Data for EMSL Project 50414 from September 2025
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Valiev, Marat [Environmental Molecular Sciences La↗
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Data for EMSL Project 50414 from September 2025
Explore the source record for details and available documents.
Valiev, Marat [Environmental Molecular Sciences La↗
Data for EMSL Project 50414 from September 2025
Explore the source record for details and available documents.
Valiev, Marat [Environmental Molecular Sciences La↗
Data for EMSL Project 50414 from September 2025
Explore the source record for details and available documents.
Valiev, Marat [Environmental Molecular Sciences La↗
Characterization of the procoagulant phenotype of amniotic fluid across gestation in rhesus macaques and humans
Background: Amniotic fluid (AF) plays a key role in fetal development, yet the evolving composition of AF and its effects of hemostasis and thrombosis are poorly understood. Objectives: Here, we aim to determine how the evolving molecular composition of AF relates to its procoagulant properties. Methods: We analyzed the proteomes, lipidomes and procoagulant properties of AF obtained by amniocentesis from rhesus macaque and human pregnancies at gestational-age matched timepoints. Results When added to human plasma, both rhesus and human AF accelerated clotting time and fibrin generation. We identified proteomic modules associated with clotting time and enriched for coagulation-related pathways. Proteins known to be involved in hemostasis were highly correlated with each other and their intensity of expression varied across gestation in both rhesus and humans. Inhibition of contact pathway did not affect the procoagulant effect of AF. Blocking tissue factor pathway inhibitor reversed the ability of AF to block the generation of FXa. The prothrombinase activity of AF was inhibited by phospholipid inhibitors. The levels of phosphatidylserine in AF were inversely correlated with clotting time. AF promoted platelet activation and secretion in plasma. Conclusions: The addition of AF to plasma enhances coagulation in a manner dependent on phospholipids as well as the presence of proteases and other proteins that directly regulate coagulation. We describe a correlation between clotting time and expression of coagulation proteins and phosphatidylserine in both rhesus and human AF, supporting the use rhesus models for future studies of AF biology.
amniotic fluid↗
Enhanced Reversibility of Iron Metal Anode with a Solid Electrolyte Interphase in Concentrated Chloride Electrolytes
Iron is a promising candidate for a cost-effective anode for large-scale energy storage systems due to its natural abundance and well-established mass production. Recently, Fe-ion batteries (FeIBs) that use ferrous ions as the charge carrier have emerged as a potential storage solution. The electrolytes in FeIBs are necessarily acidic to render the ferrous ions more anodically stable, allowing a wide operation voltage window. However, the iron anode suffers severe hydrogen evolution reaction with a low Coulombic efficiency (CE) in an acidic environment, shortening the battery cycle life. Herein, a hybrid aqueous electrolyte that forms a solid-electrolyte interphase (SEI) layer on the Fe anode surface is introduced. The electrolyte mainly comprises FeCl 2 and ZnCl 2 as cosalts, where the Zn-Cl anionic complex species of the concentrated ZnCl 2 allows dimethyl carbonate (DMC) to be miscible with the aqueous ferrous electrolyte. SEI derived from DMC's decomposition passivates the iron surface, which leads to an average CE of 98.3% and much-improved cycling stability. As a result, this advancement shows the promise of efficient and durable FeIBs.
