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At least 145 records · Page 8

Quantitative Stable-Isotope Probing (qSIP) with Metagenomics Links Microbial Physiology and Activity to Soil Moisture in Mediterranean-Climate Grassland Ecosystems

The growth and physiology of soil microorganisms, which play vital roles in biogeochemical cycling, are shaped by both current and historical soil environmental conditions. Here, we developed and applied a genome-resolved metagenomic implementation of quantitative stable isotope probing (qSIP) with an H 2 18 O labeling experiment to identify actively growing soil microorganisms and their genomic capacities. qSIP enabled measurement of taxon-specific growth because isotopic incorporation into microbial DNA requires production of new genome copies. We studied three Mediterranean grassland soils across a rainfall gradient to evaluate the hypothesis that historic precipitation levels are an important factor controlling trait selection. We used qSIP-informed genome-resolved metagenomics to resolve the active subset of soil community members and identify their characteristic ecophysiological traits. Higher year-round precipitation levels correlated with higher activity and growth rates of flagellar motile microorganisms. In addition to heavily isotopically labeled bacteria, we identified abundant isotope-labeled phages, suggesting phage-induced cell lysis likely contributed to necromass production at all three sites. Further, there was a positive correlation between phage activity and the activity of putative phage hosts. Contrary to our expectations, the capacity to decompose the diverse complex carbohydrates common in soil organic matter or oxidize methanol and carbon monoxide were broadly distributed across active and inactive bacteria in all three soils, implying that these traits are not highly selected for by historical precipitation.

54 ENVIRONMENTAL SCIENCES↗

The energetics and dynamics of confinement in flexible frameworks and molecular confinement

Porous frameworks form the chemical and structural basis for critical technologies in separations, catalysis, nuclear waste containment and biomedical applications. Hundreds of zeolites and metal organic frameworks (MOFs) have been synthesized, and their ability to separate and store hydrogen, methane and carbon dioxide has been investigated both experimentally and theoretically. Nevertheless, a fundamental and systematic molecular-level understanding of the thermodynamic and structural factors governing the stability and guest-host interactions in these materials lags behind focused studies of specific systems. Because the guest molecules interact with each other and with the host framework, molecular confinement is a finely balanced and complex phenomenon. The ability of the guest molecules to bind and diffuse through the pores is determined by the nature of the host framework which, in turn, responds to the nature and concentration of guest molecules and to pressure and temperature. The work explores how framework flexibility, tailored by structure, composition, temperature and pressure, is a general phenomenon, similar in nature but variable in extent, in both zeolites and MOFs and is part of a free energy landscape in which framework-guest interactions, pressure, and temperature result in changes in framework geometry and, in some cases, phase transitions. These subtle and/or pronounced changes in lattice geometry, energetics, and dynamics can play a decisive role in confinement and in differentiating the binding of molecules of similar size. The free energy landscape created by these structural changes links polymorphism, amorphization, “breathing,” “gate opening” and confinement. Specifically, the generality of such behavior arises from commonalities in lattice dynamics and energetics of frameworks containing a combination of strong rigid bonds and weaker more flexible deformation modes. Identifying and describing these common and collective phenomena is the focus of the research on a selected group of zeolites and MOFs. Structural studies using X-ray and neutron diffraction explore the mechanical functionality of these important materials, specifically how framework materials respond to changes in temperature, pressure and guest loading. These structural studies are combined with calorimetric measurements, using techniques uniquely developed in the participating laboratories, of heats of formation, heat capacities and entropies, and guest-host interactions. The experimental thermodynamic studies are complemented by inelastic neutron scattering studies of the lattice dynamics related both to framework vibrations and to guest-host interactions. The report below summarizes the work done at UC Davis, which is complemented by work done at BYU (Woodfield) and Virginia Tech (Ross).

