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At least 1,459 records · Page 81

Observation of dynamic atom-atom correlation in liquid helium in real space

Liquid 4 He becomes superfluid and flows without resistance below temperature 2.17 K. Superfluidity has been a subject of intense studies and notable advances were made in elucidating the phenomenon by experiment and theory. Nevertheless, details of the microscopic state, including dynamic atom–atom correlations in the superfluid state, are not fully understood. Here using a technique of neutron dynamic pair-density function (DPDF) analysis we show that 4 He atoms in the Bose–Einstein condensate have environment significantly different from uncondensed atoms, with the interatomic distance larger than the average by about 10%, whereas the average structure changes little through the superfluid transition. DPDF peak not seen in the snap-shot pair-density function is found at 2.3 Å, and is interpreted in terms of atomic tunnelling. The real space picture of dynamic atom–atom correlations presented here reveal characteristics of atomic dynamics not recognized so far, compelling yet another look at the phenomenon.

74 ATOMIC AND MOLECULAR PHYSICS↗

Review of Current Software for Analyzing Total X-ray Scattering Data from Liquids

The popularity of the pair distribution function (PDF) analysis of X-ray total scattering data has steadily grown as access to ex situ synchrotron data has expanded. Due to the broadening of the PDF user community, there is a growing demand for software that can be used to extract PDFs and is accessible to non-expert users. While user-friendly options have been developed over the past decade for fast, streamlined data analysis, care must be taken in both processing the data and understanding any limitations, especially in the case of liquids. In this review, the same scattering data are analyzed using different total X-ray scattering software, in order to compare the accuracy of the extracted structure factors and associated pair distribution functions. The goal is to assess the best practices for extracting the most accurate liquid data for each software package. The importance of absolute normalization and the application of the most appropriate corrections are emphasized via quantitative comparisons between liquid sulfur and water. Additionally, an awareness of the competing conventions used to define the PDF in crystallography and liquids/glasses is crucial for both the downstream analyses of the data and a comparison with the previous results in the literature.

Gallington, Leighanne C. (ORCID:0000000203837522)↗

A Study of Tube Extrusion Process

An upper bound solution for tube extrusion is developed in this paper. The dead zone is assumed to have the sine profile and a kinematically admissible velocity field is proposed. From the proposed velocity field, the upper bound solution on relative punch pressure and extrusion load is determined with respect to chosen process parameters. The results are compared with theoretical and experimental results from a reference to illustrate the validity of the proposed velocity field. This indicates that the analysis presented here renders better upper bound solution than that given by Ebrahimi et al.. [An upper-bound analysis of the tube extrusion process (2008) J. Mater. Process. Technol. 99:214-220].

42 ENGINEERING↗

Application of Diagnostic Analysis Tools to the Ares I Thrust Vector Control System

The NASA Ares I Crew Launch Vehicle is being designed to support missions to the International Space Station (ISS), to the Moon, and beyond. The Ares I is undergoing design and development utilizing commercial-off-the-shelf tools and hardware when applicable, along with cutting edge launch technologies and state-of-the-art design and development. In support of the vehicle s design and development, the Ares Functional Fault Analysis group was tasked to develop an Ares Vehicle Diagnostic Model (AVDM) and to demonstrate the capability of that model to support failure-related analyses and design integration. One important component of the AVDM is the Upper Stage (US) Thrust Vector Control (TVC) diagnostic model-a representation of the failure space of the US TVC subsystem. This paper first presents an overview of the AVDM, its development approach, and the software used to implement the model and conduct diagnostic analysis. It then uses the US TVC diagnostic model to illustrate details of the development, implementation, analysis, and verification processes. Finally, the paper describes how the AVDM model can impact both design and ground operations, and how some of these impacts are being realized during discussions of US TVC diagnostic analyses with US TVC designers.

