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At least 289 records · Page 16

Driving Selectivity Among Rare Earth Elements through Phase Modifiers

Phase modifiers are low molecular weight molecules added to solvent extraction separations to improve the physical performance of the separation system, for example by increasing the concentration of metal ions that can be separated or improving the compatibility of the two solvents.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

FY24 Task 4: Studies of Phosphate and Fluoride Solubility for Dissolution of High Phosphate Tank Waste

Knowledge gaps have been identified in phosphate solubility in almost every single- and multi-component system, and particularly for aluminate in phosphate/hydroxide, where uncertainties in predicted values of aluminum solubility are greater than 50%. Solubility data of multicomponent, aqueous electrolytes containing sodium hydroxide, sodium fluoride, sodium phosphate, sodium nitrite, sodium nitrate, and dissolved gibbsite are also sparse. For example, for solutions of (i) sodium nitrate and sodium phosphate, data are only available at 30 and 50 °C, and for (ii) dissolved gibbsite in sodium hydroxide and sodium phosphate, only two data points are available at 20 and 40 °C. There is no data available on mixtures of sodium hydroxide, sodium phosphate, sodium fluoride, and dissolved gibbsite. These knowledge gaps were identified in a technical review of waste solubility data and the impact of dilution on solution stabilities and will be addressed in this work to predict aluminum hydroxide and sodium phosphate solubility in multicomponent electrolytes upon dilution, and upon variation of temperature. Results will provide the technical basis to develop accurate models for (i) gibbsite solubility and mass transfer of aluminum between solid and liquid forms following the sluicing of sludge and saltcake with water; and (ii) further blending of these suspensions with bismuth from bismuth phosphate waste, and zirconium and uranium left from the fuel decladding. This work will be essential to developing a disposition path for retrieval solutions from bismuth phosphate wastes. This effort would also support sludge washing to further reduce phosphate concentration if that process were to be added back to the flowsheet in the future.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Activating a Natural Fault Zone in the Swiss Alps

One major hurdle for understanding earthquake mechanics are observational limitations. Important phenomena like strain localisation, fault dilation, and fault healing are readily studied in rock mechanical laboratory experiments and with numerical models. At the scale of natural earthquakes, however, these phenomena are often unresolvable, even by state-of-the-art observatories. To overcome this limitation, we are currently building the Earthquake Physics Testbed at the Bedretto Underground Laboratory for Geosciences and Geoenergies (BedrettoLab), an experimental testbed where we can activate an extensively instrumented natural fault zone via hydraulic stimulation. The goal of the Fault Activation and Earthquake Rupture (FEAR) project is to induce earthquakes of up to Mw~1.0 on this exceptionally well characterised and instrumented fault zone. Here we summarize the main scientific goals and current FEAR project status, and present first results from conducted experiments. We discuss how this large-scale experimental approach may allow us to tackle both fundamental science as well as practical questions on earthquake physics, induced seismicity and seismic hazard.

Meier, Men-Andrin↗

Persistent Homology Metrics Reveal Quantum Fluctuations and Reactive Atoms in Path Integral Dynamics

Nuclear quantum effects (NQEs) are known to impact a number of features associated with chemical reactivity and physicochemical properties, particularly for light atoms and at low temperatures. In the imaginary time path integral formalism, each atom is mapped onto a “ring polymer” whose spread is related to the quantum mechanical uncertainty in the particle’s position, i.e., its thermal wavelength. A number of metrics have previously been used to investigate and characterize this spread and explain effects arising from quantum delocalization, zero-point energy, and tunneling. Many of these shape metrics consider just the instantaneous structure of the ring polymers. However, given the significant interest in methods such as centroid molecular dynamics and ring polymer molecular dynamics that link the molecular dynamics of these ring polymers to real time properties, there exists significant opportunity to exploit metrics that also allow for the study of the fluctuations of the atom delocalization in time. Here we consider the ring polymer delocalization from the perspective of computational topology, specifically persistent homology, which describes the 3-dimensional arrangement of point cloud data, (i.e. atomic positions). We employ the Betti sequence probability distribution to define the ensemble of shapes adopted by the ring polymer. The Wasserstein distances of Betti sequences adjacent in time are used to characterize fluctuations in shape, where the Fourier transform and associated principal components provides added information differentiating atoms with different NQEs based on their dynamic properties. We demonstrate this methodology on two representative systems, a glassy system consisting of two atom types with dramatically different de Broglie thermal wavelengths, and ab initio molecular dynamics simulation of an aqueous 4 M HCl solution where the H-atoms are differentiated based on their participation in proton transfer reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Sampling Microbial Dynamics in the Salish Sea Estuary: Evaluating Methods to Capture Cyanobacteria and Cyanophage