36 MATERIALS SCIENCE↗

The energetics and dynamics of confinement in flexible frameworks and molecular confinement

Porous frameworks form the chemical and structural basis for critical technologies in separations, catalysis, nuclear waste containment and biomedical applications. Hundreds of zeolites and metal organic frameworks (MOFs) have been synthesized, and their ability to separate and store hydrogen, methane and carbon dioxide has been investigated both experimentally and theoretically. Nevertheless, a fundamental and systematic molecular-level understanding of the thermodynamic and structural factors governing the stability and guest-host interactions in these materials lags behind focused studies of specific systems. Because the guest molecules interact with each other and with the host framework, molecular confinement is a finely balanced and complex phenomenon. The ability of the guest molecules to bind and diffuse through the pores is determined by the nature of the host framework which, in turn, responds to the nature and concentration of guest molecules and to pressure and temperature. The work explores how framework flexibility, tailored by structure, composition, temperature and pressure, is a general phenomenon, similar in nature but variable in extent, in both zeolites and MOFs and is part of a free energy landscape in which framework-guest interactions, pressure, and temperature result in changes in framework geometry and, in some cases, phase transitions. These subtle and/or pronounced changes in lattice geometry, energetics, and dynamics can play a decisive role in confinement and in differentiating the binding of molecules of similar size. The free energy landscape created by these structural changes links polymorphism, amorphization, “breathing,” “gate opening” and confinement. Specifically, the generality of such behavior arises from commonalities in lattice dynamics and energetics of frameworks containing a combination of strong rigid bonds and weaker more flexible deformation modes. Identifying and describing these common and collective phenomena is the focus of the research on a selected group of zeolites and MOFs. Structural studies using X-ray and neutron diffraction explore the mechanical functionality of these important materials, specifically how framework materials respond to changes in temperature, pressure and guest loading. These structural studies are combined with calorimetric measurements, using techniques uniquely developed in the participating laboratories, of heats of formation, heat capacities and entropies, and guest-host interactions. The experimental thermodynamic studies are complemented by inelastic neutron scattering studies of the lattice dynamics related both to framework vibrations and to guest-host interactions. This research was a collaboration between UC Davis (A. Navrotsky) BYU (B. Woodfield) and Virginia Tech (N. Ross).

36 MATERIALS SCIENCE↗

Nonadditive Interactions Unlock Small-Particle Mobility in Binary Colloidal Monolayers

We examine the organization and dynamics of binary colloidal monolayers composed of micron-scale silica particles interspersed with smaller-diameter silica particles that serve as minority component impurities. These binary monolayers are prepared at the surface of ionic liquid droplets over a range of size ratios (σ = 0.16–0.66) and are studied with low-dose minimally perturbative scanning electron microscopy (SEM). The high resolution of SEM imaging provides direct tracking of all particle coordinates over time, enabling a complete description of the microscopic state. In these bidisperse size mixtures, particle interactions are nonadditive because interfacial pinning to the droplet surface causes the equators of differently sized particles to lie in separate planes. By varying the size ratio, we control the extent of nonadditivity in order to achieve phase behavior inaccessible to additive 2D systems. Across the range of size ratios, we tune the system from a mobile small-particle phase (σ < 0.24) to an interstitial solid (0.24 < σ < 0.33) and furthermore to a disordered glass (σ > 0.33). These distinct phase regimes are classified through measurements of hexagonal ordering of the large-particle host lattice and the lattice’s capacity for small-particle transport. Altogether, we explain these structural and dynamic trends by considering the combined influence of interparticle interactions and the colloidal packing geometry. Our measurements are reproduced in molecular dynamics simulations of 2D nonadditive disks, suggesting an efficient method for describing confined systems with reduced dimensionality representations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Free-standing ultrathin lithium metal–graphene oxide host foils with controllable thickness for lithium batteries

Thin (≤20 μm) and free-standing Li metal foils would enable precise prelithiation of anode materials and high-energy-density Li batteries. Existing Li metal foils are too thick (typically 50 to 750 μm) or too mechanically fragile for these applications. Here, we developed a facile and scalable process for the synthesis of an ultrathin (0.5 to 20 μm), free-standing and mechanically robust Li metal foil within a graphene oxide host. In addition to low areal capacities of ~0.1 to 3.7 mAh cm –2 , this Li foil also has a much-improved mechanical strength over conventional pure Li metal foil. Our Li foil can improve the initial Coulombic efficiency of graphite (93%) and silicon (79.4%) anodes to around 100% without generating excessive Li residue, and increases the capacity of Li-ion full cells by 8%. In conclusion, the cycle life of Li metal full cells is prolonged by nine times using this thin Li composite anode.