Maul, William A.↗

Two-Dimensional CsAg 5 Te 3– x S x Semiconductors: Multi-anion Chalcogenides with Dynamic Disorder and Ultralow Thermal Conductivity

Metal chalcogenides underpin a wide variety of energyrelated applications and are ideal systems for probing lattice dynamics and fundamental transport phenomena. Here we describe the synthesis and transport properties of CsAg 5 TeS 2 and its solid solution CsAg 5 Te 3-x S x (x = 1-2), new semiconductors with tunable band gaps ranging from 0.17 to 0.30 eV. CsAg 5 TeS 2 has a fully ordered two-dimensional structure that includes a group of Ag atoms in a heteroleptic tetrahedral coordination geometry (AgTe 2 S 2 ). Single-crystal X-ray diffraction indicates that the compounds crystallize in the tetragonal space group P 4/ mmm , while pair distribution function (PDF) analysis reveals off-centering at the heteroleptic Ag sites, signifying the lower-symmetry I4/ mcm space group. The underlying disorder as a phonon-blocking mechanism that helps facilitate an ultralow lattice thermal conductivity below 0.40 Wm -1 • K -1 at , ~ 300 K , highlighting the importance of local disorder in thermal transport. In conclusion, density functional theory provides additional insight into the electronic and thermal properties of the materials, which are good candidates for p-type thermoelectrics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Full Integration of Lipidomics Data into Multi-OMIC Functional Enrichment

Lipids have numerous roles critical to living systems. Many of these vital functions are tightly linked or regulated by proteins. Even though the function of many lipid-related enzymes is known, direct links between most individual lipid species and the enzymes that metabolize them are severely lacking. This missing connection impedes biological progress. A resource that allows users to quickly identify protein-lipid relationships will advance our understanding of lipid homeostasis and metabolic perturbed systems. Databases are readily available for mapping small molecule metabolites (i.e., polar metabolites) and specific oxidized fatty acid lipids (e.g., arachidonic acid derivatives) to proteins/enzymes known to be directly involved in metabolism of these molecules (e.g. SMPDB, Reactome, HMDB, BioCyc). This enables the integration of metabolite and protein (as well as transcript) data when performing functional enrichment and metabolic modeling allowing researchers to rapidly examine metabolic pathways from multiple omics sources. Currently, linking lipidomics data with proteomics data is conducted using a time-intensive, user defined, manual process. Here we propose creating a tool that will link lipidomics and proteomics data and also conduct functional enrichment analysis and visualization allowing for full statistical integration. Using text-mining approaches, we will extract lipid references from uniprot and create a database linking lipid species to enzymes directly related to their metabolism. We will also extract directional annotation, which will allow even greater specificity when linking data types and will help eliminate false positives from functional associations.

59 BASIC BIOLOGICAL SCIENCES↗

Validation of Procedures for Monitoring Crewmember Immune Function

There is ample evidence to suggest that space flight leads to immune system dysregulation, however the nature of the phenomenon as it equilibrates over longer flights has not been determined. This dysregulation may be a result of microgravity, confinement, physiological stress, radiation, environment or other mission-associated factors. The clinical risk (if any) for exploration-class space flight is unknown, but may include increased incidence of infection, allergy, hypersensitivity, hematological malignancy or altered wound healing. The objective of this Supplemental Medical Objective (SMO) is to determine the status of the immune system, physiological stress and latent viral reactivation (a clinical outcome that can be measured) during both short and long-duration spaceflight. In addition, this study will develop and validate an immune monitoring strategy consistent with operational flight requirements and constraints. Pre-mission, in-flight and post-flight blood and saliva samples will be obtained from participating crewmembers. Assays included peripheral immunophenotype, T cell function, cytokine profiles (RNA, intracellular, secreted), viral-specific immunity, latent viral reactivation (EBV, CMV, VZV), and stress hormone measurements. This study is currently ongoing. To date, 10 short duration and 5 long-duration crewmembers have completed the study. Technically, the study is progressing well. In-flight blood samples are being collected, and returned for analysis, including functional assays that require live cells. For all in-flight samples to date, sample viability has been acceptable. Preliminary data (n = 4/7; long/short duration, respectively) indicate that distribution of most peripheral leukocyte subsets is largely unaltered during flight. Exceptions include elevated T cells, reduced B/NK cells, increased memory T cells and increased central memory CD8+ T cells. General T cell function, early blastogenesis response to mitogenic stimulation, is markedly reduced in-flight. In-vivo cytokine production profiles are altered, with in-flight dysregulation observed in the Th1/Th2/Treg equilibrium. EBV specific T cell levels are increased during flight, whereas their function is reduced. VZV reactivation was observed inflight and several days post flight with highest levels measured later during long-duration flight. The shedding of CMV in the urine was detected of 4/5 long duration and 4/7 short duration crewmembers. Plasma cortisol was not elevated during flight. Further data will be required to validate the initial observations.

