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At least 613 records · Page 34

Metadynamics investigation of lanthanide solvation free energy landscapes and insights into separations energetics

Lanthanide ion solvation chemistry in nonaqueous phases is key to understanding and developing effective separation processes for these critical materials. Due to the complexity and inherent disorder of the solution phase, a comprehensive picture of the solvated metal ion is often difficult to generate solely from conventional spectroscopic approaches and electronic structure calculations, particularly in the extractant phase. In this work, we use classical molecular dynamics (MD) simulation with an advanced sampling technique, metadynamics, supplemented by experimental spectroscopy and speciation analysis, to measure lanthanide solvation free energy landscapes. We define coordination-based collective variables to probe the entire range of solvation configurations in the organic phase of lanthanum (La), europium (Eu), and lutetium (Lu) nitrate salts bound with a commonly used extractant, N,N′-dimethyl, N,N′-dioctylhexylethoxymalonamide (DMDOHEMA). The known lanthanide extraction trend of La ≈ Eu > Lu is readily explained by the measured free energy surfaces, which show consistent DMDOHEMA coordination from La to Eu, followed by loss of DMDOHEMA coordination from Eu to Lu. These simulations suggest how ligand crowding at the metal center can control selectivity, in this case resulting in the opposite extraction trend as observed with other conventional extractants, where the enthalpic contribution from increasing lanthanide charge density across the series dominates the extraction energetics. We also find that the presence of inner-sphere water, verified by time-resolved fluorescence, diversifies the accessible solvation structures. As a result, understanding solvation requires consideration of an entire thermodynamic ensemble, rather than the single dominant lowest-energy structure, as is often considered out of necessity in interpretation of spectroscopic data or in electronic structure-based ligand design approaches. In general, we demonstrate how metadynamics uniquely enables investigation of complex, multidimensional solvation energetic landscapes, and how it can explain selectivity trends where extraction is controlled by more complex mechanisms than simple charge density-based selectivity.

Wang, Xiaoyu↗

X-ray diffraction at the National Ignition Facility

We report details of an experimental platform implemented at the National Ignition Facility to obtain in situ powder diffraction data from solids dynamically compressed to extreme pressures. Thin samples are sandwiched between tamper layers and ramp compressed using a gradual increase in the drive-laser irradiance. Pressure history in the sample is determined using high-precision velocimetry measurements. Up to two independently timed pulses of x rays are produced at or near the time of peak pressure by laser illumination of thin metal foils. The quasi-monochromatic x-ray pulses have a mean wavelength selectable between 0.6 Å and 1.9 Å depending on the foil material. The diffracted signal is recorded on image plates with a typical 2 θ x-ray scattering angle uncertainty of about 0.2° and resolution of about 1°. Analytic expressions are reported for systematic corrections to 2 θ due to finite pinhole size and sample offset. A new variant of a nonlinear background subtraction algorithm is described, which has been used to observe diffraction lines at signal-to-background ratios as low as a few percent. Variations in system response over the detector area are compensated in order to obtain accurate line intensities; this system response calculation includes a new analytic approximation for image-plate sensitivity as a function of photon energy and incident angle. This experimental platform has been used up to 2 TPa (20 Mbar) to determine the crystal structure, measure the density, and evaluate the strain-induced texturing of a variety of compressed samples spanning periods 2–7 on the periodic table.

47 OTHER INSTRUMENTATION↗

Hybrid quantum-classical simulations of magic angle spinning dynamic nuclear polarization in very large spin systems

Solid-state nuclear magnetic resonance can be enhanced using unpaired electron spins with a method known as dynamic nuclear polarization (DNP). Fundamentally, DNP involves ensembles of thousands of spins, a scale that is difficult to match computationally. This scale prevents us from gaining a complete understanding of the spin dynamics and applying simulations to design sample formulations. We recently developed an ab initio model capable of calculating DNP enhancements in systems of up to ~1000 nuclei; however, this scale is insufficient to accurately simulate the dependence of DNP enhancements on radical concentration or magic angle spinning (MAS) frequency. We build on this work by using ab initio simulations to train a hybrid model that makes use of a rate matrix to treat nuclear spin diffusion. We show that this model can reproduce the MAS rate and concentration dependence of DNP enhancements and build-up time constants. Finally, we then apply it to predict the DNP enhancements in core–shell metal-organic-framework nanoparticles and reveal new insights into the composition of the particles’ shells.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Modelling pulsed field magnetization of iron-based bulk superconductors