25 ENERGY STORAGE↗

Comparative Molecular and Immunoregulatory Analysis of Extracellular Vesicles from Candida albicans and Candida auris

Candida auris is a recently described multidrug-resistant pathogenic fungus that is increasingly responsible for health care-associated outbreaks across the world. Bloodstream infections of this fungus cause death in up to 70% of cases. Aggravating this scenario, the disease-promoting mechanisms of C. auris are poorly understood. Fungi release extracellular vesicles (EVs) that carry a broad range of molecules, including proteins, lipids, carbohydrates, pigments, and RNA, many of which are virulence factors. Here, we carried out a comparative molecular characterization of C. auris and Candida albicans EVs and evaluated their capacity to modulate effector mechanisms of host immune defense. Using proteomics, lipidomics, and transcriptomics, we found that C. auris released EVs with payloads that were significantly different from those of EVs released by C. albicans. EVs released by C. auris potentiated the adhesion of this yeast to an epithelial cell monolayer, while EVs from C. albicans had no effect. C. albicans EVs primed macrophages for enhanced intracellular yeast killing, whereas C. auris EVs promoted survival of the fungal cells. Moreover, EVs from both C. auris and C. albicans induced the activation of bone marrow-derived dendritic cells. Together, our findings show distinct profiles and properties of EVs released by C. auris and by C. albicans and highlight the potential contribution of C. auris EVs to the pathogenesis of this emerging pathogen.

59 BASIC BIOLOGICAL SCIENCES↗

Proteome-wide characterization of PTMs reveals host cell responses to viral infection and identifies putative antiviral drug targets

Post-translational modifications (PTMs) are biochemical modifications that can significantly alter protein structure, function, stability, localization, and interactions with other molecules, thereby activating or inactivating intracellular processes. A growing body of research has begun to highlight the role of PTMs, including phosphorylation, ubiquitination, acetylation, and redox modifications, during virus-host interactions. Collectively, these PTMs regulate key steps in mounting the host immune response and control critical host pathways required for productive viral replication. This has led to the conception of antiviral therapeutics that focus on controlling host protein PTMs, potentially offering pathogen-agnostic treatment options and revolutionizing our capacity to prevent virus transmission. On the other hand, viruses can hijack the host cellular PTM machinery to modify viral proteins in promoting viral replication and evading immune surveillance. PTM regulation during virus-host interactions is complex and poorly mapped, and the development of effective PTM-targeted antiviral drugs will require a more comprehensive understanding of the cellular pathways essential for virus replication. In this review, we discuss the roles of PTMs in virus infection and how technological advances in mass spectrometry-based proteomics can capture systems-level PTM changes during viral infection. Additionally, we explore how such knowledge is leveraged to identify PTM-targeted candidates for developing antiviral drugs. Looking ahead, studies focusing on the discovery and functional elucidation of PTMs, either on the host or viral proteins, will not only deepen our understanding of molecular pathology but also pave the way for developing better drugs to fight emerging viruses.

Immunology↗

Heat capacity and thermodynamic functions of partially dehydrated sodium and zinc zeolite A (LTA)

Zeolite A (LTA) is an industrially important zeolite that exhibits sorption-induced framework flexibility, the thermodynamics of which are poorly understood. In this work, we report heat capacity measurements on zinc and sodium zeolite A from 1.8 to 300 K and compare the heat capacity of water in sodium zeolite A with that of water in other zeolites. The heat capacity of zeolitic water varies significantly depending on the hydration level and identity of the host zeolite, and more tightly bound water exhibits strong inflections in its heat capacity curve. This suggests a combination of effects, including differences in water-framework binding strength and hydration-dependent flexibility transitions. We also report fits of the heat capacity data using theoretical functions, and we report values for $C_{P,m}^°$,$Δ_0^TS_m^°$,$Δ_0^TH_m^°$, and $Φ_m^°$ from 0 to 300 K. These results contribute to a systematic thermodynamic understanding of the effects of cation exchange, guest molecule confinement, and sorbate-dependent flexibility transitions in zeolites.

