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At least 1,009 records · Page 56

Applying Multimodal Mass Spectrometry to Image Tumors Undergoing Ferroptosis Following In Vivo Treatment with a Ferroptosis Inducer

Epithelial ovarian cancer (EOC) is the most common form of ovarian cancer. The poor prognosis generally associated with this disease has led to the search for improved therapies such as ferroptosis-inducing agents. Ferroptosis is a form of regulated cell death that is dependent on iron and is characterized by lipid peroxidation. Precise mapping of lipids and iron within tumors exposed to ferroptosis-inducing agents may provide insight into processes of ferroptosis in vivo and ultimately assist in the optimal deployment of ferroptosis inducers in cancer therapy. In this work, we present a method for combining matrix-assisted laser desorption/ionization (MALDI) mass spectrometry imaging (MSI) with secondary ion mass spectrometry (SIMS) to analyze changes in spatial lipidomics and metal composition, respectively, in ovarian tumors following exposure to a ferroptosis inducer. Tumors were obtained by injecting human ovarian cancer tumor-initiating cells into mice, followed by treatment with the ferroptosis inducer erastin. SIMS imaging detected iron accumulation in the tumor tissue, and sequential MALDI-MS imaging of the same tissue section displayed two chemically distinct regions of lipids. Additionally, one region was associated with the iron-rich area detected with SIMS, and the other region encompassed the remainder of the tissue section. Bulk lipidomics confirmed the lipid assignments putatively assigned from the MALDI-MS data. Overall, we demonstrate the ability of multimodal MSI to identify the spatial locations of iron and lipids in the same tissue section and associate these regions with clinical pathology.

60 APPLIED LIFE SCIENCES↗

Application of pan-sharpening algorithm for correlative multimodal imaging using AFM-IR

The coupling of atomic force microscopy with infrared spectroscopy (AFM-IR) offers the unique capability to characterize the local chemical and physical makeup of a broad variety of materials with nanoscale resolution. However, in order to fully utilize the measurement capability of AFM-IR, a three-dimensional dataset (2D map with a spectroscopic dimension) needs to be acquired, which is prohibitively time-consuming at the same spatial resolution of a regular AFM scan. In this paper, we provide a new approach to process spectral AFM-IR data based on a multicomponent pan-sharpening algorithm. This approach requires only a low spatial resolution spectral and a limited number of high spatial resolution single wavenumber chemical maps to generate a high spatial resolution hyperspectral image, greatly reducing data acquisition time. As a result, we are able to generate high-resolution maps of component distribution, produce chemical maps at any wavenumber available in the spectral range, and perform correlative analysis of the physical and chemical properties of the samples. We highlight our approach via imaging of plant cell walls as a model system and showcase the interplay between mechanical stiffness of the sample and its chemical composition. We believe our pan-sharpening approach can be more generally applied to different material classes to enable deeper understanding of that structure-property relationship at the nanoscale.

36 MATERIALS SCIENCE↗

In situ plant materials hyperspectral imaging by multimodal scattering near-field optical microscopy

Plant cells are elaborate three-dimensional polymer nano-constructs with complex chemistry. The bulk response of plants to light, in the far-field, is ultimately encoded by optical scattering from these nano-constructs. Their chemical and physical properties may be acquired through their interaction with a modulated nano-tip using scattering scanning near-field optical microscopy. Here, using this technique, we present 20 nm spatial resolution mechanical, spectral and optical mappings of plant cell walls. We first address the problem of plant polymers tracking through pretreatment and processing. Specifically, cellulose and lignin footprints are traced within a set of delignified specimen, establishing the factors hindering complete removal of lignin, an important industrial polymer. Furthermore, we determine the frequency dependent dielectric function ${\epsilon }(\omega)={(n+ik)}^{2}$ of plant material in the range 28 ≤ ω ≤ 58 THz, and show how the environmental chemical variation is imprinted in the nanoscale variability of n and k . This nanometrology is a promise for further progress in the development of plant-based (meta-)materials.

