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Characterization of zirconium carbides using electron microscopy, optical anisotropy, Auger depth profiles, X-ray diffraction, and electron density calculated by charge flipping method
Samples with five different zirconium carbide compositions (C/Zr molar ratio=0.84, 0.89, 0.95, 1.05, and 1.17) have been fabricated and studied using a variety of experimental techniques. Each sample was zone refined to ensure that the end product was polycrystalline with a grain size of 10-100 {mu}m. It was found that the lattice parameter was largest for the x=0.89 composition and smallest for the x=1.17 total C/Zr composition, but was not linear; this nonlinearity is possibly explained using electron densities calculated using charge flipping technique. Among the five samples, the unit cell of the ZrC{sub 0.89} sample showed the highest electron density, corresponding to the highest carbon incorporation and the largest lattice parameter. The ZrC{sub 0.84} sample showed the lowest carbon incorporation, resulting in a larger number of carbon vacancies and resultant strain. Samples with larger carbon ratios (x=0.95, 1.05, and 1.17) showed a slight decrease in lattice parameter, due to a decrease in electron density. Optical anisotropy measurements suggest that these three samples contained significant amounts of a graphitic carbon phase, not bonded to the Zr atoms. - Graphical abstract: Characterization of zirconium carbides using electron microscopy, optical anisotropy, Auger depth profiles, X-ray diffraction, and electron density calculated by the charge flipping method. Highlights: Black-Right-Pointing-Pointer The lattice parameter variation: ZrC{sub 0.89}>ZrC{sub 0.84}>ZrC{sub 0.95}>ZrC{sub 1.05}>ZrC{sub 1.17}. Black-Right-Pointing-Pointer Surface oxygen with no correlation to the lattice parameter variation. Black-Right-Pointing-Pointer ZrC{sub 0.89} had highest electron densities correspond to highest carbon incorporation. Black-Right-Pointing-Pointer Second highest lattice parameter in ZrC{sub 0.84} due to strain. Black-Right-Pointing-Pointer Unit cell electron density order: ZrC{sub 0.95}>ZrC{sub 1.05}>ZrC{sub 1.17}.
Advancing Aerosol Chemical Characterization and Vertical Profiling over the Southern Great Plains Using Uncrewed Aerial Sampling and Offline Aerosol Mass Spectrometry
Recent advancements in uncrewed aerial systems (UASs) and particulate matter (PM) analytical techniques have provided opportunities for atmospheric research. In this study, we deployed the Department of Energy’s fixed-wing ArcticShark UAS to examine PM 2.5 composition at varying altitudes─within and above the planetary boundary layer (PBL)─over the Southern Great Plains atmospheric observatory (SGP). A total of 22 flights were conducted across March, June, and August 2023. Composite filter samples were collected during each flight and analyzed with offline aerosol mass spectrometry (AMS), complemented by on-board real-time sensors and ground-based instrumentation, to provide a comprehensive view of regional aerosol characteristics. Results show clear vertical and seasonal differences in the aerosol composition. Relative to ground-level measurements, aloft samples exhibited shifts in the distribution of organic and inorganic PM, with the organic composition varying distinctly across seasons. Particulate organic nitrogen (ON) was elevated, with bulk compositions similar in March and June but strongly altered in August, likely driven by biomass burning and enhanced photochemical activity. Combined AMS and chemical ionization mass spectrometry analyses detected amines, amides, and amino acids. PM above the planetary boundary layer was enriched in oxidized organic aerosols, while ground-level PM contained higher nitrate and sulfate. Seasonal differences in aqueous-phase processing were also observed, which were strongest in March during persistent cloud cover and weaker in the drier August period, suggesting a shift from aqueous- to gas-phase SOA formation. In conclusion, these findings highlight the value of UAS in advancing PM measurements and vertical profiling of aerosol composition.
One-Shot Synthesis and Melt Self-Assembly of Bottlebrush Copolymers with a Gradient Compositional Profile
Morphological control plays a central role in soft materials design. Herein, we report the synthesis of a gradient bottlebrush architecture and its role in directing molecular packing in the solid state. Bottlebrush copolymers with gradient interfaces were prepared via one-shot ring-opening metathesis polymerization of exo- and endo- norbornene-capped macromonomers. Kinetic studies revealed a gradient compositional profile separating the two blocks along the backbone. Side-chain symmetric gradient bottlebrush copolymers exhibited a strong tendency to assemble into cylindrical microstructures, in contrast to their block copolymer analogs with sharp interfaces. Furthermore such exquisite architectural control of the interfacial composition affords a delicate handle to direct macromolecular assembly.