Geochemistry & Geophysics↗

PLUSWIND Hourly Plant-Level Power

These data contain the hourly plant-level power time series from PLUSWIND. The time series is derived from the HRRR model and corrected for density and losses. The PLUSWIND dataset hosted on the Wind Data Hub here (https://a2e.energy.gov/project/pluswind) contains additional versions with meteorological corrections. Data are provided for years 2018 - 2021. The data hosted at this location include conversion from capacity factor output (normalized output) to total hourly production (units of MW).

17 WIND ENERGY↗

Dual Functional Ni3S2@Ni Core-Shell Nanoparticles Decorating Nanoporous Carbon as Cathode Scaffolds for Lithium-Sulfur Battery with Lean Electrolytes

Lithium-sulfur batteries are very promising for next-generation energy storage. However, most studies use flooded electrolytes to achieve a high specific capacity at the expense of lowering the specific energy. Understanding lithium-sulfur battery performance with lean electrolytes is highly desirable. Herein, a modified Pechini method is developed to synthesize a nanoporous carbon host decorated with Ni3S2@Ni particles. Such a cathode delivers enhanced specific capacities with extended cycling life in lean electrolytes, due to the dual functions of the Ni3S2 shell, which can both facilitate reaction kinetics and promote electrolyte wetting. This work highlights a strategy to rationally design cathodes for highenergy lithium-sulfur batteries.

Zhang, Yulun↗

Revolutionizing Porous Liquids: Stabilization and Structural Engineering Achieved by a Surface Deposition Strategy

Facile approaches capable of constructing stable and structurally diverse porous liquids (PLs) that can deliver high-performance applications are a long-standing, captivating, and challenging research area that requires significant attention. Here, in this work, a facile surface deposition strategy is demonstrated to afford diverse type III-PLs possessing ultra-stable dispersion, external structure modification, and enhanced performance in gas storage and transformation by leveraging the expeditious and uniform precipitation of selected metal salts. The Ag(I) species-modified zeolite nanosheets are deployed as the porous host to construct type III-PLs with ionic liquids (ILs) containing bromide anion , leading to stable dispersion driven by the formation of AgBr nanoparticles. The as-afforded type-III PLs display promising performance in CO 2 capture/conversion and ethylene/ethane separation. Property and performance of the as-produced PLs can be tuned by the cation structure of the ILs, which can be harnessed to achieve polarity reversal of the porous host via ionic exchange. The surface deposition procedure can be further extended to produce PLs from Ba(II)-functionalized zeolite and ILs containing [SO 4 ] 2– anion driven by the formation of BaSO 4 salts. The as-produced PLs are featured by well-maintained crystallinity of the porous host, good fluidity and stability, enhanced gas uptake capacity, and attractive performance in small gas molecule utilization.

36 MATERIALS SCIENCE↗

Herbivorous Fish Microbiome Adaptations to Sulfated Dietary Polysaccharides

Marine herbivorous fish that feed primarily on macroalgae, such as those from the genus Kyphosus, are essential for maintaining coral health and abundance on tropical reefs. Here, deep metagenomic sequencing and assembly of gut compartment-specific samples from three sympatric, macroalgivorous Hawaiian kyphosid species have been used to connect host gut microbial taxa with predicted protein functional capacities likely to contribute to efficient macroalgal digestion. Bacterial community compositions, algal dietary sources, and predicted enzyme functionalities were analyzed in parallel for 16 metagenomes spanning the mid- and hindgut digestive regions of wild-caught fishes. Gene colocalization patterns of expanded carbohydrate (CAZy) and sulfatase (SulfAtlas) digestive enzyme families on assembled contigs were used to identify likely polysaccharide utilization locus associations and to visualize potential cooperative networks of extracellularly exported proteins targeting complex sulfated polysaccharides. These insights into the gut microbiota of herbivorous marine fish and their functional capabilities improve our understanding of the enzymes and microorganisms involved in digesting complex macroalgal sulfated polysaccharides.

09 BIOMASS FUELS↗

Loss of Glen Canyon Dam Hydropower Plant Capabilities

The power grid in the western United States is undergoing a major transformation, driven by technological advancements, power markets, policy shifts, and evolving energy demands. The integration of variable renewable energy (VRE) resources, such as wind and solar, into the power grid has become a major driver of change. Between 2018 and 2023, about 19 gigawatts (GW) of new solar capacity and 14 GW of new wind capacity was built in the Western Interconnection (WI) region. These two VRE resources accounted for the majority of WI capacity additions. The Western Interconnection is expected to host 30 GW of wind, 40 GW of solar, and 14 GW of energy storage by 2030 (Western Electricity Coordinating Council n.d.).