Crucian, Brian↗

X-ray and neutron total scattering analysis of Hy·(Bi0.2Ca0.55Sr0.25)(Ag0.25Na0.75)Nb3O10·xH2O perovskite nanosheet booklets with stacking disorder

Ion-exchanged Aurivillius materials form perovskite nanosheet booklets wherein well-defined bi-periodic sheets, with ~11.5 Å thickness, exhibit extensive stacking disorder. The perovskite layer contents were defined initially using combined synchrotron X-ray and neutron Rietveld refinement of the parent Aurivillius structure. The structure of the subsequently ion-exchanged material, which is disordered in its stacking sequence, is analyzed using both pair distribution function (PDF) analysis and recursive method simulations of the scattered intensity. Combined X-ray and neutron PDF refinement of supercell stacking models demonstrates sensitivity of the PDF to both perpendicular and transverse stacking vector components. Further, hierarchical ensembles of stacking models weighted by a standard normal distribution are demonstrated to improve PDF fit over 1–25 Å. Recursive method simulations of the X-ray scattering profile demonstrate agreement between the real space stacking analysis and more conventional reciprocal space methods. The local structure of the perovskite sheet is demonstrated to relax only slightly from the Aurivillius structure after ion exchange.

Metz, Peter↗

Pentachlorophenol exposure causes Warburg-like effects in zebrafish embryos at gastrulation stage

Pentachlorophenol (PCP) is a prevalent pollutant in the environment and has been demonstrated to be a serious toxicant to humans and animals. However, little is known regarding the molecular mechanism underlying its toxic effects on vertebrate early development. To explore the impacts and underlying mechanisms of PCP on early development, zebrafish (Danio rerio) embryos were exposed to PCP at concentrations of 0, 20 and 50 μg/L, and microscopic observation and cDNA microarray analysis were subsequently conducted at gastrulation stage. The morphological observations revealed that PCP caused a developmental delay of zebrafish embryos in a concentration-dependent manner. Transcriptomic data showed that 50 μg/L PCP treatment resulted in significant changes in gene expression level, and the genes involved in energy metabolism and cell behavior were identified based on gene functional enrichment analysis. The energy production of embryos was influenced by PCP via the activation of glycolysis along with the inhibition of oxidative phosphorylation (OXPHOS). The results suggested that PCP acts as an inhibitor of OXPHOS at 8 hpf (hours postfertilization). Consistent with the activated glycolysis, the cell cycle activity of PCP-treated embryos was higher than the controls. These characteristics are similar to the Warburg effect, which occurs in human tumors. The microinjection of exogenous ATP confirmed that an additional energy supply could rescue PCP-treated embryos from the developmental delay due to the energy deficit. Taken together, our results demonstrated that PCP causes a Warburg-like effect on zebrafish embryos during gastrulation, and the affected embryos had the phenotype of developmental delay. - Highlights: • We treat zebrafish embryos with PCP at gastrula stage. • PCP acts as an oxidative phosphorylation inhibitor, not an uncoupler, in gastrulation. • Exogenous ATP injection will rescue the development of effected embryos. • The transcriptome of PCP-treated embryo exhibits a Warburg-like effect in tumor cell.