A direct dynamical measurement of the Milky Way's disk surface density profile, disk scale length, and dark matter profile at 4 kpc ≲ R ≲ 9 kpc
We present and apply rigorous dynamical modeling with which we infer unprecedented constraints on the stellar and dark matter mass distribution within our Milky Way (MW), based on large sets of phase-space data on individual stars. Specifically, we model the dynamics of 16,269 G-type dwarfs from SEGUE, which sample 5 kpc < R{sub GC} < 12 kpc and 0.3 kpc ≲ |Z| ≲ 3 kpc. We independently fit a parameterized MW potential and a three-integral, action-based distribution function (DF) to the phase-space data of 43 separate abundance-selected sub-populations (MAPs), accounting for the complex selection effects affecting the data. We robustly measure the total surface density within 1.1 kpc of the mid-plane to 5% over 4.5 kpc < R{sub GC} < 9 kpc. Using metal-poor MAPs with small radial scale lengths as dynamical tracers probes 4.5 kpc ≲ R{sub GC} ≲ 7 kpc, while MAPs with longer radial scale lengths sample 7 kpc ≲ R{sub GC} ≲ 9 kpc. We measure the mass-weighted Galactic disk scale length to be R{sub d} = 2.15 ± 0.14 kpc, in agreement with the photometrically inferred spatial distribution of stellar mass. We thereby measure dynamically the mass of the Galactic stellar disk to unprecedented accuracy: M {sub *} = 4.6 ± 0.3 + 3.0 (R {sub 0}/ kpc – 8) × 10{sup 10} M {sub ☉} and a total local surface density of Σ{sub R{sub 0}}(Z=1.1 kpc)=68 ± 4 M{sub ⊙} pc{sup −2} of which 38 ± 4 M {sub ☉} pc{sup –2} is contributed by stars and stellar remnants. By combining our surface density measurements with the terminal velocity curve, we find that the MW's disk is maximal in the sense that V {sub c,} {sub disk}/V {sub c,} {sub total} = 0.83 ± 0.04 at R = 2.2 R{sub d} . We also constrain for the first time the radial profile of the dark halo at such small Galactocentric radii, finding that ρ{sub DM}(r; ≈R {sub 0})∝1/r {sup α} with α < 1.53 at 95% confidence. Our results show that action-based DF modeling of complex stellar data sets is now a feasible approach that will be fruitful for interpreting Gaia data.
Impact of three-dimensional polarization profiles on spin-dependent measurements in colliding beam experiments
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Structure Prediction from Neutron Scattering Profiles: A Data Sciences Approach
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Cellulose synthase gene expression profiling of Physcomitrella patens
Abstract The cellulose synthase ( CESA ) gene family of seed plants comprises six clades that encode isoforms with conserved expression patterns and distinct functions in cellulose synthesis complex ( CSC ) formation and primary and secondary cell wall synthesis. In mosses, which have rosette CSC s like those of seed plants but lack lignified secondary cell walls, the CESA gene family diversified independently and includes no members of the six functionally distinct seed plant clades. There are seven CESA isoforms encoded in the genome of the moss Physcomitrella patens . However, only Pp CESA 5 has been characterised functionally, and little information is available on the expression of other Pp CESA family members. We have profiled Pp CESA expression through quantitative RT ‐ PCR , analysis of promoter‐reporter lines, and cluster analysis of public microarray data in an effort to identify expression and co‐expression patterns that could help reveal the functions of Pp CESA isoforms in protein complex formation and development of specific tissues. In contrast to the tissue‐specific expression observed for seed plant CESA s, each of the Pp CESA s was broadly expressed throughout most developing tissues. Although a few statistically significant differences in expression of Pp CESA s were noted when some tissues and hormone treatments were compared, no strong co‐expression patterns were observed. Along with CESA phylogenies and lack of single Pp CESA mutant phenotypes reported elsewhere, broad overlapping expression of the Pp CESA s indicates a high degree of inter‐changeability and is consistent with a different pattern of functional specialisation in the evolution of the seed plant and moss CESA families.
Application of linear least squares to the analysis of Auger electron spectroscopy depth profiles of plutonium oxides [Application of linear least squares to the analysis of AES depth profiles of plutonium oxides]
In this paper, the application of the linear least squares (LLS) methodology allows for quantitative determination of variation in material composition with depth. LLS fits were applied to decompose and enhance the interpretation of spectra obtained by Auger electron spectroscopy during depth profiles of oxidized plutonium surfaces. By means of the LLS algorithm, chemical state assignments of the Pu P 1 VV/O 45 VV, O KLL, and C KLL Auger transitions were determined and the existence of a subsurface oxycarbide layer was identified, with confirmation of the oxide and metal components provided from comparison to previous measurements of standard samples.
