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At least 1,063 records · Page 59

Characterizing Polyoxovanadate‐Alkoxide Clusters Using Vanadium K‐Edge X‐Ray Absorption Spectroscopy

Abstract A number of technologies would benefit from developing inorganic compounds and materials with specific electronic and magnetic exchange properties. Unfortunately, designing compounds with these properties is difficult because metal⋅⋅⋅metal coupling schemes are hard to predict and control. Fully characterizing communication between metals in existing compounds that exhibit interesting properties could provide valuable insight and advance those predictive capabilities. One such class of molecules are the series of Lindqvist iron‐functionalized and hexavanadium polyoxovanadate‐alkoxide clusters, which we characterized here using V K‐edge X‐ray absorption spectroscopy. Substantial changes in the pre‐edge peak intensities were observed that tracked with the V 3 d ‐electron count. The data also suggested substantial delocalization between the vanadium cations. Meanwhile, the Fe III cations were electronically isolated from the polyoxovanadate core.

Meyer, Rachel L.↗

In-situ/operando X-ray characterization of metal hydrides

Here in this article, the capabilities of soft and hard X-ray techniques, including X-ray absorption (XAS), soft X-ray emission spectroscopy (XES), resonant inelastic soft X-ray scattering (RIXS), X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD), and their application to solid-state hydrogen storage materials are presented. These characterization tools are indispensable for interrogating hydrogen storage materials at the relevant length scales of fundamental interest, which range from the micron scale to nanometer dimensions.Since nanostructuring is now well established as an avenue to improve the thermodynamics and kinetics of hydrogen release and uptake, due to properties such as reduced mean free paths of transport and increased surface-to-volume ratio, it becomes of critical importance to explicitly identify structure-property relationships on the nanometer scale. X-ray diffraction and spectroscopy are effective tools for probing size-, shape-, and structure-dependent material properties at the nanoscale. This article also discusses the recent development of in-situ soft X-ray spectroscopy cells, which enable investigation of critical solid/liquid or solid/gas interfaces under more practical conditions. These unique tools are providing a window into the thermodynamics and kinetics of hydrogenation and dehydrogenation reactions and informing a quantitative understanding of the fundamental energetics of hydrogen storage processes at the microscopic level. In particular, in-situ soft X-ray spectroscopies can be utilized to probe the formation of intermediate species, byproducts, as well as the changes in morphology and effect of additives, which all can greatly affect the hydrogen storage capacity, kinetics, thermodynamics, and reversibility.A few examples using soft X-ray spectroscopies to study these materials are discussed to demonstrate how these powerful characterization tools could be helpful to further understand the hydrogen storage systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Characterizing suburban soil and microbial properties along a soil age chronosequence

Abstract Rapid urbanization is drastically altering ecosystem processes in landscapes around the world. In particular, suburban residential neighborhoods comprise novel ecosystems with water and nutrient inputs that differ greatly from the surrounding land area. These impacts generate concern over the sustainability of urban ecosystems, especially whether they will be characterized by net carbon gain or loss over time. To address this knowledge gap, we established a chronosequence of residential yards in Southern California to test how urban soils change after development. We predicted that urbanized soils would experience shifts in physical characteristics and microbial function over time consistent with ecological succession theory, but residential soils would maintain novel moisture and nutrient regimes compared to undeveloped soils, never “recovering” to a pre‐developed state. We compared different vegetation types to quantify impacts of homeowner landscaping choices and characterized yard soils and their microbial communities. We found that yard soils were nutrient‐ and moisture‐enriched compared to an adjacent undeveloped ecosystem, and turfgrass was associated with higher levels of water and nitrogen. Despite high respiration rates, yard soils accumulated carbon and nitrogen over time. We conclude that suburban residential soils comprise dynamic and heterogeneous ecosystems that are highly influenced by landscaping choices and management practices, and warrant closer study at small management‐relevant scales.