25 ENERGY STORAGE↗
Anions in Corrosion: Influence of Polymer Electrolytes on the Interfacial Ion Transfer Kinetics of Cu at Au(111) Surfaces
The corrosion kinetics of metals in the presence of polymer electrolytes—which are often used in devices for the electrochemical production of hydrogen, hydrocarbons, and alcohols—is convoluted by transport and ill-defined reactive interfaces which mask the fundamental reaction kinetics. Underpotential-deposited monolayers of Cu at Au(111) surfaces provide a structurally welldefined active site for interfacial ion transfer, with a fixed number of sites available for adsorption. Here, we investigate the adsorption behavior of Cu at Au(111) surfaces across a series of sulfate and sulfonate electrolytes, to understand how anion structure influences the kinetics of elementary interfacial ion-transfer reactions. The influence of anion structure is most significant at high adsorbate coverage, with similar adsorption isotherms and kinetics observed for all three molecular sulfates and sulfonates. In contrast, a suspended perfluorosulfonic acid ionomer reduced both the equilibrium coverage of Cu as well as the standard exchange rate at Au(111) at low coverages of Cu. These results suggest that electrocatalyst corrosion is inhibited for metal nanoparticles supported at polymer electrolytes due to changes in adsorbate coverage as well as suppressed kinetics for interfacial ion transfer.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Metabolomic and transcriptomic remodeling of bone marrow myeloid cells in response to maternal obesity
Maternal obesity puts the offspring at high risk of developing obesity and cardiometabolic diseases in adulthood. Here, we utilized a mouse model of maternal high-fat diet (HFD)-induced obesity that recapitulates metabolic perturbations seen in humans. We show increased adiposity in the offspring of HFD-fed mothers (Off-HFD) when compared with the offspring of regular diet-fed mothers (Off-RD). We have previously reported significant immune perturbations in the bone marrow of newly weaned Off-HFD. Here, we hypothesized that lipid metabolism is altered in the bone marrow of Off-HFD versus Off-RD. To test this hypothesis, we investigated the lipidomic profile of bone marrow cells collected from 3-week-old Off-RD and Off-HFD. Diacylglycerols (DAGs), triacylglycerols (TAGs), sphingolipids, and phospholipids were remarkably different between the groups, independent of fetal sex. Levels of cholesteryl esters were significantly decreased in Off-HFD, suggesting reduced delivery of cholesterol. These were accompanied by age-dependent progression of mitochondrial dysfunction in bone marrow cells. We subsequently isolated CD11b+ myeloid cells from 3-wk-old mice and conducted metabolomic, lipidomic, and transcriptomic analyses. The lipidomic profiles of myeloid cells were similar to those of bone marrow cells and included increases in DAGs and decreased TAGs. Transcriptomics revealed altered expression of genes related to immune pathways, including macrophage alternative activation, B-cell receptors, and transforming growth factor-β signaling. All told, this study revealed lipidomic, metabolomic, and gene expression abnormalities in bone marrow cells broadly, and in bone marrow myeloid cells particularly, in the newly weaned offspring of mothers with obesity, which might at least partially explain the progression of metabolic and cardiovascular diseases in their adulthood.
RNA sequencing↗
Continuous flow photochemical synthesis of metal–ceramic composite microparticles
We developed a UV-assisted microfluidic system to synthesize FeCrAl–Al 2 O 3 composite microparticles for additive manufacturing. Here, the system ensures precise particle size, morphology, and elemental distribution control. Increasing the dispensing pressure while keeping the oil flow rate constant resulted in larger microparticles. Laser fusing revealed FeCrAl and Al 2 O 3 phases, showing their potential as feedstocks for 3D printed heterogeneous materials such as FeCrAl/Al 2 O 3 bi-phase materials.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Aqueous Zr/Hf IV ‐Oxo Cluster Speciation and Separation
Abstract Many industrial separations of chemically‐similar elements are achieved by solvent extraction, exploiting differences in speciation and solubility across aqueous‐organic interfaces. We recently identified [OM 4 (OH) 6 (SCN) 12 ] 4− (OM 4 , M=Zr/Hf IV ) tetrahedral oxoclusters as the main species in industrial processes that produce nuclear‐grade Zr and Hf from crude ore. However, isostructural/isoelectronic OM 4 ‐oxoclusters do not explain selective extraction of Hf into the organic phase. Here we have characterized heterometal Hf−Zr clusters in solution and the solid‐state yielding key information about their fundamentally different chemistry that engenders separation. Clusters prepared with both ammonium (industrial process) and tetramethylammonium counter cations revealed that 1) heterometal clusters (instead of a mixture of homometal clusters) assemble, and 2) Hf‐rich OM 4 selectively precipitates over Zr‐rich OM 4 , providing a separation process that does not require an organic extractant. Mass spectrometry, small‐angle X‐ray scattering, solution‐state 1 H nuclear magnetic resonance (NMR) spectroscopy, and solid‐state 17 O NMR evidence both mixed‐metal speciation and selective Hf‐precipitation. Raman spectroscopy suggests greater Zr‐ligand lability than Hf‐ligand lability, consistent with higher aqueous solubility of Zr‐rich clusters, enabling both extraction and precipitation‐based separation. Fundamentally, we also identify a key difference between these chemically similar elements that has enabled diversification of Zr‐polyoxocation chemistry over the last decade, while Hf‐polyoxocation chemistry lags.