36 MATERIALS SCIENCE↗

Domain configuration changes under electric field-induced antiferroelectric-ferroelectric phase transitions in NaNbO{sub 3}-based ceramics

We recently developed a feasible crystal chemistry strategy to stabilize the antiferroelectricity in NaNbO{sub 3} through a chemical substitution to decrease the tolerance factor and increase the average electronegativity of the system [Shimizu et al., Dalton Trans. 44, 10763 (2015) and Guo et al., J. Appl. Phys. 117, 214103 (2015)]. Two novel lead-free antiferroelectric (AFE) solid solutions, (1-x)NaNbO{sub 3}-xCaZrO{sub 3} and (1-x)NaNbO{sub 3}-xSrZrO{sub 3}, have been found to exhibit the double polarization hysteresis typical of a reversible AFE ↔ ferroelectric (FE) phase transition. In this study, as demonstrated by (1-x)NaNbO{sub 3}-xCaZrO{sub 3} system, the influence of chemical modification and electrical poling on the AFE/FE phase stability was investigated, primarily focusing on the microstructural and crystallographic evolutions. Together with the macroscopic polarization hysteresis measurements, a well-demonstrated structure-property relationship was presented. It was found that the CaZrO{sub 3} substitution into NaNbO{sub 3} can effectively destabilize the FE Q phase and correspondingly lead to a spontaneous reverting to AFE P phase. In contrast to the reversible AFE ↔ FE phase transition, the domain morphology evolution exhibits irreversible nature with a growing process of the orientational domains after applying electric field. Moreover, a multiple-zone axes electron diffraction map of P and Q phases has been summarized and is believed to be an efficient diagram to determine the AFE/FE nature of the NaNbO{sub 3}-based systems.

36 MATERIALS SCIENCE↗

Exploration of lattice Hamiltonians for functional and structural discovery via Gaussian process-based exploration–exploitation

Statistical physics models ranging from simple lattice to complex quantum Hamiltonians are one of the mainstays of modern physics that have allowed both decades of scientific discovery and provided a universal framework to understand a broad range of phenomena from alloying to frustrated and phase separated materials to quantum systems. Traditionally, exploration of the phase diagrams corresponding to multidimensional parameter spaces of Hamiltonians was performed using a combination of basic physical principles, analytical approximations, and extensive numerical modeling. However, exploration of complex multidimensional parameter spaces is subject to the classic dimensionality problem, and the behaviors of interest concentrated on low dimensional manifolds remain undiscovered. Here, we demonstrate that a combination of exploration and exploration–exploitation with Gaussian process modeling and Bayesian optimization allows effective exploration of the parameter space for lattice Hamiltonians and effectively maps the regions at which specific macroscopic functionalities or local structures are maximized. We argue that this approach is general and can be further extended well beyond the lattice Hamiltonians to effectively explore the parameter space of more complex off-lattice and dynamic models.

42 ENGINEERING↗

Structure analysis of simulated molecular clouds with the Δ-variance

Here, we employ the Δ-variance analysis and study the turbulent gas dynamics of simulated molecular clouds (MCs). Our models account for a simplified treatment of time-dependent chemistry and the non-isothermal nature of the gas. We investigate simulations using three different initial mean number densities of n 0 = 30, 100 and 300 cm -3 that span the range of values typical for MCs in the solar neighbourhood. Furthermore, we model the CO line emission in a post-processing step using a radiative transfer code. We evaluate Δ-variance spectra for centroid velocity (CV) maps as well as for integrated intensity and column density maps for various chemical components: the total, H 2 and 12 CO number density and the integrated intensity of both the 12 CO and 13 CO (J = 1 → 0) lines. The spectral slopes of the Δ-variance computed on the CV maps for the total and H 2 number density are significantly steeper compared to the different CO tracers. We find slopes for the linewidth–size relation ranging from 0.4 to 0.7 for the total and H 2 density models, while the slopes for the various CO tracers range from 0.2 to 0.4 and underestimate the values for the total and H 2 density by a factor of 1.5–3.0. We demonstrate that optical depth effects can significantly alter the Δ-variance spectra. Furthermore, we report a critical density threshold of 100 cm -3 at which the Δ-variance slopes of the various CO tracers change sign. We thus conclude that carbon monoxide traces the total cloud structure well only if the average cloud density lies above this limit.