Suratt, Andie [Department of Ecology and Evolution↗

Simulation-based characterization of the variability of earthquake risk to buildings in the near-field

Recent advancements in high performance computing platforms and computational workflow for regional-scale simulations are enabling unprecedented modeling of fault-to-structure earthquake processes. Regional simulations resolving ground motions at frequencies relevant to engineered systems are becoming computationally viable and provide a new capability to improve understanding of the geographical distribution and intensity of risk to buildings and critical infrastructure. As computational capabilities advance, it is essential to move beyond illustrative single rupture realizations for scenario earthquake events towards the development of a full suite of rupture realizations that appropriately characterize the range of risk to building systems. The work described in this article investigates the application of a suite of fault rupture realizations with the objective of assessing near-fault, site-specific seismic demand variability for building structures. A representative high-performance regional-scale computational model is utilized to execute ground motion and building response simulations based on 18 kinematic rupture realizations of an M7 strike-slip scenario earthquake. The fault rupture models for the scenario earthquake are created by systematically perturbing the hypocenter location and stochastically generating rupture parameters (slip, rise time, rake angle) to represent a breadth of ground motion intensities resulting from the spatial and temporal variabilities of an earthquake rupture process. The resulting seismic demand variability for three-story (short period) and forty-story (long period) steel moment-resisting frame buildings is characterized in terms of the median and distribution of peak inter-story drift ratio for a range of near-fault sites. The full suite of 18 fault rupture realizations and approximately 280,000 nonlinear dynamic building simulations indicate that the three-story building undergoes higher median seismic demand and significantly greater variability of demand at a given site than the forty-story building, which has important implications for the level of certainty in predicting building performance during an earthquake. The simulations performed provide deeper insight into the relationship between fault rupture parameterization and building response, which is essential information for developing a representative suite of rupture realizations for specific earthquake scenarios.

58 GEOSCIENCES↗

Synthesis and Characterization of Tris(oxazolinyl)borato Copper(II) and Copper(I) Complexes

The reaction of To M Tl (To M =tris(4,4-dimethyl-2-oxazolinyl)phenylborate) and CuBr 2 in benzene at 60 °C provides To M CuBr (1) as an entry-point into tris(oxazolinyl)phenylborato copper chemistry. In this work, To M CuO t Bu (2) and To M CuOAc (3) are prepared by the reactions of To M CuBr with KO t Bu and NaOAc, respectively. To M CuO t Bu is transformed into (To M CuOH) 2 (4) through hydrolysis. NMR, FT-IR, and EPR spectroscopies are used to determine the electronic and structural properties of these copper(II) compounds, and the solid-state structures were characterized by X-ray crystallography. Reduction of copper is observed upon treatment of To M CuO t Bu with phenylsilane in an attempt to synthesize monomeric copper(II) hydride. To M Cu (5) and To M 2 Cu (6) were independently synthesized and characterized for comparison.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

An insight into microscopy and analytical techniques for morphological, structural, chemical, and thermal characterization of cellulose

Cellulose obtained from plants is a bio-polysaccharide and the most abundant organic polymer on earth that has immense household and industrial applications. Hence, the characterization of cellulose is important for determining its appropriate applications. In this article, we review the characterization of cellulose morphology, surface topography using microscopic techniques including optical microscopy, transmission electron microscopy, scanning electron microscopy, and atomic force microscopy. Additionally, other physicochemical characteristics like crystallinity, chemical composition, and thermal properties are studied using techniques including X-ray diffraction, Fourier transform infrared, Raman spectroscopy, nuclear magnetic resonance, differential scanning calorimetry, and thermogravimetric analysis. This review may contribute to the development of using cellulose as a low-cost raw material with anticipated physicochemical properties.

59 BASIC BIOLOGICAL SCIENCES↗

Electron Microscopy Transfer System to Protect Atmosphere‐Sensitive Materials for Scanning Electron Microscopy Characterization

Atmosphere- and/or moisture-sensitive materials can be challenging to characterize using electron microscopy techniques due to sample preparation workflows that generally require exposure to ambient conditions. Here, we describe a novel preparation method that uses aluminum foil in combination with a commercial cryo-EM transfer system to circumvent undesired exposure to the atmosphere. First, hygroscopic MgCl 2 was used as a model material, and prepared samples (both protected and unprotected) were placed in a controlled-humidity environment (> 80% relative humidity) for various exposure lengths (circa seconds to hours). Following this, the effectiveness of the sample preparation method was determined by comparing qualitative photos and quantitative X-ray diffraction patterns between the two sample subsets. The combined results of these experiments suggest that the outlined preparation method effectively protects MgCl 2 from atmospheric contamination compared to MgCl 2 samples that had no protective measures taken. Finally, the preparation method was utilized to protect a highly hygroscopic crystalline BaO thin film for characterization via scanning electron microscopy, thereby demonstrating a functional application of the outlined preparation technique and an additional use for the commercial cryo-EM transfer system beyond its intended application.

atmosphere-sensitive materials↗

Shear and combustion characterization of printable ammonium perchlorate composite propellant formulations