Roseborough, Alexander [Department of Chemistry Or↗
Effect of LPBF Processing Parameters on Inconel 718 Lattice Structures: Geometrical Characteristics, Surface Morphology, and Mechanical Properties
Laser Powder Bed Fusion (LPBF) enables the additive manufacturing of complex lattice structures. However, the fabrication of lattice structures via LPBF poses challenges in achieving the intended geometrical accuracy due to their inherent complexity. This study investigates the effects of LPBF processing parameters, specifically laser power and scanning speed, on the geometrical characteristics, surface quality, and mechanical behavior of Inconel 718 lattices structures. The results reveal that processing parameters required for the fabrication of near-full dense structures do not translate effectively to lattice configurations, as variations in energy input influence lattice geometry and surface quality. In this work, strut thickness, open-pore size, open-cell porosity, and surface roughness were measured, and the mechanical properties of the lattices were evaluated under shear loading. The findings indicate that lower energy inputs, achieved by reducing laser power and increasing scanning speed, yield porous structures but lead to mechanical degradation. In contrast, high energy inputs lead to lattices with enhanced strength but result in undesirable open-pore blockage and dimensional inaccuracies. These findings provide insights into tailoring LPBF parameters for dimensional accuracy in lattices and correlating the processing parameters to mechanical performance and surface roughness.
36 MATERIALS SCIENCE↗
Integrated soft snake robot for gamma spectroscopy of radiologically contaminated ducting
Anticipated growth in the number and complexity of nuclear facilities entering the decommissioning phase of their lifespan requires innovative methods of mitigating radiological and safety hazards for workers. Advancements in robotics provide opportunities for remote characterization of radiologically contaminated ducts and pipes, reducing worker exposure. However, the nuclear decommissioning industry has shown a hesitancy in adopting new technology due to concerns regarding capital costs and a lack of demonstration data in representative environments. This work aims to leverage novel soft robotics to develop and demonstrate a sensor-integrated characterization tool for contaminated ducting systems. Two gamma spectrometers – one scintillation-based and one solid-state – were selected and integrated into a pneumatically-actuated snake-like soft robot using stretchable electronic cabling. The robot was then demonstrated at the Idaho National Laboratory’s Critical Infrastructure Test Range Complex. The robot maneuvered through a pseudo-constrained corridor containing several sealed sources and the integrated spectrometers collected spectra at various points along the path of travel. Both spectrometers successfully collected spectra with identifiable, isotope-specific peaks. To evaluate the effect of contamination buildup on the collected spectra, the robot with the integrated scintillation detector was tested using a liquid radioactive source. The resulting spectra showed little detection interference from the liquid contamination; however, a short-lived isotope was used which may not be representative of longer-lived contamination.
11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
Activating magnetite ores for aqueous ironmaking at high current densities
Low-temperature electrochemical cells reducing iron oxides to metal in alkaline electrolytes can support fully electrified steelmaking processes. Previous studies on these cells have primarily focused on high-surface-area hematite, Fe 2 O 3 , reactants whereas attempts to reduce suspensions of magnetite, Fe 3 O 4 —one of the two feedstocks for existing ironmaking reactors—have generally been limited to low rates of reaction (<30 mA cm −2 ). Here, in this study, we control the crystalline domain size of Fe 2 O 3 and Fe 3 O 4 particles in 10 M NaOH electrolytes to study how the nanoscale morphology of oxides controls the rate of electrochemical ironmaking. Rotating-ring disk electrode measurements of Fe 2+ , in situ Raman spectroscopy of the electrode surface, and ex situ electron microscopy were consistent with a hypothesized passivation process at Fe 3 O 4 surfaces that may prevent the continuous formation of soluble intermediates. Sufficiently small (<100 nm diameter) oxide particles yielded Fe partial current densities >160 mA cm −2 , a fivefold increase relative to previously reported rates for Fe 3 O 4 suspensions and comparable to active Fe 2 O 3 . Electron microscopy revealed that electrodeposited films were composed of micron-scale crystalline Fe domains with a porous film of Fe 3 O 4 nanoparticles and supports a model where Fe is grown primarily from soluble Fe 2+ intermediates. Based on these insights, inactive blast-furnace-grade iron-oxides were transformed into high surface area nanoparticles (1.6 to 229.2 m 2 g −1 ) via reprecipitation, leading to a ninefold enhancement in faradaic efficiency and an Fe partial current density of 120 mA cm −2 . When integrated with chlor-iron cells producing reagents for reprecipitation, this approach could lead to a cost-competitive process for electrochemical ironmaking from industrially relevant feedstocks.