79 ASTRONOMY AND ASTROPHYSICS↗

Dynamics of resonant low-energy electron attachment to ethanol-producing hydroxide anions

Here, the dynamics of dissociative electron attachment to ethanol is experimentally investigated at the Feshbach resonance formed with incident electron energies near 9.5 eV. Highly differential laboratory-frame momentum distributions of OH – fragments are measured for a series of energies spanning the resonance width, using the velocity-map-imaging technique. The OH – kinetic-energy distribution indicates that the C-O breaking dissociation process could either be a three-body dissociation or a two-body dissociation with significant rovibrational excited fragments. The small, but significant, anisotropy in the OH – angular distribution provides signatures of the molecular symmetry of the associated resonant state under the axial recoil approximation, which assumes the dissociation is much faster than any rotation of the dissociation axis. Within these assumptions, the 9.5-eV Feshbach resonance can be assigned to the electronic transition from the ($10a'$) orbital with its ground-state C s symmetry to the empty ($4a''$) level, involving the simultaneous electron attachment. This dynamics could be a model for C-O dissociation in larger alcohols and ethers.

74 ATOMIC AND MOLECULAR PHYSICS↗

Design and Implementation of Distributed Ultra-High Temperature Sensing System With a Single Crystal Fiber

Modern high-temperature processes, such as fossil energy production, nuclear reactors, and chemical reactors lack robust, distributed sensing systems to map temperatures in these high-value harsh-environment systems. Regular silica-fiber-based distributed temperature sensing systems usually only operate at temperatures below about 800 °C. In this paper, we present the design, implementation, and testing of a distributed ultra-high temperature sensing system using Raman scattering intensity, which operates from room temperature to above 1400 °C. Consideration is given to the impacts of thermal radiation, fluorescence, and the multimode nature of unclad single-crystal fiber to optimize the system. Results from picosecond and sub-nanosecond lasers were compared. Measurements were taken with a ~2 m sapphire optical fiber, which represents the longest commercially available length. Here, a spatial resolution of 12.4 cm and position standard deviation of 0.28 mm were achieved up to the maximum testing temperature of 1400 °C, which is a new record for distributed temperature sensing systems.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Final Report on Small Particle Speciation for Forensics Analysis by Soft X-ray Scanning Transmission X-ray Microscopy

Materials of interest for nuclear forensic science are often highly heterogeneous, containing complex mixtures of actinide compounds in a wide variety of matrices. Scanning transmission X-ray microscopy (STXM) is ideally suited to study such materials, as it can be used to chemically image specimens by acquiring X-ray absorption near-edge spectroscopy (XANES) data with 25 nm spatial resolution. In particular, STXM in the soft X-ray synchrotron radiation regime (approximately 120 – 2000 eV) can collect spectroscopic information from the actinides and light elements in a single experiment. Thus, STXM combines the chemical sensitivity of X-ray absorption spectroscopy with high spatial resolution in a single non-destructive characterization method. This report describes the application of STXM to a broad range of nuclear materials. Where possible, the spectroscopic images obtained by STXM are compared with information derived from other analytical methods, and used to make inferences about the process history of each material. STXM measurements can yield information including the morphology of a sample, “elemental maps” showing the spatial distribution of major chemical constituents, and XANES spectra from localized regions of a sample, which may show spatial variations in chemical composition.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

National Opacity Program - Tri-Lab Assessment of Measurements and Models (Milestone 7720)

Opacity-on-NIF has obtained opacity data under conditions similar to those achieved by the entirely different Opacity-on-Z platform. From low- and high-Z elements at different anchor points, rigorously compare the opacity data between the laboratories and to multiple opacity theory models. Compare and assess the data acquisition and processing methods for obtaining opacities and for measuring/inferring sample conditions. Explain, or develop hypotheses for, any discrepancies. Map progress to the National Opacity Strategy and define future directions.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Milestone 7720: National Opacity Program - Tri-Lab Assessment of Measurements and Models

Opacity-on-NIF has obtained opacity data under conditions similar to those achieved by the entirely different Opacity-on-Z platform. From low- and high-Z elements at different anchor points, rigorously compare the opacity data between the laboratories and to multiple opacity theory models. Compare and assess the data acquisition and processing methods for obtaining opacities and for measuring/inferring sample conditions. Explain, or develop hypotheses for, any discrepancies. Map progress to the National Opacity Strategy and define future directions.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

