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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 91 records · Page 5

Learning nuclear cross sections across the chart of nuclides with graph neural networks

We explore the use of deep learning techniques to learn how nuclear cross sections change as we add or remove protons and neutrons. As a proof of principle, we focus on the neutron-induced reactions in the fast energy regime. Our approach follows a two-stage learning framework. First, we apply representation learning to encode cross section data into a latent space using either variational autoencoders (VAEs) or implicit neural representations (INRs). Then, we train graph neural networks (GNNs) on the resulting embeddings to predict missing values across the nuclear chart by leveraging the topological structure of neighboring isotopes. We demonstrate accurate cross section predictions within a 9 × 9 block of missing nuclei. We also find that the optimal GNN training strategy depends on the type of latent representation used, with VAE embeddings performing best under end-to-end optimization in the original space, while INR embeddings achieve better results when the GNN is trained only in the latent space. Furthermore, using clustering algorithms, we map groups of latent vectors into regions of the nuclear chart and show that VAEs and INRs can discover some of the neutron magic numbers. These findings suggest that deep-learning models based on the representation encoding of cross sections combined with graph neural networks hold significant potential in augmenting nuclear theory models, e.g., by providing reliable estimates of covariances of cross sections, including cross-material covariances.

Machine learning↗

Engineering a photoenzyme to use red light

Photoenzymatic reactions involving flavin-dependent “ene”-reductases (EREDs) rely on protein-templated charge transfer (CT) complexes between the cofactor and substrate for radical initiation. These complexes typically absorb in the blue region of the electromagnetic spectrum. Here, we engineered an ERED to form CT complexes that absorb red light. Mechanistic studies indicate that red-light activity is due to the growth of a red-absorbing shoulder off the previously identified cyan absorption feature. Molecular dynamics simulations, docking, and excited-state calculations suggest that the cyan feature involves a π→π* transition on flavin, whereas the red-light absorption is a π→π* transition between flavin and the substrate. Furthermore, differences in the electronic transition are due to changes in the substrate-binding conformation and allosteric tuning of the electronic structure of the cofactor-substrate complex. Microenvironment tuning of the CT complex for red-light activity is observed with other engineered photoenzymatic reactions, highlighting this effect’s generality.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Targeted mutagenesis and high-throughput screening of diversified gene and promoter libraries for isolating gain-of-function mutations

Targeted mutagenesis of a promoter or gene is essential for attaining new functions in microbial and protein engineering efforts. In the burgeoning field of synthetic biology, heterologous genes are expressed in new host organisms. Similarly, natural or designed proteins are mutagenized at targeted positions and screened for gain-of-function mutations. Here, we describe methods to attain complete randomization or controlled mutations in promoters or genes. Combinatorial libraries of one hundred thousands to tens of millions of variants can be created using commercially synthesized oligonucleotides, simply by performing two rounds of polymerase chain reactions. With a suitably engineered reporter in a whole cell, these libraries can be screened rapidly by performing fluorescence-activated cell sorting (FACS). Within a few rounds of positive and negative sorting based on the response from the reporter, the library can rapidly converge to a few optimal or extremely rare variants with desired phenotypes. Library construction, transformation and sequence verification takes 6–9 days and requires only basic molecular biology lab experience. Screening the library by FACS takes 3–5 days and requires training for the specific cytometer used. Further steps after sorting, including colony picking, sequencing, verification, and characterization of individual clones may take longer, depending on number of clones and required experiments.

59 BASIC BIOLOGICAL SCIENCES↗

Towards defect engineering in hexagonal MoS 2 nanosheets for tuning hydrogen evolution and nitrogen reduction reactions

