several orders of magnitude below the conductance quantum 1 G 0 and often results in an exponential decay in conductance with length. Here, we demonstrate a chemically robust, air-stable, and highly tunable molecular wire platform comprised of open-shell donor−acceptor macromolecules that exhibit remarkably high conductance close to 1 G 0 over a length surpassing 20 nm under low bias, with no discernible decay with length. Single-molecule transport measurements and ab initio calculations show that the ultralong-range resonant transport arises from extended π-conjugation, a narrow bandgap, and diradical character, which synergistically enables excellent alignment of frontier molecular orbitals with the electrode Fermi energy. The implementation of this long-sought-after transport regime within molecular materials offers new opportunities for the integration of manifold properties within emerging nanoelectronic technologies.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Visualizing the Three-Dimensional Arrangement of Hydrogen Atoms in Organic Molecules by Coulomb Explosion Imaging

Structure-sensitive methods based on femtosecond light or electron pulses are now making it possible to measure how molecular structures change during light-induced processes. Despite significant progress, high-fidelity imaging of nuclear positions remains a challenge even for relatively small molecular systems and, notably, regarding the positions of hydrogen atoms. As demonstrated in recent work, X-ray-induced Coulomb explosion imaging (CEI) may overcome this obstacle, as its sensitivity does not depend on the mass of the imaged atoms. The photoinduced ring opening of the heterocyclic molecule 2(5 H )-thiophenone has attracted recent interest. Here, in this work, we show that CEI offers a powerful route to imaging the peripheral H atoms in this molecule and thus, more generally, to tracking detailed nuclear motions (e.g., isomerizations) in organic molecules on ultrafast time scales. Specifically, we record momentum-space Coulomb explosion images that report on the three-dimensional positioning of all nuclei within the molecule, for instance, distinguishing H atoms in C–H bonds that lie within or are directed out of the plane defined by the heavy atoms. The prospect of imaging peripheral H atoms to probe photochemical dynamics is explored by coupling ab initio molecular dynamics with classical Coulomb explosion simulations, thereby differentiating potential photoproduct isomers, including those whose structures primarily differ in the position of the hydrogens.

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

Photo-DAC: Light-Driven Ambient-Temperature Direct Air Capture by a Photobase

Direct air capture (DAC) may reduce atmospheric CO 2 concentrations to preindustrial levels, yet the high energies and temperatures involved in current DAC technologies hinder large-scale deployment. In the case of aqueous-based CO 2 absorbents, a large energetic penalty is associated with heating and boiling off water, as required for thermally driven solvent regeneration. This could be avoided via photochemically driven pH swings involving photoacids or photobases, and harnessing abundant and renewable solar energy, though efficient solvent regeneration and recycling in a realistic multicycle DAC process remains challenging. Herein, we report a photochemically driven DAC process (photo-DAC) in which atmospheric CO 2 capture by an aqueous glycylglycine (GlyGly) solution is enabled through a pH swing by a pyridine-substituted diiminoguanidine (PyDIG) photobase. Upon irradiation with UV light, the PyDIG photobase undergoes photoisomerization from the E,E to the Z,Z isomer, corresponding to a pK a increase of 2.8 units that activates GlyGly for DAC through deprotonation. After the GlyGly/PyDIG solvent is saturated with atmospheric carbon dioxide, leaving it in the dark under ambient conditions leads to the isomerization of PyDIG from the Z,Z back to the E,E isomer, which is accompanied by a pH drop and CO 2 release. To demonstrate the recyclability of the GlyGly/PyDIG solvent, we have completed six consecutive DAC cycles, with a measured average cyclic capacity in the range of 0.21–0.26 mol CO 2 per mol of GlyGly/PyDIG. These results open the prospect for energy-efficient DAC cycles completed entirely at ambient conditions, thereby avoiding the significant energy penalties associated with heating and boiling aqueous solvents.

Einkauf, Jeffrey D. [Oak Ridge National Laboratory↗
DOE OSTI2020

Embedding Methods for Quantum Chemistry: Applications from Materials to Life Sciences

Quantum mechanical embedding methods hold the promise to transform not just the way calculations are performed, but to significantly reduce computational costs and improve scaling for macro molecular systems containing hundreds if not thousands of atoms. The field of embedding has grown increasingly broad with many approaches of different intersecting flavors. Here, we lay out the methods into two streams: QM:MM and QM:QM, showcasing the advantages and disadvantages of both. We provide a review of the literature, the underpinning theories including our contributions, and we highlight current applications with select examples spanning both materials and life sciences. Lastly, we conclude with prospects and future outlook on embedding, and our view on the use of universal test case scenarios for cross comparisons of the many available (and future) embedding theories.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Evaluation of Differential Peptide Loading on Tandem Mass Tag-Based Proteomic and Phosphoproteomic Data Quality

Global and phosphoproteome profiling has demonstrated great utility for the analysis of clinical specimens. One major barrier to the broad clinical application of proteomic profiling is the large amount of biological material required, particularly for phosphoproteomics—currently on the order of 25 mg wet tissue weight, depending on tissue type. For hematopoietic cancers such as acute myeloid leukemia (AML), the sample requirement is in excess of 10 million (1E7) peripheral blood mononuclear cells (PBMCs). Throughout the course of a prospective study, this requirement will certainly exceed what is obtainable from many of the individual patients/timepoints. For this reason, we were interested in examining the impact of differential peptide loading across multiplex channels on proteomic data quality. Methods: To achieve this, we tested a range of channel loading amounts (20, 40, 100, 200, and 400 µg of tryptic peptides, or approximately the material obtainable from 5E5, 1E6, 2.5E6, 5E6, and 1E7 AML patient cells) to assess proteome coverage, quantification reproducibility and accuracy in experiments utilizing isobaric tandem mass tag (TMT) labeling. As expected, we found that fewer missing values are observed in TMT channels with higher peptide loading amounts compared to those with lower loading. Moreover, channels with lower loading amounts have greater quantitative variability than channels with higher loading amounts. Statistical analysis of the differences in means among the five loading groups showed that the 20 µg loading group was significantly different from the 400 µg loading group. However, no significant differences were detected among the 40, 100, 200 and 400 µg loading groups. Conclusions: These assessment data demonstrate the practical limits of loading differential quantities of peptides across channels in TMT multiplexes, and provide a basis for designing the optimal clinical proteomics study when specimen quantities are limited.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Infrasound From a Buried Chemical Explosion Recorded on a Balloon in the Lower Stratosphere