Seven formulations of ammonium perchlorate composite propellant (APCP) are developed and their properties relevant for successful additive manufacture are characterized. Extrusion in a custom-built 3D printing system and spindle viscometry are used to collect viscosity measurements of curing primary and non-curing secondary versions of the formulations. The formulations that behave similarly to a Bingham plastic, with apparent viscosities between 4 and 8 thousand Pa*s at 30 minutes post-mix, are determined to be most suitable for printing applications. Measurements of one material show a yield stress of 1 kPa. Ambient pressure burn rates of 2.0–2.9 mm/s were measured for the compositions tested. All measured burn rates were comparable to the lower end of typical burn rates for APCP. In conclusion, the results of the characterization demonstrate a propellant suitable for use in a 3D printing system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Rapid paper spray mass spectrometry characterization of uranium and exemplar molecular species

The ability to detect and quantify the presence of specific inorganic elements and complexes is essential for environmental monitoring and nuclear safeguards applications. In this work, paper spray ionization mass spectrometry (PSI–MS) was used for the rapid chemical and isotopic characterization of trace inorganic species collected on cotton swipe substrates. Here, the direct analysis of cotton swipes using this ambient ionization technique led to fast sample analysis that retained original chemical information of the source material with minimal sample preparation. Mass spectra were collected on an atmospheric pressure ionization, high–resolution mass spectrometer for solutions containing uranyl acetate, uranyl chloride, uranyl nitrate, and uranyl tri– n –butylphosphate (uranyl–TBP) complexes. Gadolinium nitrate was used as an internal standard for the quantitative analysis of uranium. To demonstrate the ability to characterize inorganic contaminants in the presence of uranium, a multi–element inorganic standard containing U, Bi, Pb, Cd, Fe, and Zn was deposited onto cotton substrates and directly analyzed without purification. All elements doped on the cotton substrate were detected with strong signal–to–noise (S/N) ratios (S/N~1000 for UO 2 + on multi–element doped swipes) and high integrated intensities (>10 5 counts) from collection periods of approximately 1 min. Limits of detection were determined to be approximately 94 ng for UO 2 + and uranyl acetate through the measurement of ppb level solutions. The rapid analysis of uranium and other inorganic–containing samples while still retaining original chemical information (e.g. uranyl complexation) was demonstrated. Qualitative detection and speciation were achieved in less than 1 min of analysis. For uranium isotopic quantitation, longer accumulations (>15 min) can be sustained to improve the accuracy of minor 235 U isotopic abundance measurements to approximately 1% error.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Recent In Situ/Operando Characterization of Lithium-Sulfur Batteries

To address the ever-increasing energy demand due to the increase in the population and at the same time depleting fossil fuel reserves, new energy storage systems, such as batteries, are being developed. Among various battery systems, Li-S batteries have comparatively high theoretical energy density and lower cost, making Li-S batteries very promising for next-generation secondary batteries. However, the current energy density and capacity decay with cycling of Li-S batteries do not fulfill the industrialization needs. To overcome the drawbacks of Li-S batteries and improve its performance, better mechanism understanding is necessary. A great deal of ex situ characterization research has been conducted making a lot of progress in the understanding of the working mechanism. Considering the complexity of the intermediate lithium polysulfides and the inherent multi-electron reaction pathways, advanced in situ/operando techniques are highly required. In this chapter, recent progress of a few typical in situ/operando characterization techniques used in Li-S battery studies is reviewed. These techniques provide more in-depth understanding of Li-S batteries in different aspects and could be enlightening for other energy storage systems too.

Yang, Yan↗

3D Characterization of the Columnar-to-Equiaxed Transition in Additively Manufactured Inconel 718

Additive manufacturing (AM) provides enormous processing flexibility, enabling novel part geometries and optimized designs. Access to a local heat source further permits the potential for local microstructure control on the scale of individual melt pools, which can enable local control of part properties. In order to design tailored processing strategies for target microstructures, models predicting the columnar-to-equiaxed transition must be extended to the high solidification velocities and complex thermal histories present in AM. Here, we combine 3D characterization with advanced modeling techniques to develop a more complete understanding of the solidification process and evolution of microstructure during electron beam melting (EBM) of Inconel 718. Full calibration of existing microstructure prediction models demonstrates the differences between AM processes and more conventional welding techniques, underlying the need for accurate determination of key parameters that can only be measured directly in 3D. The ability to combine multisensor data in a consistent 3D framework via data fusion algorithms is essential to fully leverage these advanced characterization approaches. Thermal modeling provides insight on microstructure development within isolated solidification events and demonstrates the role of Marangoni effects on controlling solidification behavior.