A Fusion of Geothermal and InSAR Data with Machine Learning for Enhanced Deformation Forecasting at the Geysers

The Geysers geothermal field in California is experiencing land subsidence due to the seismic and geothermal activities taking place. This poses a risk not only to the underlying infrastructure but also to the groundwater level which would reduce the water availability for the local community. Because of this, it is crucial to monitor and assess the surface deformation occurring and adjust geothermal operations accordingly. In this study, we examine the correlation between the geothermal injection and production rates as well as the seismic activity in the area, and we show the high correlation between the injection rate and the number of earthquakes. This motivates the use of this data in a machine learning model that would predict future deformation maps. First, we build a model that uses interferometric synthetic aperture radar (InSAR) images that have been processed and turned into a deformation time series using LiCSBAS, an open-source InSAR time series package, and evaluate the performance against a linear baseline model. The model includes both convolutional neural network (CNN) layers as well as long short-term memory (LSTM) layers and is able to improve upon the baseline model based on a mean squared error metric. Then, after getting preprocessed, we incorporate the geothermal data by adding them as additional inputs to the model. This new model was able to outperform both the baseline and the previous version of the model that uses only InSAR data, motivating the use of machine learning models as well as geothermal data in assessing and predicting future deformation at The Geysers as part of hazard mitigation models which would then be used as fundamental tools for informed decision making when it comes to adjusting geothermal operations.

Yazbeck, Joe (ORCID:0000000302235260)↗

R Coronae Borealis Star Evolution: Simulating 3D Merger Events to 1D Stellar Evolution Including Large-scale Nucleosynthesis

R Coronae Borealis (RCB) stars are rare hydrogen-deficient carbon-rich variable supergiants thought to be the result of dynamically unstable white dwarf mergers. In this article, we attempt to model RCB stars through all the relevant timescales by simulating a merger event in Octo-tiger, a 3D adaptive mesh refinement (AMR) hydrodynamics code, and mapping the post-merger object into MESA, a 1D stellar evolution code. We then post-process the nucleosynthesis on a much larger nuclear reaction network to study the enhancement of s-process elements. We present models that match observations or previous studies in most surface abundances, isotopic ratios, early evolution, and lifetimes. We also observe similar mixing behavior to previous modeling attempts that result in the partial He-burning products visible on the surface in observations. However, we do note that our subsolar models lack any enhancement in s-process elements, which we attribute to a lack of hydrogen in the envelope. We also find that the 16 O/ 18 O isotopic ratio is very sensitive to initial hydrogen abundance and increases outside of the acceptable range with a hydrogen mass fraction greater than 10 -4 .

79 ASTRONOMY AND ASTROPHYSICS↗

Future climate emulations using quantile regressions on large ensembles

The study of climate change and its impacts depends on generating projections of future temperature and other climate variables. For detailed studies, these projections usually require some combination of numerical simulation and observations, given that simulations of even the current climate do not perfectly reproduce local conditions. We present a methodology for generating future climate projections that takes advantage of the emergence of climate model ensembles, whose large amounts of data allow for detailed modeling of the probability distribution of temperature or other climate variables. The procedure gives us estimated changes in model distributions that are then applied to observations to yield projections that preserve the spatiotemporal dependence in the observations. We use quantile regression to estimate a discrete set of quantiles of daily temperature as a function of seasonality and long-term change, with smooth spline functions of season, long-term trends, and their interactions used as basis functions for the quantile regression. A particular innovation is that more extreme quantiles are modeled as exceedances above less extreme quantiles in a nested fashion, so that the complexity of the model for exceedances decreases the further out into the tail of the distribution one goes. We apply this method to two large ensembles of model runs using the same forcing scenario, both based on versions of the Community Earth System Model (CESM), run at different resolutions. The approach generates observation-based future simulations with no processing or modeling of the observed climate needed other than a simple linear rescaling. The resulting quantile maps illuminate substantial differences between the climate model ensembles, including differences in warming in the Pacific Northwest that are particularly large in the lower quantiles during winter. We show how the availability of two ensembles allows the efficacy of the method to be tested with a “perfect model” approach, in which we estimate transformations using the lower-resolution ensemble and then apply the estimated transformations to single runs from the high-resolution ensemble. Finally, we describe and implement a simple method for adjusting a transformation estimated from a large ensemble of one climate model using only a single run of a second, but hopefully more realistic, climate model.