Combined computational and experimental approaches were used to evaluate defective 2H-MoS 2 nanosheets for their activity and selectivity for hydrogen evolution reaction (HER) and nitrogen reduction reaction (NRR). Density functional theory calculations were used to understand the relationship between HER and NRR activity on the ideal basal MoS 2 plane, seven grain-boundaries, ten single-/few-atom vacancies and anti-sites, and zigzag and armchair edge sites. The results confirm that 2H-MoS 2 should contain several defects with high activity for HER: armchair and zigzag edges, VS vacancy, MoS 2 anti-site, and S-S and Mo-Mo grain boundaries. Considering Gibbs free energy change for all the steps in the NRR mechanism and kinetic barriers for a key NRR step, we have found that activation of perspective NRR selective sites in 2H-MoS 2 , namely V MoS6 and clusters of S-vacancies, would require large overpotential, conditions at which HER dominates. The DFT conclusions are supported by the electrochemical studies of NRR activity and selectivity under aqueous conditions, which show an increase in NRR activity but a decrease in Faradaic efficiency as applied cell potential becomes more negative. The results of this work therefore highlight the challenges in activating natural 2H-MoS 2 for NRR, which would require additional material engineering or reaction condition optimization as a way to suppress HER, decrease the NRR overpotential or preferentially both.

2H-MoS2↗

Fast estimation of reaction rates in spherical and non-spherical porous catalysts

Here we present a methodology for modeling multi-step reaction rates in porous catalyst particles for use in CFD-DEM and two fluid models. Single-step effectiveness factors based on a Thiele modulus, while useful, cannot accurately capture the cascading reaction systems common in high temperature vapor-phase chemical reactors like fluidized catalytic cracking units and catalytic biomass fast pyrolysis systems. Instead, multi-step effectiveness vectors derived from steady-state solutions to the governing reaction-diffusion equations are needed. Solutions for various catalyst shapes are presented, including spheres, cylinders, and prisms. Computational challenges inherent in repeated evaluation of reaction rates with diffusion limitations are discussed, and an efficient implementation based on pre-computed lookup tables is proposed and demonstrated on a simulation of a fluidized bed reactor. Open-source code is provided for the compilation of reaction rate tables for use in ODE, DEM, and two-fluid models.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effects of diffusion barriers on reaction wave stability in Co/Al reactive multilayers

Bimetallic, reactive multilayers are uniformly structured materials composed of alternating sputter-deposited layers that may be ignited to produce self-propagating mixing and formation reactions. These nanolaminates are most commonly used as rapid-release heat sources. The specific chemical composition at each metal/metal interface determines the rate of mass transport in a mixing and formation reaction. The inclusion of engineered diffusion barriers at each interface will not only inhibit solid-state mixing but also may impede the self-propagating reactions by introducing instabilities to wavefront morphology. Here, this work examines the effect of adding diffusion barriers on the propagation of reaction waves in Co/Al multilayers. The Co/Al system has been shown to exhibit a reaction propagation instability that is dependent on the bilayer thickness, which allows for the occurrence of unstable modes in otherwise stable designs from the inclusion of diffusion barriers. Based on the known stability criteria in the Co/Al multilayer system, the way in which the inclusion of diffusion barriers changes a multilayer's heat of reaction, thermal conductivity, and material mixing mechanisms can be determined. These factors, in aggregate, lead to changes in the wavefront velocity and stability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Catalytic Reaction Triggered by Magnetic Induction Heating Mechanistically Distinguishes Itself from the Standard Thermal Reaction

As a recent advancement in chemical engineering, magnetic induction heating (MIH) is utilized to initiate the intended reactions by enabling the self-heating of the ferromagnetic catalyst particles. While MIH can be energy-efficient and industrially scalable, its full potential has been underappreciated in catalysis because of the perception that MIH is merely an alternative heating approach. Unexpectedly, we show that the MIH-triggered reaction could go beyond standard thermal catalysis. Specifically, by probing the representative Pt/Fe 3 O 4 catalysts with CO oxidation in both thermal and MIH modes with consistent temperature profiles and catalyst structures, we found that the MIH mode boosts the reactivity more than 25 times by modifying Pt-FeO x interfacial synergies and promoting facile oxidation of the adsorbed carbonyl species by atomic oxygen. Further, as we preliminarily observed, this beneficial MIH-catalysis can be translational to other thermal reactions, potentially paving the way to launch MIH-catalysis as a distinct reaction category.