TEM↗
The role of the Pt-group dehydrogenation catalyst in alkane metathesis for polyolefin deconstruction
Recent proposed approaches in the depolymerization of waste plastics employ an olefin intermediate to produce alkanes or alkenes using olefin metathesis in tandem chemistry. Here, in this study, we investigated the role of the dehydrogenation catalyst on reaction rate, kinetics, and product distribution in heterogeneous tandem dehydrogenation and olefin metathesis (alkane metathesis) of three different alkane reactants, including polyethylene. We found that many properties to which alkane dehydrogenation rates were sensitive-including metal composition, nanoparticle size, and surface doping of Re species also controlled activity in Tandem D/OM. When comparing Pd, Pt, and Pt 3 Sn 1 , supported Pd in tandem with a Re 2 O 7 olefin metathesis catalyst showed four-fold higher activity (surface area basis) compared to Pt or Pt 3 Sn 1 catalysts on the same support, mainly due to differences in the rate of hydrogenation. Catalyst preparation resulted in metal nanoparticles partially covered by ReO x , as seen from elemental mapping. Co-location of Re 2 O 7 and Pd correlated with increased rates of hydrogenation (i.e., an increase in the rate of alkane formation and simultaneous lowering of the rate of alkene formation), with a reaction order in catalyst study that further supported this conclusion. The Pd and Re 2 O 7 system displayed marked improvement compared to Pt or Pt 3 Sn 1 with Re 2 O 7 , and previous work, in the depolymerization rate of a linear polyethylene feedstock, with over 94 % reduction in polymer molecular weight in 15 h at 190 °C using less catalyst and increased reactant loadings, while keeping solvent to polymer consumption below 2.5.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Building a predictive model for polycyclic aromatic hydrocarbon dosimetry in organotypically cultured human bronchial epithelial cells using benzo[ a ]pyrene
The airway epithelium is a primary route of exposure for inhaled toxicants, and organotypic culture models represent an important advancement for toxicity testing compared to simple in vitro models that may lack metabolic capability and multicellular structure/communication associated with the bronchial epithelium in vivo. A quantitative understanding of chemical dosimetry is key for interpreting and extrapolating study results; however, dosimetry is understudied in organotypic models limiting ability to predict toxicity. We developed a dosimetry model for primary human bronchial epithelial cells (HBECs) cultured at the air-liquid interface (ALI) using benzo[a]pyrene (BAP), a representative polycyclic aromatic hydrocarbon. Dose and time course evaluation of metabolite formation and enzyme activity and expression were utilized to parameterize a cellular dosimetry model to improve the utility of ALI-HBECs for assessing chemical risk. Dosimetry analysis demonstrated absorption of BAP into cells and an increase in Phase 1 and 2 metabolites over time that correlated with regulation of metabolizing enzymes. BAP was cleared from cells by 48 h after exposure, and the primary metabolites generated in ALI-HBECs were BAP-3-phenol, BAP-4,5-dihydrodiol, BAP-7,8-dihydrodiol, BAP-9,10-dihydrodiol, BAP-7,8,9,10-tetrol, BAP-3-phenol-glucuronide, BAP-4,5-dihydrodiol-glucuronide, and BAP-9,10-dihydrodiol-glucuronide. The resulting dosimetry model described BAP and 7,8-dihydrodiol toxicokinetics in ALI-HBECs and suggested active excretion of 7,8-dihydrodiol. Overall, this study demonstrates metabolic competency of ALI-HBECs for BAP metabolism, demonstrates the usefulness of complex in vitro systems for human-relevant toxicity data, and exhibits how in silico models can be utilized for understanding the dosimetry of test compounds to aid in in vitro to human extrapolation of toxicity data for risk assessments.