Abstract Bulk superconductors can be used as super-strength quasi-permanent magnets capable of providing magnetic flux densities considerably superior to conventional permanent magnets. This makes them attractive for several engineering applications that rely on strong magnetic fields like rotating machines, NMR/MRI and magnetic drug delivery systems. Recently, the authors reported a record trapped magnetic field in an iron-based bulk superconductor: 2.83 T was trapped in potassium-doped barium iron arsenide (Ba, K)Fe 2 As 2 (or Ba122) at 5 K. Of particular significance is that the strength and temporal stability of this magnetic field exceeds the requirements of MRI machines, indicating iron-based bulks can now perform at levels demanded by engineering applications. One crucial challenge for their practical use, however, is the need to apply and remove an external magnetic field to magnetize them. Pulsed field magnetization (PFM) shows great promise as a practical method of magnetizing bulks, but the process generates heat in the bulk that is detrimental to its superconducting performance and ability to act as a super-strength magnet. In this paper, coupled electromagnetic–thermal numerical models are used to simulate the PFM of iron-based bulk superconductors. Here we focus on the recent-record-breaking, fine-grain polycrystalline K-doped Ba122 bulks. The impact that the specific J c ( B ) characteristics and thermal properties of the Ba122 material—all of which have been experimentally measured from state-of-the-art samples—have on the magnetic flux dynamics and thermal behaviour during PFM, including the final trapped field, is investigated. We show that because the thermal properties are similar to those of REBa 2 Cu 3 O 7 −δ bulks, a similar response to pulsed fields is obtained. A maximum trapped field of ∼0.81 T (∼43.3% of the maximum trapped field capability under ideal, field-cooling conditions) was simulated at 5 K, with a magnetization efficiency of ∼54%. The modelling framework provides a fast and flexible tool for optimising the practical PFM process at different operating temperatures to maximise the trapped field in state-of-the-art Ba122 bulks and to guide the design of future experiments.

bulk superconductors↗

Transient local secondary structure in the intrinsically disordered C‐term of the Albino3 insertase

Albino3 (Alb3) is an integral membrane protein fundamental to the targeting and insertion of light‐harvesting complex (LHC) proteins into the thylakoid membrane. Alb3 contains a stroma‐exposed C‐terminus (Alb3‐Cterm) that is responsible for binding the LHC‐loaded transit complex before LHC membrane insertion. Alb3‐Cterm has been reported to be intrinsically disordered, but precise mechanistic details underlying how it recognizes and binds to the transit complex are lacking, and the functional roles of its four different motifs have been debated. Using a novel combination of experimental and computational techniques such as single‐molecule fluorescence resonance energy transfer, circular dichroism with deconvolution analysis, site‐directed mutagenesis, trypsin digestion assays, and all‐atom molecular dynamics simulations in conjunction with enhanced sampling techniques, we show that Alb3‐Cterm contains transient secondary structure in motifs I and II. The excellent agreement between the experimental and computational data provides a quantitatively consistent picture and allows us to identify a heterogeneous structural ensemble that highlights the local and transient nature of the secondary structure. This structural ensemble was used to predict both the inter‐residue distance distributions of single molecules and the apparent unfolding free energy of the transient secondary structure, which were both in excellent agreement with those determined experimentally. We hypothesize that this transient local secondary structure may play an important role in the recognition of Alb3‐Cterm for the LHC‐loaded transit complex, and these results should provide a framework to better understand protein targeting by the Alb3‐Oxa1‐YidC family of insertases.