Impact of 3D polarization profiles on spin-dependent measurements in colliding beam experiments
We derive the effect of 3-dimensional polarization profiles on the measured polarization in polarimeters, as well as the observed polarization and the polarization-weighted luminosity (figure of merit) in single and double spin measurements in colliding beam experiments.
HDEV Depot Load Profile Generation Code (Code to Generate Heavy-Duty Electric Truck Depot Load Profiles) [SWR-21-72]
Code developed to generate heavy-duty electric truck depot load profiles for the study, "Heavy-Duty Truck Electrification and the Impacts of Depot Charging on Electricity Distribution Systems", by Borlaug et al., published in 2021. This software is provided as-is without dedicated support. The programming environment for this study may be reproduced with conda (installed via the Anaconda website): conda env create -f environment.yml To activate the environment: conda activate hdev-depot-charging-2021
Clostridium thermocellum transcriptomic profiles after exposure to furfural or heat stress
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Improved control of electron computer-generated holographic grating groove profiles using ion beam gas-assisted etching
In a transmission electron microscope, electrons are described by matter-waves with wavelengths five orders of magnitude smaller than optical electromagnetic waves. Analogous to optical holography, electron wavefronts can be shaped using nanoscale holographic gratings. Here we demonstrate a novel, scalable nanofabrication method for creating off-axis holographic gratings that demonstrate near ideal diffraction efficiencies for binary, sinusoidal, and blazed grating groove profiles. We show that this method can produce up to 50 µm diameter area gratings that diffract up to 68% of the transmitted electron wave into a desired diffraction order with less than 7% into any other order. Additionally, we find that the amount of inelastically scattered electrons from the material gratings remaining in the coherent diffraction orders from the gratings is negligible in the far field.
24-hour human urine and serum profiles of bisphenol A: Evidence against sublingual absorption following ingestion in soup
Extensive first-pass metabolism of ingested bisphenol A (BPA) in the gastro-intestinal tract and liver restricts blood concentrations of bioactive BPA to < 1% of total BPA in humans and non-human primates. Absorption of ingested BPA through non-metabolizing tissues of the oral cavity, recently demonstrated in dogs, could lead to the higher serum BPA concentrations reported in some human biomonitoring studies. We hypothesized that the extensive interaction with the oral mucosa by a liquid matrix, like soup, relative to solid food or capsules, might enhance absorption through non-metabolizing oral cavity tissues in humans, producing higher bioavailability and higher serum BPA concentrations. Concurrent serum and urine concentrations of d6-BPA, and its glucuronide and sulfate conjugates, were measured over a 24 hour period in 10 adult male volunteers following ingestion of 30 μg d6-BPA/kg body weight in soup. Absorption of d6-BPA was rapid (t{sub 1/2} = 0.45 h) and elimination of the administered dose was complete 24 h post-ingestion, evidence against any tissue depot for BPA. The maximum serum d6-BPA concentration was 0.43 nM at 1.6 h after administration and represented < 0.3% of total d6-BPA. Pharmacokinetic parameters, pharmacokinetic model simulations, and the significantly faster appearance half-life of d6-BPA-glucuronide compared to d6-BPA (0.29 h vs 0.45 h) were evidence against meaningful absorption of BPA in humans through any non-metabolizing tissue (< 1%). This study confirms that typical exposure to BPA in food produces picomolar to subpicomolar serum BPA concentrations in humans, not nM concentrations reported in some biomonitoring studies.
Material Profile Influences in Bulk-Heterojunctions
he morphology in mixed bulk-heterojunction films are compared using three different quantitative measurement techniques. We compare the vertical composition changes using high-angle annular dark-field scanning transmission electron microscopy with electron tomography and neutron and x-ray reflectometry. The three measurement techniques yield qualita-tively comparable vertical concentration measurements. The presence of a metal cathode during thermal annealing is observed to alter the fullerene concentration throughout the thickness of the film for all measurements. However, the abso-lute vertical concentration of fullerene is quantitatively different for the three measurements. The origin of the quantitative measurement differences is discussed. The authors thank Luna Innovations, Inc. for donating the endohedral fullerenes used in this study and Plextronics for the P3HT. They are gratefully thank the National Science Foundation Energy for Sustainability Program, Award No. 0933435. This work benefited from the use of the Lujan Neutron Scattering Center at Los Alamos Neutron Science Center funded by the DOE Office of Basic Energy Sciences and Los Alamos National Laboratory under DOE Contract DE-AC52-06NA25396. This research was also supported in part by Laboratory Directed Research & Development program at PNNL. The Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy under contract DE-AC05-76RL01830.