Polonsky, Andrew↗

Experimental Characterization of OpenMP Offloading Memory Operations and Unified Shared Memory Support

The OpenMP specification recently introduced support for unified shared memory, allowing implementation to leverage underlying system software to provide a simpler GPU offloading model where explicit mapping of variables is optional. Support for this feature is becoming more available in different OpenMP implementations on several hardware platforms. A deeper understanding of the different implementation’s execution profile and performance is crucial for applications as they consider the performance portability implications of adopting a unified memory offloading programming style. This work introduces a benchmark tool to characterize unified memory support in several OepnMP compilers and runtimes, with emphasis on identifying discrepancies between different OpenMP implementations as to how they various memory allocation strategies interact with unified shared memory. The benchmark tool is used to characterize OpenMP compilers on three leading High Performance Computing platforms supporting different CPU and device architectures. The benchmark tool is used to assess the impact of enabling unified shared memory on the performance of memory-bound code, highlighting implementation differences that should be accounted for when applications consider performance portability across platforms and compilers.

Elwasif, Wael↗

Characterizing 4-string contact interaction using machine learning

Abstract The geometry of 4-string contact interaction of closed string field theory is characterized using machine learning. We obtain Strebel quadratic differentials on 4-punctured spheres as a neural network by performing unsupervised learning with a custom-built loss function. This allows us to solve for local coordinates and compute their associated mapping radii numerically. We also train a neural network distinguishing vertex from Feynman region. As a check, 4-tachyon contact term in the tachyon potential is computed and a good agreement with the results in the literature is observed. We argue that our algorithm is manifestly independent of number of punctures and scaling it to characterize the geometry ofn-string contact interaction is feasible.

Physics↗

Characterizing Topological Order with Matrix Product Operators

One of the most striking features of gapped quantum phases that exhibit topological order is the presence of long-range entanglement that cannot be detected by any local order parameter. The formalism of projected entangled-pair states is a natural framework for the parameterization of gapped ground state wavefunctions which allows one to characterize topological order in terms of the virtual symmetries of the local tensors that encode the wavefunction. In their most general form, these symmetries are represented by matrix product operators acting on the virtual level, which leads to a set of algebraic rules characterizing states with topological quantum order. This construction generalizes the concepts of $\mathsf G$- and twisted injectivity; the corresponding matrix product operators encode all topological features of the theory and provide a complete picture of the ground state manifold on the torus. We show how the string-net models of Levin and Wen fit within this formalism and in doing so provide a particularly intuitive interpretation of the pentagon equation for F-symbols as the pulling of matrix product operators through the string-net tensor network. Our approach paves the way to finding novel topological phases beyond string nets and elucidates the description of topological phases in terms of entanglement Hamiltonians and edge theories.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Efficacy of perfusion CT in differentiating of pancreatic ductal adenocarcinoma from mass-forming chronic pancreatitis and characterization of isoattenuating pancreatic lesions

Purpose: Multidetector computed tomography (MDCT) is routinely used in the diagnosis of pancreatic ductal adenocarcinoma (PDAC), but it may be inadequate in some cases, especially mass-forming chronic pancreatitis (MFCP) and isoattenuating pancreatic lesions. Perfusion CT (pCT) may help resolve this problem. The aim of this study was to evaluate whether pCT could help differentiating PDAC from MFCP and in characterization of isoattenuating pancreatic lesions. Materials and methods: This prospective study included 89 cases of pancreatic lesions detected by MDCT and further analyzed with pCT. Sixty-one cases with final pathological diagnosis PDAC and 12 cases with MFCP were included from the study. Blood volume (BV), blood flow (BF), mean transit time (MTT), and permeability surface area product (PS) maps were obtained. Perfusion values obtained from the lesions and normal parenchyma were compared. Results: Compared with normal parenchyma, BV, BF, PS were lower and MTT was longer in PDAC and MFCP (p < 0.05). Compared with MFCP, BV, BF, PS were lower and MTT was longer in PDAC (p < 0.001). Compared with normal parenchyma, BV, BF, PS were lower and MTT was longer in isoattenuating lesions, (p < 0.001). Cutoff values of 7.60 mL/100 mL, 64.43 mL/100 mL/min, 28.08 mL/100 mL/min for BV, BF, PS, respectively, provided 100% sensitivity and specificity and 7.47 s for MTT provided 98.3% sensitivity, 80% specificity for distinguishing PDAC from MFCP. Conclusion: pCT is a useful technology that can be helpful in overcoming the limitations of routine MDCT in diagnosing PDAC and characterization of isoattenuating lesions.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