Okoto, Patience S.↗

Probing the state of hydrogen in δ − AlOOH at mantle conditions with machine learning potential

Hydrous and nominally anhydrous minerals are a fundamental class of solids of enormous significance to geophysics. They are the water carriers in the deep geological water cycle and impact structural, elastic, plastic, and thermodynamic properties and phase relations in Earth's forming aggregates (rocks). They play a critical role in the geochemical and geophysical processes that shape the planet. Their complexity has prevented predictive calculations of their properties, but progress in materials simulations ushered by machine-learning potentials is transforming this state of affairs. Here, we adopt a hybrid approach that combines deep learning potentials (DPs) with the strongly constrained and appropriately normed meta-generalized gradient approximation functional to simulate a prototypical hydrous system. We illustrate the success of this approach to simulate δ − AlOOH ( δ ) , a phase capable of transporting water down to near the core-mantle boundary of the Earth ( ∼ 2900 km depth and ∼ 135 GPa ) in subducting slabs. A high-throughput sampling of phase space using molecular dynamics simulations with DPs sheds light on the hydrogen-bond behavior and proton diffusion at geophysical conditions. These simulations provide a pathway for a deeper understanding of these crucial components that shape Earth's internal state. Published by the American Physical Society 2024

Luo, Chenxing (ORCID:0000000341166851)↗

Gnu-RL: A Precocial Reinforcement Learning Solution for Building HVAC Control Using a Differentiable MPC Policy

Reinforcement learning (RL) was first demonstrated to be a feasible approach to controlling heating, ventilation, and air conditioning (HVAC) systems more than a decade ago. However, there has been limited progress towards a practical and scalable RL solution for HVAC control. While one can train an RL agent in simulation, it is not cost-effective to create a model for each thermal zone or building. Likewise, existing RL agents generally take a long time to learn and are opaque to expert interrogation, making them unattractive for real-world deployment. To tackle these challenges, we propose Gnu-RL: a novel approach that enables practical deployment of RL for HVAC control and re- quires no prior information other than historical data from exist- ing HVAC controllers. To achieve this, Gnu-RL adopts a recently- developed Differentiable Model Predictive Control (MPC) policy, which encodes domain knowledge on planning and system dynam- ics, making it both sample-efficient and interpretable. Prior to any interaction with the environment, a Gnu-RL agent is pre-trained on historical data using imitation learning, which enables it to match the behavior of the existing controller. Once it is put in charge of controlling the environment, the agent continues to improve its policy end-to-end, using a policy gradient algorithm. We evaluate Gnu-RL on both an EnergyPlus model and a real- world testbed. In both experiments, our agents were directly de- ployed in the environment after offline pre-training on expert demonstration. In the simulation experiment, our approach saved 6.6% energy compared to the best published RL result for the same environment, while maintaining a higher level of occupant comfort. Next, Gnu-RL was deployed to control the HVAC of a real-world conference room for a three-week period. Our results show that Gnu-RL saved 16.7% of cooling demand compared to the existing controller and tracked temperature set-point better.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Single-Cell Discovery and Multiomic Characterization of Therapeutic Targets in Multiple Myeloma

Multiple myeloma (MM) is a highly refractory hematologic cancer. Targeted immunotherapy has shown promise in MM but remains hindered by the challenge of identifying specific yet broadly representative tumor markers. We analyzed 53 bone marrow (BM) aspirates from 41 MM patients using an unbiased, high-throughput pipeline for therapeutic target discovery via single-cell transcriptomic profiling, yielding 38 MM marker genes encoding cell-surface proteins and 15 encoding intracellular proteins. Of these, 20 candidate genes were highlighted that are not yet under clinical study, 11 of which were previously uncharacterized as therapeutic targets. The findings were cross-validated using bulk RNA sequencing, flow cytometry, and proteomic mass spectrometry of MM cell lines and patient BM, demonstrating high overall concordance across data types. Independent discovery using bulk RNA sequencing reiterated top candidates, further affirming the ability of single-cell transcriptomics to accurately capture marker expression despite limitations in sample size or sequencing depth. Target dynamics and heterogeneity were further examined using both transcriptomic and immuno-imaging methods. In summary, this study presents a robust and broadly applicable strategy for identifying tumor markers to better inform the development of targeted cancer therapy.