13 HYDRO ENERGY↗

Evaluation of Nuclear Spent Fuel Disposal in Clay-Bearing Rock - Process Model Development and Experimental Studies

This report represents the milestone deliverable M2SF-23SN010301072 “Evaluation of Nuclear Spent Fuel Disposal in Clay-Bearing Rock - Process Model Development and Experimental Studies” The report provides a status update of FY23 activities for the work package Argillite Disposal work packages for the DOE-NE Spent Fuel Waste Form Science and Technology (SFWST) Program. Clay-rich geological media (often referred as shale or argillite) are among the most abundant type of sedimentary rock near the Earth’s surface. Argillaceous rock formations have the following advantageous attributes for deep geological nuclear waste disposal: widespread geologic occurrence, found in stable geologic settings, low permeability, self-sealing properties, low effective diffusion coefficient, high sorption capacity, and have the appropriate depth and thickness to host nuclear waste repository concepts. The DOE R&D program under the Spent Fuel Waste Science Technology (SFWST) campaign has made key progress (through experiment, modeling, and testing) in the study of chemical and physical phenomena that could impact the long-term safety assessment of heat-generating nuclear waste disposition in clay/shale/argillaceous rock. International collaboration activities comprising field-scale heater tests, field data monitoring, and laboratory-scale experiments provide key information on changes to the engineered barrier system (EBS) material exposed high thermal loads. Moreover, consideration of direct disposal of large capacity dual-purpose canisters (DPCs) as part of the back-end SNF waste disposition strategy has generated interest in improving our understanding of the effects of elevated temperatures on the engineered barrier system (EBS) design concepts. Chemical and structural analyses of sampled bentonite material from laboratory tests at elevated temperatures are key to the characterization of thermal effects affecting bentonite clay barrier performance. The knowledge provided by these experiments is crucial to constrain the extent of sacrificial zones in the EBS design during the thermal period. Thermal, hydrologic, mechanical, and chemical (THMC) data collected from heater tests and laboratory experiments have been used in the development, validation, and calibration of THMC simulators to model near-field coupled processes. This information leads to the development of simulation approaches to assess issues on coupled processes involving porous media flow, transport, geomechanical phenomena, chemical interactions with barrier/geologic materials, and the development of EBS concepts. These lines of knowledge are central to the design of deep geological backfilled repository concepts where temperature plays a key role in the EBS behavior, potential interactions with host rock, and long-term performance in the safety assessment.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Engineering Nannochloropsis oceanica for the production of diterpenoid compounds

Abstract Photosynthetic microalgae like Nannochloropsis hold enormous potential as sustainable, light‐driven biofactories for the production of high‐value natural products such as terpenoids. Nannochloropsis oceanica is distinguished as a particularly robust host with extensive genomic and transgenic resources available. Its capacity to grow in wastewater, brackish, and sea waters, coupled with advances in microalgal metabolic engineering, genome editing, and synthetic biology, provides an excellent opportunity. In the present work, we demonstrate how N. oceanica can be engineered to produce the diterpene casbene—an important intermediate in the biosynthesis of pharmacologically relevant macrocyclic diterpenoids. Casbene accumulated after stably expressing and targeting the casbene synthase from Daphne genkwa (DgTPS1) to the algal chloroplast. The engineered strains yielded production titers of up to 0.12 mg g −1 total dry cell weight (DCW) casbene. Heterologous overexpression and chloroplast targeting of two upstream rate‐limiting enzymes in the 2‐C‐methyl‐ d ‐erythritol 4‐phosphate pathway, Coleus forskohlii 1‐deoxy‐ d ‐xylulose‐5‐phosphate synthase and geranylgeranyl diphosphate synthase genes, further enhanced the yield of casbene to a titer up to 1.80 mg g −1 DCW. The results presented here form a basis for further development and production of complex plant diterpenoids in microalgae.