60 APPLIED LIFE SCIENCES↗

FBI fingerprint identification automation study. AIDS 3 evaluation report. Volume 3: Operational feasibility

An evaluation is presented which is defined as the adequacy of system design with known functional and performance requirements. The proposed Rockwell International AIDS 3 card, document and data flow are presented to summarize the concepts involved and the relationships between functions. The analysis and evaluation includes a study of system capability, processing rates, search requirements and response accuracy as well as a consideration of operational components and hardware integration. Results indicate that the AIDS 3 System concept is operationally feasible if production capacity is slightly enhanced but that operational complexity, hardware integration and a lack of conceptual data pertinent to some of the functions are areas of concern.

Mulhall, B. D. L.↗

Coral and Seawater Metagenomes Reveal Key Microbial Functions to Coral Health and Ecosystem Functioning Shaped at Reef Scale

The coral holobiont is comprised of a highly diverse microbial community that provides key services to corals such as protection against pathogens and nutrient cycling. The coral surface mucus layer (SML) microbiome is very sensitive to external changes, as it constitutes the direct interface between the coral host and the environment. Here, we investigate whether the bacterial taxonomic and functional profiles in the coral SML are shaped by the local reef zone and explore their role in coral health and ecosystem functioning. The analysis was conducted using metagenomes and metagenome-assembled genomes (MAGs) associated with the coral Pseudodiploria strigosa and the water column from two naturally distinct reef environments in Bermuda: inner patch reefs exposed to a fluctuating thermal regime and the more stable outer reefs. The microbial community structure in the coral SML varied according to the local environment, both at taxonomic and functional levels. The coral SML microbiome from inner reefs provides more gene functions that are involved in nutrient cycling (e.g., photosynthesis, phosphorus metabolism, sulfur assimilation) and those that are related to higher levels of microbial activity, competition, and stress response. In contrast, the coral SML microbiome from outer reefs contained genes indicative of a carbohydrate-rich mucus composition found in corals exposed to less stressful temperatures and showed high proportions of microbial gene functions that play a potential role in coral disease, such as degradation of lignin-derived compounds and sulfur oxidation. The fluctuating environment in the inner patch reefs of Bermuda could be driving a more beneficial coral SML microbiome, potentially increasing holobiont resilience to environmental changes and disease.

59 BASIC BIOLOGICAL SCIENCES↗

Control of electronic properties of 2D carbides (MXenes) by manipulating their transition metal layers

In this paper, a transition from metallic to semiconducting-like behavior has been demonstrated in two-dimensional (2D) transition metal carbides by replacing titanium with molybdenum in the outer transition metal (M) layers of M 3 C 2 and M 4 C 3 MXenes. The MXene structure consists of n + 1 layers of near-close packed M layers with C or N occupying the octahedral site between them in an [MX] n M arrangement. Recently, two new families of ordered 2D double transition metal carbides MXenes were discovered, M' 2 M"C 2 and M' 2 M" 2 C 3 – where M' and M" are two different early transition metals, such as Mo, Cr, Ta, Nb, V, and Ti. The M' atoms only occupy the outer layers and the M" atoms fill the middle layers. In other words, M' atomic layers sandwich the middle M"–C layers. Using X-ray atomic pair distribution function (PDF) analysis on Mo 2 TiC 2 and Mo 2 Ti 2 C 3 MXenes, we present the first quantitative analysis of structures of these novel materials and experimentally confirm that Mo atoms are in the outer layers of the [MC] n M structures. The electronic properties of these Mo-containing MXenes are compared with their Ti 3 C 2 counterparts, and are found to be no longer metallic-like conductors; instead the resistance increases mildly with decreasing temperatures. Density functional theory (DFT) calculations suggest that OH terminated Mo–Ti MXenes are semiconductors with narrow band gaps. Measurements of the temperature dependencies of conductivities and magnetoresistances have confirmed that Mo 2 TiC 2 T x exhibits semiconductor-like transport behavior, while Ti 3 C 2 T x is a metal. Finally, this finding opens new avenues for the control of the electronic and optical applications of MXenes and for exploring new applications, in which semiconducting properties are required.