Usefulness of rapid kV-switching dual energy CT in renal tumor characterization

Purpose: To investigate whether iodine content can discriminate between benign or malignant renal tumors, malign tumor subtypes, low-grade and high-grade tumors on rapid kv-switching dual-energy CT (rsDECT). Methods: This prospective study enrolled 95 patients with renal tumors who underwent rsDECT for tumor characterization between 2016 and 2018. Attenuation on true and virtual unenhanced images, absolute enhancement and enhancement ratio and iodine content of each lesion on nephrographic phase iodine density images were measured. Histopathological diagnosis was obtained following either surgery or core biopsy. Results: Eighty-five tumors were renal cell carcinoma (RCC) (56 clear cell, 20 papillary, 9 chromophobe) and 10 were benign (6 angiomyolipoma,4 oncocytoma). 46 tumors were low-grade and 23 high-grade. There was significant difference between iodine content of clear cell and non-clear cell (papillary + chromophobe) RCC (p < 0.001). However, no significant iodine content differences were found between papillary and chromophobe RCC, benign and malignant tumors, low-grade and high-grade tumors. The best cut-off iodine content for differentiating clear cell from non-clear cell RCC was 3.2 mg/ml and clear cell from papillary RCC was 2.9 mg/ml with a high sensitivity and specificity. Also, significant difference was found between attenuation values of true and virtual unenhanced images (p = 0.007). Mean iodine content, absolute enhancement and enhancement ratio were highly correlated. Conclusion: rsDECT contributes to renal tumor characterization by showing higher iodine content in clear cell RCCs compared with non-clear cell RCCs.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

Extended abdominopelvic MRI versus CT at the time of adnexal mass characterization for assessing radiologic peritoneal cancer index (PCI) prior to cytoreductive surgery

Purpose: To evaluate whether extending the MRI scan to include the abdomen at the time of adnexal mass characterization could replace additional CT for peritoneal cancer index (PCI) assessment. Methods: After institutional review board approval for this prospective study, 36 consecutive females with ovarian and FT malignancies were included. All patients signed an informed consent. Patients underwent preoperative CT (32 patients) and MRI (36 patients). Images were interpreted by 2 independent observers. Surgical data were available in 27 patients. Region-by-region analysis was performed for detection rates of peritoneal carcinomatosis (PC). Inter-observer agreement for each region was evaluated by kappa statistics. Radiologic PCI was calculated by CT and MRI independently and inter-observer agreement for CT and MRI as well as agreement between radiologic and surgical PCI were evaluated by weighted-kappa statistics. Results: On region-by-region analysis, the highest detection rates of PC were noted at the central abdomen and pelvis. Detection rates were higher by MRI than CT, mainly in bowel serosal surface, pelvis, and right upper abdomen regions. Inter-observer agreement of MRI was higher than CT in most regions. The median PCI by CT was 5 and 4 for the first and second observers (range 0–21 for both observers), respectively. The median PCI by MRI was 6 (range 0–23 for both observers). The inter-observer agreement of PCI was excellent by both CT and MRI (k = 0.876 and k = 0.912, respectively). The agreement between CT and surgical PCI was 0.660 and 0.590 for the first and second observers, respectively. The agreement between MRI and surgical PCI was 0.797 and 0.798 for the first and second observers, respectively. Conclusions: Extending MRI scan to include the abdomen at the time of adnexal mass characterization allows accurate estimation of PC, with better results than CT, obviating the need for dedicated CT scan of abdomen and pelvis for imaging of PC.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

Characterization of partially observed epidemics through Bayesian inference: application to COVID-19

We demonstrate a Bayesian method for the "real-time'" characterization and forecasting of partially observed COVID-19 epidemic. Characterization is the estimation of infection spread parameters using daily counts of symptomatic patients.The method is designed to help guide medical resource allocation in the early epoch of the outbreak. The estimation problem is posed as one of Bayesian inference and solved using a Markov chain Monte Carlo technique. The data used in this study was sourced before the arrival of the second wave of infection in July 2020. The proposed modeling approach, when applied at the country level, generally provides accurate forecasts at the regional, state and country level. The epidemiological model detected the flattening of the curve in California, after public health measures were instituted.The method also detected different disease dynamics when applied to specific region of New Mexico

60 APPLIED LIFE SCIENCES↗