CO oxidation↗

Complete integration of carbene-transfer chemistry into biosynthesis

Biosynthesis is an environmentally benign and renewable approach that can be used to produce a broad range of natural and, in some cases, new-to-nature products. However, biology lacks many of the reactions that are available to synthetic chemists, resulting in a narrower scope of accessible products when using biosynthesis rather than synthetic chemistry. A prime example of such chemistry is carbene-transfer reactions. Although it was recently shown that carbene-transfer reactions can be performed in a cell and used for biosynthesis, carbene donors and unnatural cofactors needed to be added exogenously and transported into cells to effect the desired reactions, precluding cost-effective scale-up of the biosynthesis process with these reactions. Here, in this paper, we report the access to a diazo ester carbene precursor by cellular metabolism and a microbial platform for introducing unnatural carbene-transfer reactions into biosynthesis. The α-diazoester azaserine was produced by expressing a biosynthetic gene cluster in Streptomyces albus. The intracellularly produced azaserine was used as a carbene donor to cyclopropanate another intracellularly produced molecule—styrene. The reaction was catalysed by engineered P450 mutants containing a native cofactor with excellent diastereoselectivity and a moderate yield. Our study establishes a scalable, microbial platform for conducting intracellular abiological carbene-transfer reactions to functionalize a range of natural and new-to-nature products and expands the scope of organic products that can be produced by cellular metabolism.

59 BASIC BIOLOGICAL SCIENCES↗

Consistency of $^{16}O(n,α)$ cross sections

The evaluated $^{16}O(n,α)$ cross sections in the ENDF/B-VIII.0 nuclear data library remain uncertain because of systematic discrepancies in the measured data. In the energy region below the first excited state, R-matrix analyses rely heavily on the inverse reaction, and in particular, they rely on the measured $^{13}C(α,n)^{16}O$ cross sections reported by Bair et al. in 1973 and Harissopulos et al. in 2005. The Harissopulos cross section values are systematically lower than those previously reported by Bair. Here, drawing on the available experimental information, this paper briefly describes and demonstrates that the two sets of measured cross sections are consistent.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Enhancement of Two Heterogeneous Reactions in the Production of the Medical Isotope 188 W

We report the efficiency of heterogeneous reactions is influenced by kinetic conditions with an emphasis on reactants in different phases to have effective interactions. Optimal interactions of reactants rely on the rational design of the equipment and engineering parameters for the reaction process, especially for the process on a large scale. 188 W production at the Oak Ridge National Laboratory is such an example. In processing the irradiated 186 W metal target for the 188 W product, two of the heterogeneous reactions are essential ones: (1) the gas–solid reaction of O 2 + W to form WO 3 and (2) the gas–liquid reaction of OsO 4 being absorbed by the NaOH sorbent. Better understanding of the two reactions has led to revisions to the design of the quartz reaction vessel (gas–solid reaction) and the scrubbing system (gas–liquid reaction). The optimized quartz vessel resulted in less heating hours, whereas a more efficient OsO 4 scrubbing system ensured that all volatile OsO 4 was qualitatively captured.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Flavin-dependent halogenases catalyze enantioselective olefin halocyclization

Abstract Halocyclization of alkenes is a powerful bond-forming tool in synthetic organic chemistry and a key step in natural product biosynthesis, but catalyzing halocyclization with high enantioselectivity remains a challenging task. Identifying suitable enzymes that catalyze enantioselective halocyclization of simple olefins would therefore have significant synthetic value. Flavin-dependent halogenases (FDHs) catalyze halogenation of arene and enol(ate) substrates. Herein, we reveal that FDHs engineered to catalyze site-selective aromatic halogenation also catalyze non-native bromolactonization of olefins with high enantioselectivity and near-native catalytic proficiency. Highly selective halocyclization is achieved by characterizing and mitigating the release of HOBr from the FDH active site using a combination of reaction optimization and protein engineering. The structural origins of improvements imparted by mutations responsible for the emergence of halocyclase activity are discussed. This expansion of FDH catalytic activity presages the development of a wide range of biocatalytic halogenation reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Methods for isothermal molecular amplification with nanoparticle-based reactions

The present method of detection involves increasing an amount of analyte molecules by an isothermal molecular amplification approach. In the present approach a starting molecule of interest may be amplified through a reaction it induces with specifically engineered and functionalized particles, namely protected particles A and storage particles B. This reaction may result in a set of output DNA molecules that is larger in number than the input DNA molecules. Thus the reaction between nanoparticles for amplification of a certain DNA sequence (input DNA molecules) may occur when there is a match with a targeted molecule (stored molecules on storage particles B) and if the DNA sequence of the input DNA molecules does not match (partially or completely) the targeted molecule the reaction may not occur. Without a certain molecular input of the input DNA molecule the reaction may not occur.