54 ENVIRONMENTAL SCIENCES↗

THE PHYSICAL ENVIRONMENT AROUND IRAS 17599–2148: INFRARED DARK CLOUD AND BIPOLAR NEBULA

We present a multiscale and multiwavelength study to investigate the star formation process around IRAS 17599–2148, which is part of an elongated filamentary structure (EFS) (extension ∼21 pc) seen in the Herschel maps. Using the Herschel data analysis, at least six massive clumps (M {sub clump} ∼ 777–7024 M {sub ⊙}) are found in the EFS with a range of temperature and column density of ∼16–39 K and ∼(0.6–11) × 10{sup 22} cm{sup −2} (A {sub V} ∼ 7–117 mag), respectively. The EFS hosts cold gas regions (i.e., infrared dark cloud) without any radio detection and a bipolar nebula (BN) linked with the H ii region IRAS 17599–2148, tracing two distinct environments inferred through the temperature distribution and ionized emission. Based on virial analysis and higher values of self-gravitating pressure, the clumps are found unstable against gravitational collapse. We find 474 young stellar objects (YSOs) in the selected region, and ∼72% of these YSOs are found in the clusters distributed mainly toward the clumps in the EFS. These YSOs might have spontaneously formed due to processes not related to the expanding H ii region. At the edges of BN, four additional clumps are also associated with YSO clusters, which appear to be influenced by the expanding H ii region. The most massive clump in the EFS contains two compact radio sources traced in the Giant Metre-wave Radio Telescope 1.28 GHz map and a massive protostar candidate, IRS 1, prior to an ultracompact H ii phase. Using the Very Large Telescope/NACO near-infrared images, IRS 1 is resolved with a jet-like feature within a 4200 au scale.

79 ASTRONOMY AND ASTROPHYSICS↗

Proof of principle study: synchrotron X-ray fluorescence microscopy for identification of previously radioactive microparticles and elemental mapping of FFPE tissues

Biobanks containing formalin-fixed, paraffin-embedded (FFPE) tissues from animals and human atomic-bomb survivors exposed to radioactive particulates remain a vital resource for understanding the molecular effects of radiation exposure. These samples are often decades old and prepared using harsh fixation processes which limit sample imaging options. Optical imaging of hematoxylin and eosin (H&E) stained tissues may be the only feasible processing option, however, H&E images provide no information about radioactive microparticles or radioactive history. Synchrotron X-ray fluorescence microscopy (XFM) is a robust, non-destructive, semi-quantitative technique for elemental mapping and identifying candidate chemical element biomarkers in FFPE tissues. Still, XFM has never been used to uncover distribution of formerly radioactive micro-particulates in FFPE canine specimens collected more than 30 years ago. In this work, we demonstrate the first use of low-, medium-, and high-resolution XFM to generate 2D elemental maps of ~ 35-year-old, canine FFPE lung and lymph node specimens stored in the Northwestern University Radiobiology Archive documenting distribution of formerly radioactive micro-particulates. Additionally, we use XFM to identify individual microparticles and detect daughter products of radioactive decay. The results of this proof-of-principle study support the use of XFM to map chemical element composition in historic FFPE specimens and conduct radioactive micro-particulate forensics.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