60 APPLIED LIFE SCIENCES↗

Molecular simulation data for 'Data-guided Multi-Map variables for ensemble refinement of molecular movies'

These trajectories, scripts, and analysis performed on Summit underly the work published as 'Data-guided Multi-Map variables for ensemble refinement of molecular movies'. The trajectories include equilibrium and non-equilibrium sampling of ADK, CODH, and FLPP3, the scripts used to build the systems, and the scripts used to analyze the output. The directory structure is explained further in an internal README file.

59 BASIC BIOLOGICAL SCIENCES↗

Molecular mechanics of Staphylococcus aureus adhesin, CNA, and the inhibition of bacterial adhesion by stretching collagen

Bacterial adhesion to collagen, the most abundant protein in humans, is a critical step in the initiation and persistence of numerous bacterial infections. In this study, we explore the collagen binding mechanism of the multi-modular cell wall anchored collagen adhesin (CNA) in Staphylococcus aureus and examine how applied mechanical forces can modulate adhesion ability. The common structural-functional elements and domain organization of CNA are present across over 50 genera of bacteria. Through the use of molecular dynamics models and normal mode analysis, we shed light on the CNA’s structural and conformational dynamics and its interactions with collagen that lead to collagen binding. Our results suggest that the linker region, CNA 165-173 , acts as a hinge exhibiting bending, extensional, and torsional modes of structural flexibility and its residues are key in the interaction of the CNA-collagen complex. Steered molecular dynamics simulations were conducted with umbrella sampling. During the course of these simulations, the ‘locking’ latch from the CNA N2 domain was dissociated from its groove in the CNA N1 domain, implying the importance of the latch for effective ligand binding. Finally, we observed that the binding efficiency of the CNA N1-N2 domains to collagen decreases greatly with increasing tensile force application to the collagen peptides. Thus, CNA and similar adhesins might preferentially bind to sites in which collagen fibers are cleaved, such as in wounded, injured, or inflamed tissues, or in which the collagenous tissue is less mature. As alternative techniques for control of bacterial infection are in-demand due to the rise of bacterial antibiotic resistance, results from our computational studies with respect to the mechanoregulation of the collagen binding site may inspire new therapeutics and engineering solutions by mechanically preventing colonization and/or further pathogenesis.

Science & Technology - Other Topics↗

Integration of LIBS with Machine Learning for Real-Time Monitoring of Feedstock in H 2 Gasification Applications

This project, funded by the U.S. Department of Energy (DOE) – Office of Fossil Energy under Award Number DE-FE0032177, aimed to assess the feasibility of an integrated Laser-Induced Breakdown Spectroscopy (LIBS) system with advanced machine learning (ML) models for real-time characterization and potential control of hydrogen gasifiers running on waste materials as feedstocks. This was a multidisciplinary effort that encompassed the acquisition and standardized analysis of individual and blended feedstocks—comprising biomass, coal waste, and plastic waste, followed by the development of a dynamic LIBS bench system for material sample analysis and development of predictive ML models. Comprehensive laboratory testing enabled the creation of a robust elemental dataset that served as the foundation for ML model training. Techniques such as Random Forest, Gradient Boosting, Support Vector Regression, and Neural Networks were employed to predict key feedstock properties, including higher heating value (HHV), moisture content, thermal conductivity, and ash composition with high accuracy. The results were validated against experimental data and demonstrated strong potential for real-time application in gasifier control systems. The project concluded with a study on the integration of the LIBS+ML approach for gasifier control and a techno-economic analysis of the implementation of the approach into hydrogen (H 2 ) gasification systems. Dissemination of results was carried out at a DOE meeting. This work establishes a scalable framework for automated, in-line feedstock quality assessment, offering significant implications for process optimization and emissions reduction in hydrogen production.