Introduction: Picocyanobacteria from the genera Prochlorococcus and Synechococcus thrive across the globe in aquatic environments, have relatively small genomes, and have growth dynamics regulated by both viral interactions and abiotic conditions, making them excellent model organisms for exploring host-pathogencoevolution. Methods: We developed and refined methods to sample and sequence cyanobacteria, cyanophages, and measured features of their abiotic environment. Results: The protocol described herein can successfully discriminate large-cell eukaryotic organisms, but size fractionation of picocyanobacteria appears to be affected by the presence of free DNA, multicellular structures, and abundant tycheposons. Our preferred final protocol from this exploratory effort included a combination of in-line and single vacuum flask filtrations, which reduced filtration processing time by over threefold in some cases compared to other tested methods, such as a fully in-line sequence or in-site filtrations. We successfully extracted an average of approximately 400–1200 ng for all filter fractions, with some variations between kits. Discussion: The protocol described herein can successfully discriminate large-cell eukaryotic organisms, but size fractionation of picocyanobacteria appears to be affected by the presence of free DNA, multicellular structures, and abundant tycheposons.

Salish Sea↗

Direct and Indirect Measurements for a Better Understanding of the Primordial Nucleosynthesis

The Big Bang Nucleosynthesis (BBN) model is a great success of nuclear astrophysics due to the outstanding agreement between observational and predicted light elements abundances. One exception, however, is the so-called “lithium problem.” In this context, experimental efforts to measure the relevant reactions have been brought to an increased level of accuracy in measuring primordial abundances, and the introduction of indirect methods has allowed researchers to overcome the natural limitations of direct measurements in the energy range of interest for BBN. Here we review the results obtained from the application of the Trojan Horse Method to some of the most influential reactions of the standard network, such as 2 H(d,p) 3 H, 2 H(d,n) 3 He, 3 He(d,p) 4 He, 7 Li(p,α) 4 He, and 7 Be(n,α) 4 He. The relevant cross sections have been then used as new inputs to a classical BBN code, resulting in important constraints that make suggestions for a possible solution for the lithium problem outside of nuclear physics.

79 ASTRONOMY AND ASTROPHYSICS↗

Association of Mesoscale Auroral Structures and Breakups With Energetic Particle Injections at Geosynchronous Orbit

Geomagnetic substorms are associated with characteristic energetic particle injection signatures at geosynchronous orbit that are often dispersionless in both electrons and ions near the magnetic local time sector of auroral onset locations and are dispersed farther away from this region. Although the precise mechanism responsible for the coherent injection signatures at geosynchronous orbit have been the topic on considerable ongoing debate for decades, recent work on bursty bulk flows (BBFs) in the tail have led to the hypothesis that they may be the result of multiple, overlapping flow bursts penetrating into the inner magnetosphere from more distant downtail reconnection sites. Since auroral streamers are thought to be ionospheric signatures of BBFs in the tail, they can be used as proxies for testing this hypothesis. Using high resolution auroral imagery from the POLAR/VIS instrument combined with multi-spacecraft observations of energetic particle injections at geosynchronous orbit, we examine the association of mesoscale auroral structures with particle injection signatures over many hours during the 9 November 1998 storm. We find that the explosive types of auroral activations, such as pseudo-breakups and substorm onset breakups, are associated with the more intense and well-defined dispersed injection signatures, while intervals of isolated streamer activity appear to be associated with smaller dispersed “injectionlet” signatures. Furthermore, intervals of sustained, intense, and late expansion phase/recovery phase streamer activity appear to be associated with sustained elevated dispersed particle fluxes. These results are consistent with the hypothesis that it is the overlapping effects of sustained, intense multiple flow bursts penetrating toward the Earth that result in classical substorm particle injection signatures at geosynchronous orbit. However, it is also suggested that torches/omega-band tongues are the prime fate of braking isolated flow bursts (streamers) rather than the development of breakups, bulges, and substorm current wedge formation. A statistical analysis is presented showing that 93% of the observed torches evolved from streamers, 93% of streamers arriving in the equatorward regions of the bulge led to torches, 10.5% of such streamers led to breakups (either pseudo-breakups or substorm onsets), and only 3.5% of such streamers led to substorm onsets.