36 MATERIALS SCIENCE↗

An extended structure-function model and its application to the analysis of solar wind intermittency

An extended structure-function model is developed by including the new effect in the p-model of Meneveau and Sreenivasan (1987a), i.e., that the averaged energy cascade rate changes with scale, a situation which has been found to prevail in non-fully-developed turbulence in the inner solar wind. This model is useful for the small-scale fluctuations in the inner heliosphere, where the turbulence is not fully developed and cannot be explained quantitatively by any of the previous intermittency turbulence models. With two model parameters, the intrinsic index of the energy spectrum, alpha and the fragmentation fraction p, the model can fit, for the first time, all the observed scaling exponents of the structure functions, which are calculated for time lags ranging from 81 seconds to 0.7 hours from the Helios solar wind data. From the cases we studied we can establish for p neither a clear radial evolution trend, nor a solar-wind-speed, or stream-structure dependence, or a systematic anisotropy for both the flow velocity and magnetic field component fluctuations. Generally, p has values between 0. 7 and 0.8. However, in some cases in low-speed wind p has somewhat higher values for the magnetic components, especially for the radial component. In high-speed wind, the inferred intrinsic spectral indices (alpha) of the velocity and magnetic field components are about equal, while the experimental spectral indices derived from the observed power spectra differ. The magnetic index is somewhat larger than the index of the velocity spectrum. For magnetic fluctuations in both high- and low-speed winds, the intrinsic exponent alpha has values which are near 1.5, while the observed spectral exponent has much higher values.

Tu, C.-Y.↗

Functional reconstitution of Drosophila melanogaster NMJ glutamate receptors

The Drosophila larval neuromuscular junction (NMJ), at which glutamate acts as the excitatory neurotransmitter, is a widely used model for genetic analysis of synapse function and development. Despite decades of study, the inability to reconstitute NMJ glutamate receptor function using heterologous expression systems has complicated the analysis of receptor function, such that it is difficult to resolve the molecular basis for compound phenotypes observed in mutant flies. In this paper, we find that Drosophila Neto functions as an essential component required for the function of NMJ glutamate receptors, permitting analysis of glutamate receptor responses in Xenopus oocytes. Finally, in combination with a crystallographic analysis of the GluRIIB ligand binding domain, we use this system to characterize the subunit dependence of assembly, channel block, and ligand selectivity for Drosophila NMJ glutamate receptors.

59 BASIC BIOLOGICAL SCIENCES↗

Structure and Dynamics of Polysulfide Clusters in a Nonaqueous Solvent Mixture of 1,3-Dioxolane and 1,2-Dimethoxyethane