01 COAL, LIGNITE, AND PEAT↗

Transformational Opacity Platforms on the Z Facility: A Design Study

The goal of this one-year LDRD is to study novel experimental approaches to provide benchmark spectral opacity measurements at the most extreme conditions beyond existing measurements (i.e. 2x temperature, ~5x density). These conditions correspond to those at half the solar radius and would provide a unique and novel test for stellar physics. These conditions are also relevant to advance stockpile stewardship research. The basic idea is to embed a sample inside the z-pinch dynamic hohlraum on the Z facility and obtain its opacity from either 1) its self-emission or 2) its absorption from using a capsule backlighter. This study evaluates the feasibility, limitations to these two approaches from a design approach. We found that emission-based perspective gives, at best, an opacity accuracy of about 20% for the current studied pinch conditions due to the limit of LTE approximation and radiation transport effects. The capsule-backlighter-based approach overcomes this limitation although some specific design questions remain to be answered. Promising designs are proposed for follow-on Z experiments. Future designs would help maintain Z relevancy in relation to ignition-enabled platforms at NIF.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Design and Production for Maximum Structural Efficiency With Respect to Fiber Orientation With Increased Understanding of Hybrid Fiber Flow Behavior

Discontinuous fiber-reinforced thermoplastic composites have gained considerable attention in automotive, aerospace, and other industries, due to their high-rate of production combined with their ability to attain complex and intricate shapes. Among other high-rate thermoplastic manufacturing processes, injection-molding is one of the most common manufacturing methods due to fast production and high surface finishing of complex geometries. Fiber orientation in discontinuous fiber composites plays a pivotal role in determining the mechanical, electrical, and thermomechanical properties, underscoring the necessity to comprehend fiber orientation in injection molded parts. Among different fiber types, glass and carbon fibers are most common in the composite industries. The recent trend of hybrid composites comprising both glass fiber (GF) and carbon fiber (CF) is also gaining importance in the automotive industry. Hybrid fiber options allow designers to optimize the balance between glass and carbon fibers by leveraging the high durability and low cost of GF while the strength and lightweight properties of CF. Consequently, comparing the fiber oriented distribution (FOD) of injection molded composites containing GF, CF, and a hybrid of GF/CF is critical to investigating the local mechanical properties of intricate structures for high-end applications. In Phase I of this project, FOD in injection-molded panels with respect to distance from the gate was analyzed using X-ray computed tomography (X-CT) for GF, CF, and hybrid CF/GF (CGF) reinforced nylon 66. To understand the reason behind the FOD with different fiber types, computational fluid dynamics (CFD) and rheology were performed. Samples were extracted at three locations: near the gate, center, and opposite end. Thickness of the layers of typical skin-shell-core type FOD varies with fiber type and location. GF achieved flow direction alignment (in shell) earlier than viscous CF and CGF near the gate, whereas CF showed the highest flow-direction alignment at the center due to shear induced orientation. At the opposite end, GF experienced more backflow than others indicating faster mold filling owing to its lower viscosity. Hybrid CGF exhibited GF-dominated center and CF-dominated end region. The numerical model used to obtain FOD and rheological predictions for the CF and GF composites served to corroborate the trends observed in the experimental trials. The FOD responses across fiber types and location were reflected in their longitudinal and transverse properties. Only GF showed higher longitudinal modulus over transverse modulus near the gate attributed to rapid alignment, whereas CF and CGF exhibited opposite trend. However, fountain flow enhanced the longitudinal modulus over transverse modulus with the distance for all, particularly for CF. This study offers insights into mold filling behavior of different fibers which are critical in optimizing injection molding conditions for tailored final properties.

36 MATERIALS SCIENCE↗

PROBING THE DEEP END OF THE MILKY WAY WITH KEPLER : ASTEROSEISMIC ANALYSIS OF 854 FAINT RED GIANTS MISCLASSIFIED AS COOL DWARFS

Asteroseismology has proven to be an excellent tool to determine not only global stellar properties with good precision, but also to infer the stellar structure, dynamics, and evolution for a large sample of Kepler stars. Prior to the launch of the mission, the properties of Kepler targets were inferred from broadband photometry, leading to the Kepler Input Catalog (KIC). The KIC was later revised in the Kepler Star Properties Catalog, based on literature values and an asteroseismic analysis of stars that were unclassified in the KIC. Here, we present an asteroseismic analysis of 45,400 stars that were classified as dwarfs in the Kepler Star Properties Catalog. We found that around 2% of the sample shows acoustic modes in the typical frequency range that put them in the red-giant category rather than the cool dwarf category. We analyze the asteroseismic properties of these stars, derive their surface gravities, masses, and radii, and present updated effective temperatures and distances. We show that the sample is significantly fainter than the previously known oscillating giants in the Kepler field, with the faintest stars reaching down to a Kepler magnitude of Kp ∼ 16. We demonstrate that 404 stars are at distances beyond 5 kpc and that the stars are significantly less massive than for the original Kepler red-giant sample, consistent with a population of distant halo giants. A comparison with a galactic population model shows that up to 40 stars might be genuine halo giants, which would increase the number of known asteroseismic halo stars by a factor of 4. The detections presented here will provide a valuable sample for galactic archeology studies.