Gang, Oleg↗

Numerical Investigation of Ammonia/n-Heptane Dual-Fuel Spray Flames Using Large Eddy Simulations

Diesel engines are extensively used in heavy-duty transportation, power generation, and marine vehicles due to their superior thermal efficiency and extended high-load operability compared to spark ignition (SI) engines. However, combustion in diesel engines is generally characterized by locally rich fuel–air mixtures and high combustion temperatures, causing significant amounts of soot and NO x emissions from these engines. Utilizing carbon-free alternative fuels and enhancing fuel efficiency represent promising strategies to mitigate greenhouse gas (GHG) and other emissions in the heavy-duty transportation sector. In this context, ammonia (NH 3 ), as a hydrogen carrier, has received significant attention as a viable substitute for hydrocarbon fuels due to its carbon-free composition, relatively high energy density, and well-established infrastructure. Many previous studies have considered combustion and emission characteristics of ammonia-hydrocarbon fuel blends in engines and simplified flames. But, detailed investigations on the effects of ammonia on the performance of hydrocarbon fuels under engine conditions are lacking. In the present study, we perform large eddy simulations (LES) of the ignition and flame processes in a constant-volume combustion reactor, where n-heptane is injected in an ammonia/air ambient mixture in a diesel-like environment. A detailed and validated reaction mechanism containing 302 species and 1981 reactions is employed. The Engine Combustion Network Spray H experimental data is used to validate the spray model under both non-reacting and reacting conditions. Dual-fuel combustion is simulated using the well-stirred reactor (WSR) approach. Results are presented for two spray cases: (1) single fuel (SF) with n-heptane injected into a mixture of air and combustion products and (2) dual-fuel (DF) with the injection of n-heptane in a mixture of air, ammonia, and combustion products. It is observed that the presence of ammonia has a significant effect on the ignition and flame development processes. With ammonia addition, both the first- and second-stage ignition delay times increase, but the effect of ammonia on the second-stage ignition is significantly more prominent. In addition, the ignition kernel size and growth rate decrease noticeably. For SF spray, the main ignition is characterized by multiple ignition kernels near the spray tip, whereas for DF spray, a single relatively small ignition kernel forms and grows slowly in the downstream direction. The flame development and the final quasi-steady flame structure are also modified due to ammonia. Here, the outcome of this research would enable a better understanding of ammonia–diesel dual-fuel spray flame behavior and guide the development of associated engine combustion strategies.

ammonia↗

Atomic-scale insights into topotactic transformations in an extra-large-pore zeolite using time-resolved 3D electron diffraction

Understanding the atomic-scale structural dynamics of phase transformations is crucial for developing materials and tailoring their properties. However, many materials are obtained as polycrystalline powders with large unit cells and/or complex structures, making it challenging to investigate detailed structural changes using conventional X-ray diffraction techniques. Here we employ time-resolved three-dimensional electron diffraction to reveal the topotactic reactions and transformations that convert the extra-large-pore silicate zeolite ECNU-45 into ECNU-46. ECNU-45 features three-dimensional interconnecting 24 × 10 × 10-ring channels, while ECNU-46 consists of one-dimensional 24-ring channels connected to 10-ring pockets. ECNU-45 and ECNU-46 are both examples of pure silicate zeolites with pore openings larger than 22-ring. Our findings indicate changes at six distinct tetrahedral silicon sites, involving atom displacement, addition and removal of framework atoms through bond breakage and formation. This work presents the synthesis of zeolites and also provides atomic-level insights into the dynamic processes of topotactic reactions. Our results have implications for advancing materials engineering and understanding complex solid-state reactions at an atomic scale.