79 ASTRONOMY AND ASTROPHYSICS↗

Pathophysiological Integration of Metabolic Reprogramming in Breast Cancer

Metabolic changes that facilitate tumor growth are one of the hallmarks of cancer. The triggers of these metabolic changes are located in the tumor parenchymal cells, where oncogenic mutations induce an imperative need to proliferate and cause tumor initiation and progression. Cancer cells undergo significant metabolic reorganization during disease progression that is tailored to their energy demands and fluctuating environmental conditions. Oxidative stress plays an essential role as a trigger under such conditions. These metabolic changes are the consequence of the interaction between tumor cells and stromal myofibroblasts. The metabolic changes in tumor cells include protein anabolism and the synthesis of cell membranes and nucleic acids, which all facilitate cell proliferation. They are linked to catabolism and autophagy in stromal myofibroblasts, causing the release of nutrients for the cells of the tumor parenchyma. Metabolic changes lead to an interstitium deficient in nutrients, such as glucose and amino acids, and acidification by lactic acid. Together with hypoxia, they produce functional changes in other cells of the tumor stroma, such as many immune subpopulations and endothelial cells, which lead to tumor growth. Thus, immune cells favor tissue growth through changes in immunosuppression. This review considers some of the metabolic changes described in breast cancer.

60 APPLIED LIFE SCIENCES↗

Intermediate Molecular Phenotypes to Identify Genetic Markers of Anthracycline-Induced Cardiotoxicity Risk

Cardiotoxicity due to anthracyclines (CDA) affects cancer patients, but we cannot predict who may suffer from this complication. CDA is a complex trait with a polygenic component that is mainly unidentified. We propose that levels of intermediate molecular phenotypes (IMPs) in the myocardium associated with histopathological damage could explain CDA susceptibility, so variants of genes encoding these IMPs could identify patients susceptible to this complication. Thus, a genetically heterogeneous cohort of mice (n = 165) generated by backcrossing were treated with doxorubicin and docetaxel. We quantified heart fibrosis using an Ariol slide scanner and intramyocardial levels of IMPs using multiplex bead arrays and QPCR. We identified quantitative trait loci linked to IMPs (ipQTLs) and cdaQTLs via linkage analysis. In three cancer patient cohorts, CDA was quantified using echocardiography or Cardiac Magnetic Resonance. CDA behaves as a complex trait in the mouse cohort. IMP levels in the myocardium were associated with CDA. ipQTLs integrated into genetic models with cdaQTLs account for more CDA phenotypic variation than that explained by cda-QTLs alone. Allelic forms of genes encoding IMPs associated with CDA in mice, including AKT1, MAPK14, MAPK8, STAT3, CAS3, and TP53, are genetic determinants of CDA in patients. Two genetic risk scores for pediatric patients (n = 71) and women with breast cancer (n = 420) were generated using machine-learning Least Absolute Shrinkage and Selection Operator (LASSO) regression. Thus, IMPs associated with heart damage identify genetic markers of CDA risk, thereby allowing more personalized patient management.

60 APPLIED LIFE SCIENCES↗

Scalable and Quench-Free Processing of Metal Halide Perovskites in Ambient Conditions

With the rise of global warming and the growing energy crisis, scientists have pivoted from typical resources to look for new materials and technologies. Perovskite materials hold the potential for making high-efficiency, low-cost solar cells through solution processing of Earth-abundant materials; however, scalability, stability, and durability remain key challenges. In order to transition from small-scale processing in inert environments to higher throughput processing in ambient conditions, the fundamentals of perovskite crystallization must be understood. Classical nucleation theory, the LaMer relation, and nonclassical crystallization considerations are discussed to provide a mechanism by which a gellan gum (GG) additive—a nontoxic polymeric saccharide—has enabled researchers to produce quality halide perovskite thin-film blade coated in ambient conditions without a quench step. Furthermore, we report on the improved stability and durability properties inherent to these films, which feature improved morphologies and optoelectronic properties compared to films spin-coated in a glovebox with antisolvent. We tune the amount of GG in the perovskite precursor and study the interplay between GG concentration and processability, morphological control, and increased stability under humidity, heat, and mechanical testing. The simplicity of this approach and insensitivity to environmental conditions enable a wide process window for the production of low-defect, mechanically robust, and operationally stable perovskites with fracture energies among the highest obtained for perovskites.

14 SOLAR ENERGY↗

Evolutionary Origins of Metabolic Reprogramming in Cancer

Metabolic changes that facilitate tumor growth are one of the hallmarks of cancer. These changes are not specific to tumors but also take place during the physiological growth of tissues. Indeed, the cellular and tissue mechanisms present in the tumor have their physiological counterpart in the repair of tissue lesions and wound healing. These molecular mechanisms have been acquired during metazoan evolution, first to eliminate the infection of the tissue injury, then to enter an effective regenerative phase. Cancer itself could be considered a phenomenon of antagonistic pleiotropy of the genes involved in effective tissue repair. Cancer and tissue repair are complex traits that share many intermediate phenotypes at the molecular, cellular, and tissue levels, and all of these are integrated within a Systems Biology structure. Complex traits are influenced by a multitude of common genes, each with a weak effect. This polygenic component of complex traits is mainly unknown and so makes up part of the missing heritability. Here, we try to integrate these different perspectives from the point of view of the metabolic changes observed in cancer.