79 ASTRONOMY AND ASTROPHYSICS↗

Effects of Interactions Between Produced Formation Fluid and Rock Matrix on Pore Structure of Caney Shale, Southern Oklahoma

ABSTRACT: Rock-fluid interactions change properties of shales during exploitation. To investigate effects of rock-fluid interactions on pore structure of shales matrix after hydraulic fracturing, powder samples from two late Mississippian Caney Shale cores in the Ardmore Basin, southern Oklahoma, were used to react with formation produced fluid from the field in the batch reactor analysis. X-ray diffraction for mineralogy and Low-pressure nitrogen adsorption isotherms for pore structure were measured for original, after-7days, and after-30days samples. Results show that the samples consist mainly of quartz, followed by clay minerals, carbonates, and feldspar. The pore sizes of micropore (<2 nm) and mesopore (2-50 nm) increase 14%-233% due to dissolution of pyrite, feldspar, and carbonates after 7 days. Due to the transformation from smectite to illite and the increase of pore size, the specific surface area (SSA) decreases after 7-days interactions. After 30-days interactions, the micropore volume slightly increases and the mesopore and macropore volume decreases. Due to the decrease of pore size, the SSA of 30-days reacted samples increases correspondingly and is lower (for the clay-rich sample) or higher (for the calcareous sample) than that of the unreacted samples. Findings improve our understanding of dynamic alteration of shale properties during production. 1. INTRODUCTION Energy demand will continuously grow owing to the increasing global population as well as energy consumption (EIA, 2023). On the other hand, shale gas and oil reshaped the energy market in the United States, enabling the United States to become a net-export of natural gas country in 2017 (EIA, 2023). However, shale reservoirs are challenging tight formations that are still poorly understood in the extraction and production of hydrocarbons (Ross and Bustin, 2009; Curtis et al., 2012; Xiong et al., 2015, 2021a; Li Y. et al., 2016; Gong et al., 2019a; Benge et al., 2021; Awejori et al., 2022; Huang et al., 2022). One of the most challenging topics is the rock-fluid interactions post hydraulic fracturing and its subsequent impacts on the pore structures of fractured formation matrix.

Xiong, Fengyang↗

Investigative study of holographic recording materials development

The potential of certain cis-trans isomers and doped LiNbO3 for the holographic read/write/erase memory application was investigated. The cis-trans work involved the photochemical investigation of a number of potential materials as well as specific molecular engineering efforts on alpha-methyl stilbene and its derivatives. These efforts resulted in an increase in the change in index of refraction, and thereby, in potential recording utility, of an order of magnitude. The work on LiNbO3 was directed toward a preliminary investigation of the dynamics of the writing process. Several samples and a variety of writing conditions were investigated. An unexpected and as yet unexplained improvement in material behavior with continued recycling was observed. In addition, some effort was devoted to an analysis of the physical conditions under which several current theories of the optical damage process are valid.

Source record↗

Boxy isophotes, discs and dust lanes in elliptical galaxies

CCD images of 42 elliptical and S0 galaxies are examined for low-contrast structures or subtle distortions of the isophotes from perfect ellipses. 75 percent of the galaxies have isophotes completely describable as concentric ellipses to within the photometry errors. 'Boxy' isophotes, stellar discs, and dust lanes are detected in the remaining 25 percent of the sample. The boxy elliptical galaxies appear dynamically indistinguishable from normal ellipticals and are therefore different from boxy bulges, which rotate rapidly. Most of the galaxies with faint discs, however, appear dynamically similar to S0 galaxies. Nearly edge-on dust lanes are found in four galaxies, which suggests that dust lanes may commonly occur in elliptical galaxies.

Lauer, T. R.↗