Benzo[a]pyrene↗
Pathways to Electrochemical Ironmaking at Scale Via the Direct Reduction of Fe 2 O 3
Electrochemical ironmaking can provide an energy efficient, zero-emissions alternative to traditional methods of ironmaking, but the scalability of low-temperature electrochemical cells may be constrained by reactor throughput and the availability of acceptable feedstocks. Electrodes directly converting solid iron-oxide particles to metal circumvent traditional mass-transport limitations but are sensitive to both the particle size and nanoscale morphology of reactants. Furthermore, the effect of these properties on reactor throughput has not been systematically studied at model electrowinning surfaces. Here, we have used size-controlled, homologous α-Fe 2 O 3 particles to study how the nanoscale morphology of oxides influences the obtainable current density toward Fe metal and integrated these results in a technoeconomic model for alkaline iron electrowinning systems. Micron-scale α-Fe 2 O 3 with nanoscale porosity can be used to form Fe at current densities commensurate with industrial water electrolysis (>0.6 A cm –2 ) in the absence of external convection, providing a path to cost-competitive and scalable ironmaking using electrochemistry.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Gut microbiome changes with micronutrient supplementation in children with attention–deficit/hyperactivity disorder: the MADDY study
Micronutrients have demonstrated promise in managing inattention and emotional dysregulation in children with attention-deficit/hyperactivity disorder (ADHD). The biological mechanism by which micronutrients improve these symptoms remains unclear. One plausible pathway is through the gut-brain axis, the bi-directional communication network that links the gastrointestinal tract with the brain. This study examines changes in gut microbiome composition and diversity after micronutrients supplementation in children with ADHD (N=44) and sheds light on potential mechanisms responsible for the response to micronutrients as measured by clinician-rated global impression. Participants from this investigation represent a sub-group of the Micronutrients for ADHD in Youth (MADDY) study, a double blind randomized controlled study in which participants received either micronutrients or a placebo for 8 weeks, followed by an 8-week open label extension with micronutrients for all participants. Stool samples collected at baseline, week 8, and week 16 were analyzed using 16S rRNA amplicon sequencing targeting the V4 hypervariable region. Pairwise compositional analyses served as the primary means for investigating changes in gut microbiome composition between micronutrients versus placebo groups and responders versus non-responders. A significant change in microbial evenness, as measured by alpha diversity, was observed following micronutrients, and the phylum Actinobacteriota decreased in the micronutrients group compared to placebo. Additionally, two bacterial families: Rikenellaceae and Oscillospiraceae, exhibited a significant increase in change of gut microbiome composition following micronutrients between responders and non-responders. These findings suggest that micronutrients modulated the composition of the gut microbiome and point towards specific bacterial changes associated with response to micronutrients.
60 APPLIED LIFE SCIENCES↗
Computational capacity in hydrodynamic real-time hybrid simulation applied to simulate the dynamic response of floating offshore wind turbines
Real-time hybrid simulation (RTHS) mitigates similitude distortions in model-scale tests of floating offshore wind turbines (FOWTs) by coupling physical experiments with numerical models in real time. The coupling requires faster-than-real-time numerical computations to satisfy temporal similitude with the physical experiment, presenting a bottleneck for using more complex numerical models in RTHS. This paper presents a hydrodynamic-RTHS (hydro-RTHS) framework for FOWTs that simulates the hydrodynamics physically and the aerodynamics numerically with sensor feedback from the physical testing. The framework adapts the three-loop hardware architecture to leverage greater computational resources and mitigate strict temporal requirements, enabling more computationally demanding numerical analyses in hydro-RTHS. The three-loop hardware architecture integrates multiple machines, each dedicated to either numerical analysis or RTHS controls, with a rate-transition algorithm to synchronize the tasks executed across the different machine processors. Virtual and physical tests verified and validated the hydro-RTHS framework, respectively. The ”virtual” tests, which approximates the physical domain numerically, verified the RTHS framework with respect to a numerical full-scale complete FOWT model simulated in the open-source software, OpenFAST. The virtual tests were able to maintain comparable control signals while enabling greater computational resources for the numerical calculations. Real-world physical tests demonstrated that the hydro-RTHS framework computes aerodynamic forces similar to the complete OpenFAST model, validating the hydro-RTHS framework using the three-loop hardware architecture. Findings show that the hydro-RTHS framework with the three-loop hardware architecture is computationally efficient, with reserve capacity to simulate more complex problems due to the customized software, hardware, and rate-transition algorithm.
17 WIND ENERGY↗