60 APPLIED LIFE SCIENCES↗

Exploration of the Electronic and Catalytic Properties of [Co 5 MS 8 (PEt 3 ) 5 ] 1+ Nanoclusters: A Computational Study

Recent studies have demonstrated the relative stability of undercoordinated hexanuclear cobalt sulfide nanoclusters (NCs) with different charge states. Considering that these small metal NCs have atomically precise structures and high reactivity due to the open shell of the transition metals, and provide selectivity toward ligand loss, they are a vital model for catalysis. In this paper, the electronic structures of these NCs are investigated. These NCs are then used as the reference state to analyze the catalytic properties with respect to hydrogen evolution reaction (HER) and CO 2 reduction (CO 2 R). Further, to understand the effect of heteroatom incorporation, the geometry and reactivity of ten different metal dopants are analyzed. This work shows that the type of metal incorporation greatly affects the electronic structure and formation energies for ligand binding and catalysis. Particularly, the d-orbital occupancy in the cobalt atoms remains largely unchanged, while the heteroatom greatly influences the reactivity of the undercoordinated NCs. Most notably, this work highlights that transition metals in [Co 5 MS 8 (PEt 3 ) 5 ] 1+ NCs would competitively prefer electrochemical adsorption of H over COOH, while the main group metals prefer COOH adsorption.

catalysis↗

A Search for FeH in Hot-Jupiter Atmospheres with High-dispersion Spectroscopy

Most of the molecules detected thus far in exoplanet atmospheres, such as water and CO, are present for a large range of pressures and temperatures. In contrast, metal hydrides exist in much more specific regimes of parameter space, and so can be used as probes of atmospheric conditions. Iron hydride (FeH) is a dominant source of opacity in low-mass stars and brown dwarfs, and evidence for its existence in exoplanets has recently been observed at low resolution. We performed a systematic search of archival CARMENES near-infrared data for signatures of FeH during transits of 12 exoplanets. These planets span a large range of equilibrium temperatures (600 ≲ T eq ≲ 4000 K) and surface gravities (2.5 ≲ logg ≲ 3.5). We did not find a statistically significant FeH signal in any of the atmospheres, but obtained potential low-confidence signals (signal-to-noise ratio ~ 3) in two planets, WASP-33b and MASCARA-2b. Previous modeling of exoplanet atmospheres indicate that the highest volume mixing ratios (VMRs) of 10 -7 to 10 -9 are expected for temperatures between 1800 and 3000 K and log g≳3. The two planets for which we find low-confidence signals are in the regime where strong FeH absorption is expected. We performed injection and recovery tests for each planet and determined that FeH would be detected in every planet for VMRs ≫10 -6 , and could be detected in some planets for VMRs as low as 10 -9.5 . Additional observations are necessary to conclusively detect FeH and assess its role in the temperature structures of hot-Jupiter atmospheres.

79 ASTRONOMY AND ASTROPHYSICS↗

NASA’s Pandora SmallSat Mission: Simulated Modeling and Retrieval of Near-infrared Exoplanet Transmission Spectra

Pandora is a SmallSat mission dedicated to understanding exoplanets and their host stars by disentangling the impact of stellar heterogeneity on exoplanet transmission spectra. Selected as a NASA Astrophysics Pioneers mission in 2021, Pandora will provide simultaneous long-term visible photometric monitoring (0.4–0.7 μm) and low-resolution near-infrared (NIR) spectroscopy (0.9–1.6 μm) of transiting systems for the purposes of monitoring host star variability and characterizing exoplanetary atmospheres. Pandora’s year-long prime mission from 2026 to 2027 coincides with the middle of a decade defined by targeted efforts for atmospheric characterization of exoplanets, offering a key opportunity to leverage this new resource to maximize science with JWST and other observatories. Here we investigate Pandora’s anticipated performance for the general exoplanet population accessible to transit spectroscopy, from hot Jupiters to temperate sub-Neptunes. By modeling the atmospheres of five test cases broadly consistent with the bulk properties of HD 209458b, HD 189733b, WASP-80 b, HAT-P-18 b, and K2-18 b, we find that Pandora may provide abundance constraints as precise as ∼1.0 dex for main atmospheric absorbers such as H 2 O and CH 4 . Then, we explore the synergies between Pandora and JWST. Our results suggest that targets with JWST data in the NIR can benefit from the addition of Pandora observations and result in more reliable abundance estimates than with JWST data alone. Moreover, Pandora can serve the community by providing precursory observations of targets of interest for JWST atmospheric characterization. We conclude by outlining strategies for the use of Pandora as a standalone observatory and in synergy with JWST.

79 ASTRONOMY AND ASTROPHYSICS↗