Molecular clustering and associated dynamic processes of lithium polysulfide species were unraveled using classical molecular dynamics and ab initio metadynamics calculations. The spectroscopic signatures of polysulfide clusters were analyzed using a multimodal analysis including experimental and computational nuclear magnetic resonance (NMR) and X-ray absorption spectroscopies. Lithium polysulfide solutes (Li 2 S 4 , Li 2 S 6 , and Li 2 S 8 ) and their mixtures in a 1,3-dioxolane and 1,2-dimethoxyethane (DOL/DME) solvent undergo aggregation driven by intramolecular lithium–sulfur (Li–S) interactions, leading to distributions of cluster sizes, which could critically influence the functioning of lithium–sulfur batteries. Representative polysulfide clusters with systematic increases in molecular size were extracted from the classical molecular dynamics trajectories for subsequent structural and spectroscopic property calculations using density functional theory analysis. Structural analysis of these clusters reveals progressively decreasing solvent involvement in Li+ coordination varying from Li 2 S 4 to Li 2 S 8 , with more pronounced variation and changes in DME compared with those in DOL. These observations are reflected in the analysis of the experimental and theoretical 7 Li and 17 O NMR chemical shifts and pulsed field gradient-NMR diffusion measurements. A comparison of experimental and theoretical S K-edge X-ray absorption near edge spectra shows that relatively large lithium sulfide chain clusters are likely to occur in the DOL/DME-solvated lithium sulfide systems. Ab initio metadynamics simulations and NMR analysis indicate that Li + solvated by only the solvent can occur through Li + dissociation from sulfide chains. However, the occurrence of “sulfide-free” Li + is a minor mechanism compared with the dynamic aggregation and shuttling processes of polysulfide solvates in DOL/DME-based electrolytes of Li–S batteries. Overall, atomistic insights gained about clustering and lithium exchange dynamics will be critical for the predictive understanding of the polysulfide shuttling and nucleation process that dictates the Li–S battery performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Composition–Structure–Activity Correlation of Platinum–Ruthenium Nanoalloy Catalysts for Ethanol Oxidation Reaction

Understanding the evolution of the composition and atomic structure of nanoalloy catalysts in the ethanol oxidation reaction (EOR) is essential for the design of active and robust catalysts for direct ethanol fuel cells. This article describes a study of carbon-supported platinum–ruthenium electrocatalysts (PtRu/C) with different bimetallic compositions and their activities in the EOR, an important anode reaction in direct ethanol fuel cells (DEFCs). The study focused on establishing the relationship between the catalyst’s composition, atomic structure, and catalytic activity for the EOR. Ex situ and in situ synchrotron high-energy X-ray diffraction (HE-XRD) experiments coupled with atomic pair distribution function (PDF) analysis and in situ energy-dispersive X-ray (EDX) analysis were employed to probe the composition and structural evolution of the catalysts during the in situ EOR inside a membrane electrode assembly (MEA) in the fuel cell. The results revealed an intriguing composition–structure–activity relationship for the PtRu electrocatalysts under EOR experimental conditions. In particular, the alloy with a Pt/Ru ratio of ~50:50 was found to exhibit a maximum EOR activity as a function of the bimetallic composition. This composition–activity relationship coincides with the relationship between the Pt interatomic distances and coordination numbers and the bimetallic composition. Notably, the catalytic activities of the PtRu electrocatalysts showed a significant improvement during the EOR, which can be related to atomic-level structural changes in the nanoalloys occurring during the EOR, as indicated by in situ HE-XRD/PDF/EDX data. Here, the findings shed some new light on the mechanism of the ethanol oxidation reaction over bimetallic alloy nanocatalysts, which is important for the rational design and synthesis of active nanoalloy catalysts for DEFCs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Towards Mitigating Electron Beam-Induced Damage in MOFs Using Low Dose Electron Microscopy for In-Situ Room-Temperature Measurements

Metal-Organic Frameworks (MOFs) have emerged as a versatile class of materials with applications in gas storage and separation, catalysis, and drug delivery [1]. Understanding their damage mechanisms in under various environmental conditions is crucial for optimizing performance and stability [2]. This study employs a combination of Length Structural Coherence (LSC) analysis in electron scattering and Electron Energy Loss Spectroscopy (EELS) to elucidate the damage mechanisms in two representative MOFs. MIL101(Fe), and MIL101(Cr). Here, the primary objective is to reveal structural and chemical changes that occur under electron beam irradiation in Scanning Transmission Electron Microscopy (STEM), both in the pristine state and during in-situ CO and CO 2 adsorption. By combining LSC in Radial Distribution Function (RDF) analysis with EELS, comprehensive insights into the nanoscale alterations are obtained and correlated to the electron dose rate.

dos Santos, Gabriel T. [Northwestern University, E↗