Global Trends of ASME "N-Stamp" Certifications for Nuclear Component Vendors

Historically, nuclear component manufacturing vendors, from small businesses through large conglomerates, have felt compelled to obtain an American Society for Mechanical Engineers (ASME) Nuclear Certification, known colloquially as an "N-stamp", to assure supply chain quality standards that will be acceptable to regulators and safety concerns. Since the N-stamp quality standard is a U.S.-origin code, combined with the apparent decline in the U.S. nuclear industry alongside the growth of the Asian nuclear industry, there is the question of whether the rest of the world, including new entrants to the nuclear industry, also regard N-stamp as a needed certification. This study addresses this question through analysis of the entire N-stamp database of holders, and former holders, of N-stamp certificates of all types and for all regions worldwide from 1989-2020 (the dates available in the database). From this 30 years of data, we find that actually U.S.-based vendors still consistently obtain the largest number of N-stamps worldwide over all time periods, but also find that the countries participating in the N-stamp certification process has broadly expanded beyond just North America, Japan, S. Korea and Western Europe (the primary N-stamp recipients before the mid-2000's). We produced global heats maps and bar charts to illustrate our findings, as well as further investigation into why the data shows changes over time and region. We note that nuclear entities involved with Soviet-type reactors do not participate in the N-stamp process, but instead pursue the Russian version PNAE, which is substantially similar to the ASME code. We conclude that at least from the N-stamp database, the United States nuclear component manufacturing industry is alive and well, although there have been some consolidations, and that the ASME N-stamp appears to still be a valued certificate worldwide, including in China which now ranks second only to the United States in obtaining N-stamp certificates in recent years. We further note that the vendors of new reactor types, in particular High Temperature Gas-Cooled Reactors (HTGRs) and Small Modular Reactors (SMRs), are actively engaged with ASME (and other U.S.-based nuclear standards bodies such as the American Nuclear Society and Nuclear Energy Institute) to coordinate updates to the ASME N-Stamp criteria to ensure applicability of the code for these new designs. Implications of these findings include the following: The global use of the U.S.-origin N-stamp certification supports the view that, despite the decline of the U.S. nuclear industry, the United States remains an esteemed global leader in the area of nuclear safety. As the U.S. Government works to revitalize the U.S. nuclear industry, especially in the area of exports, it may be beneficial to leverage the global standing of the N-stamp certification. The findings indicate that the N-stamp database would be a useful tool for the U.S. Government to use to track the growth of the civil nuclear industry in foreign countries, under certain circumstances. The Excel-format N-stamp database produced as part of this study may be a useful tool for this purpose. N-stamp data may be a useful tool for foreign governments to use to identify nuclear manufacturers within their own country, especially to identify "targets" for outreach on nuclear export control compliance. The U.S. Government could carry this message to foreign partners during bilateral engagements or as part of Nuclear Suppliers Group (NSG) discussions on industry outreach.

42 ENGINEERING↗

X-ray chemical imaging for assessing redox microsites within soils and sediments

Redox reactions underlie several biogeochemical processes and are typically spatiotemporally heterogeneous in soils and sediments. However, redox heterogeneity has yet to be incorporated into mainstream conceptualizations and modeling of soil biogeochemistry. Anoxic microsites, a defining feature of soil redox heterogeneity, are non-majority oxygen depleted zones in otherwise oxic environments. Neglecting to account for anoxic microsites can generate major uncertainties in quantitative assessments of greenhouse gas emissions, C sequestration, as well as nutrient and contaminant cycling at the ecosystem to global scales. However, only a few studies have observed/characterized anoxic microsites in undisturbed soils, primarily, because soil is opaque and microsites require µm-cm scale resolution over cm-m scales. Consequently, our current understanding of microsite characteristics does not support model parameterization. To resolve this knowledge gap, we demonstrate through this proof-of-concept study that X-ray fluorescence (XRF) 2D mapping can reliably detect, quantify, and provide basic redox characterization of anoxic microsites using solid phase “forensic” evidence. First, we tested and developed a systematic data processing approach to eliminate false positive redox microsites, i.e., artefacts, detected from synchrotron-based multiple-energy XRF 2D mapping of Fe (as a proxy of redox-sensitive elements) in Fe-“rich” sediment cores with artificially injected microsites. Then, spatial distribution of Fe II and Fe III species from full, natural soil core slices (over cm-m lengths/widths) were mapped at 1–100 µm resolution. These investigations revealed direct evidence of anoxic microsites in predominantly oxic soils such as from an oak savanna and toeslope soil of a mountainous watershed, where anaerobicity would typically not be expected. We also revealed preferential spatial distribution of redox microsites inside aggregates from oak savanna soils. We anticipate that this approach will advance our understanding of soil biogeochemistry and help resolve “anomalous” occurrences of reduced products in nominally oxic soils.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