Du, Zhi‐Yan↗

Phase Stability and Kinetics of Topotactic Dual Ca 2+ –Na + Ion Electrochemistry in NaSICON NaV 2 (PO 4 ) 3

Recent reports of reversible calcium plating and stripping have rekindled interest in the development of Ca-ion batteries (CIBs) as next-generation energy storage devices. This technology has the potential to overcome the limitations of conventional Li-ion batteries, but CIBs are plagued by a paucity of suitable cathode materials. To date, NaSICON-structured NaV 2 (PO 4 ) 3 has been demonstrated as a successful cathode candidate, exhibiting reversible (de)intercalation of 0.6 mol Ca 2+ along with stable cycling performance. However, a complex multiphase mixture forms on discharge so the Ca-ion charge storage mechanism in the NaSICON framework is poorly understood. Here in this work, we report on an investigation of the structure and/or Na + /Ca 2+ environment(s) of a variety of chemically prepared NaSICON Ca x Na y V 2 (PO 4 ) 3 phases which were characterized using synchrotron XRD, SEM-EDS, 23 Na NMR, and TEM. Highly calciated CaV 2 (PO 4 ) 3 , Ca 1.5 V 2 (PO 4 ) 3 , and CaNaV 2 (PO 4 ) 3 phases can be prepared at high temperature, but -unlike Ca 0.6 NaV 2 (PO 4 ) 3 -these materials are electrochemically inactive. To better understand the fundamental factors impacting successful Ca 2+ electrochemistry in this system, DFT was employed to examine the Ca x Na y V 2 (PO 4 ) 3 phase diagram and Ca 2+ diffusion mechanism. Theoretical insights show that phase separation into Na-rich and Ca-rich phases is a reason for the capacity limitation and demonstrate that Na + ions in the host materials assist the migration of neighboring Ca 2+ ions, enabling reversible electrochemistry in Ca x Na y V 2 (PO 4 ) 3 . This investigation of fundamental principles affecting reversible Ca 2+ (de)intercalation in Ca x Na y V 2 (PO 4 ) 3 allows for the development of design principles to enable the discovery of a variety of successful cathodes for CIBs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A Multidimensional Operando Study Showing the Importance of the Electrode Macrostructure in Lithium Sulfur Batteries

Lithium sulfur batteries are one of the most promising next-generation energy storage technologies, because of their impressive theoretical energy density, low materials cost, and relative safety. However, incomplete understanding of their underlying operation mechanisms has hindered their further development and commercialization. In this work, to gain a better understanding of the operation mechanisms in the lithium sulfur battery, three macroscopically different (woven and nonwoven) and microscopically similar (made from the same carbon fibers) free-standing carbon felts are used as the conductive matrices to show how the macrostructure influences the redox reactions and the electrochemical performance. Additionally, an operando radiography and simultaneous in situ electrochemical impedance spectroscopy study are performed to highlight the differences of the carbon hosts and how they compare electrochemically in a lithium sulfur battery. The electrochemical results show that the carbon host with a more open structure results in increased capacity as well as a higher diffusion coefficient. The operando radiography shows that the open structures are more conducive to efficient redox reactivity in forming solid sulfur species, mostly in the form of elongated needlelike structures identified as β-S8, near the end of charge, which is corroborated by the impedance data. The data also reveal a “breathing” mechanism, where the polysulfides are pushed to the edges during discharge and pulled back during charge. Furthermore, it is also revealed that the “breathing” process is a limiting factor in the high rate performance. Overall, this study shows that there is a close relationship between the macrostructure of the carbon matrix and the electrochemical performance of the sulfur cathode.

25 ENERGY STORAGE↗

Beyond single tetrahedron physics of the breathing pyrochlore compound Ba 3 ⁢Yb 2 ⁢Zn 5 ⁢O 11

Recently, a new class of quantum magnets, the so-called breathing pyrochlore spin systems, have attracted much attention due to their potential to host exotic emergent phenomena. Here, we present magnetometry, heat capacity, thermal conductivity, muon-spin relaxation, and polarized inelastic neutron scattering measurements performed on high-quality single crystal samples of the breathing pyrochlore compound Ba 3 ⁢Yb 2 ⁢Zn 5 ⁢O 11 . We interpret these results using a simplified toy model and provide insight into the low-energy physics of this system beyond the single tetrahedron physics proposed previously.

36 MATERIALS SCIENCE↗