Inorganic chemistry↗

Enhanced accuracy through ensembling of randomly initialized auto-regressive models for dynamical systems

Computational mechanics simulations using traditional finite element methods (FEM) require prohibitively expensive computational resources for real-time engineering applications, design optimization, and digital twin implementations. While machine learning (ML) surrogate models offer significant computational speedups, autoregressive ML models for time-dependent mechanical systems suffer from error accumulation that compromises long-term prediction reliability - a critical concern for engineering applications where accuracy over extended time horizons is essential for safety and performance assessments. Here, we propose a deep ensemble framework specifically designed to address this challenge in computational mechanics applications, where multiple ML surrogate models with random weight initializations are trained in parallel and their predictions aggregated during inference. This approach leverages statistical diversity to maximize information gain from a fixed set of training data and to mitigate error propagation, while maintaining the computational efficiency that makes ML surrogates attractive for engineering practice. We validate the framework on three representative problems spanning critical areas of computational mechanics: stress field evolution in heterogeneous microstructures under complex loading (relevant to advanced materials design and composite analysis), planetary-scale shallow water dynamics (applicable to environmental and geotechnical engineering), and Gray-Scott reaction-diffusion systems (relevant to mass transport and chemical process engineering). Across all test cases, the ensemble approach demonstrates consistent error reduction of 15-33% compared to individual models. The codes for this work are available on GitHub (https://github.com/Graham-Brady-Research-Group/AutoregressiveEnsemble_SpatioTemporal_Evolution).

autoregressive prediction↗

Combustion-Pele: An Exascale Capability for Improving Engine Design

Combustion, the complex chemical reaction made possible by igniting a mixture of fuel and oxygen to produce heat and light, serves as the nation’s primary source of power generation and the linchpin of the transportation industry. For more than 100 years, internal combustion engines (ICEs) have been converting energy from the burning of fuel—gasoline, for example—into a mechanical process that makes vehicles move. Recently, ICEs have come under heavy scrutiny for their contribution to greenhouse gas emissions, yet combustion-based systems are projected to dominate the marketplace for decades. Exascale systems are helping researchers design new high-efficiency, low-emission combustion engines that operate at much lower temperatures to maintain the nation’s energy security and limit negative environmental impacts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Prospects for Engineering Biophysical CO 2 Concentrating Mechanisms into Land Plants to Enhance Yields

Although cyanobacteria and algae represent a small fraction of the biomass of all primary producers, their photosynthetic activity accounts for roughly half of the daily CO 2 fixation that occurs on Earth. These microorganisms are able to accomplish this feat by enhancing the activity of the CO 2 -fixing enzyme Rubisco using biophysical CO 2 concentrating mechanisms (CCMs). Biophysical CCMs operate by concentrating bicarbonate and converting it into CO 2 in a compartment that houses Rubisco (in contrast with other CCMs that concentrate CO 2 via an organic intermediate, such as malate in the case of C 4 CCMs). This activity provides Rubisco with a high concentration of its substrate, thereby increasing its reaction rate. The genetic engineering of a biophysical CCM into land plants is being pursued as a strategy to increase crop yields. This review focuses on the progress toward understanding the molecular components of cyanobacterial and algal CCMs, as well as recent advances toward engineering these components into land plants.

59 BASIC BIOLOGICAL SCIENCES↗

De novo protein design of photochemical reaction centers

Abstract Natural photosynthetic protein complexes capture sunlight to power the energetic catalysis that supports life on Earth. Yet these natural protein structures carry an evolutionary legacy of complexity and fragility that encumbers protein reengineering efforts and obfuscates the underlying design rules for light-driven charge separation. De novo development of a simplified photosynthetic reaction center protein can clarify practical engineering principles needed to build new enzymes for efficient solar-to-fuel energy conversion. Here, we report the rational design, X-ray crystal structure, and electron transfer activity of a multi-cofactor protein that incorporates essential elements of photosynthetic reaction centers. This highly stable, modular artificial protein framework can be reconstituted in vitro with interchangeable redox centers for nanometer-scale photochemical charge separation. Transient absorption spectroscopy demonstrates Photosystem II-like tyrosine and metal cluster oxidation, and we measure charge separation lifetimes exceeding 100 ms, ideal for light-activated catalysis. This de novo-designed reaction center builds upon engineering guidelines established for charge separation in earlier synthetic photochemical triads and modified natural proteins, and it shows how synthetic biology may lead to a new generation of genetically encoded, light-powered catalysts for solar fuel production.

59 BASIC BIOLOGICAL SCIENCES↗