Abstract Infrasound waveforms generated by natural and anthropogenic phenomena contain important clues about the size and nature of the event. We show that sensors on balloons in the lower stratosphere can record faithful representations of the near‐source acoustic wave field at unprecedented range. The acoustic signature of a buried chemical explosion recorded at a range of 56 km and an altitude of 21.8 km was nearly identical to that recorded on the ground 0.5 km from the epicenter, but absent on a ground sensor located 46 km away. Our results demonstrate that balloon‐borne infrasound techniques greatly increase the range at which well‐preserved acoustic representations of near‐source physics can be acquired, and that their propagation is simple to model. Our work has implications for monitoring remote regions of the earth for explosions, volcanic eruptions, and other phenomena. It also supports the prospect of balloon‐based infrasound seismology on Venus.

Bowman, Daniel C.↗
DOE OSTI2024

Research to Confront Climate Change Complexity: Intersectionality, Integration, and Innovative Governance

Abstract Climate impacts increasingly unfold in interlinked systems of people, nature, and infrastructure. The cascading consequences are revealing sometimes surprising connections across sectors and regions, and prospects for climate responses also depend on complex, difficult‐to‐understand interactions. In this commentary, we build on the innovations of the United States Fifth National Climate Assessment to suggest a framework for understanding and responding to complex climate challenges. This approach involves: (a) integration of disciplines and expertise to understand how intersectionality shapes complex climate impacts and the wide‐ranging effects of climate responses, (b) collaborations among diverse knowledge holders to improve responses and better encompass intersectionality, and (c) sustained experimentation with and learning about governance approaches capable of handling the complexity of climate change. Together, these three pillars underscore that usability of climate‐relevant knowledge requires transdisciplinary coordination of research and practice. We outline actionable steps for climate research to incorporate intersectionality, integration, and innovative governance, as is increasingly necessary for confronting climate complexity and sustaining equitable, ideally vibrant climate futures.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

The Largest Ever Recorded Heatwave—Characteristics and Attribution of the Antarctic Heatwave of March 2022

An unprecedented heatwave impacted East Antarctica in March 2022, peaking at 39°C above climatology, the largest temperature anomaly ever recorded globally. We investigate the causes of the heatwave, the impact of climate change, and a climate model's ability in simulating such an event. The heatwave, which was skillfully forecast, resulted from a highly anomalous large-scale circulation pattern that advected an Australian airmass to East Antarctica in 4 days and produced record atmospheric heat fluxes. Southern Ocean sea surface temperatures anomalies had a minimal impact on the heatwave's amplitude. Simulations from a climate model fail to simulate such a large temperature anomaly mostly due to biases in its large-scale circulation variability, showcasing a pathway for future model improvement in simulating extreme heatwaves. The heatwave was made 2°C warmer by climate change, and end of 21st century heatwaves may be an additional 5–6°C warmer, raising the prospect of near-melting temperatures over the interior of East Antarctica.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Induced Polarization of Clayey Rocks and Soils: Non‐Linear Complex Conductivity Models

Abstract The past decades have witnessed the increased applications of induced polarization (IP) method in the critical zone studies with ubiquitous clay minerals. Although IP outperforms traditional electrical and electromagnetic methods through its unique ability to measure quadrature conductivity, the nonlinearity that quadrature conductivity behaves with salinities and frequencies greatly tortures IP practitioners, as (a) salinity‐dependency makes the quadrature conductivity a varyingly unstable parameter to quantitatively estimate hydraulic properties and clay content; (b) frequency‐dependent Cole‐Cole and Debye/Warburg decomposition models, although mathematically sound, physically mingle the properties of pore water and clay minerals and are empirical in nature. From basic principles, we demonstrate that quadrature conductivity remains a hybrid property involving both clay and water, and develop relevant models to distinguish them. Our models are validated by theories, experiments, simulations, and comparisons, all of which proclaim considerable advantages over previous models and offer the prospect of quantitative applications.

58 GEOSCIENCES↗
DOE OSTI2020

Ten years of spasers and plasmonic nanolasers

Ten years ago, three teams experimentally demonstrated the first spasers, or plasmonic nanolasers, after the spaser concept was first proposed theoretically in 2003. An overview of the significant progress achieved over the last 10 years is presented here, together with the original context of and motivations for this research. After a general introduction, we first summarize the fundamental properties of spasers and discuss the major motivations that led to the first demonstrations of spasers and nanolasers. This is followed by an overview of crucial technological progress, including lasing threshold reduction, dynamic modulation, room-temperature operation, electrical injection, the control and improvement of spasers, the array operation of spasers, and selected applications of single-particle spasers. Research prospects are presented in relation to several directions of development, including further miniaturization, the relationship with Bose–Einstein condensation, novel spaser-based interconnects, and other features of spasers and plasmonic lasers that have yet to be realized or challenges that are still to be overcome.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