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At least 199 records · Page 11

IrGe 4 : A Predicted Weyl-Metal with a Chiral Crystal Structure

Polycrystalline IrGe4 was synthesized by annealing elements at 800 °C for 240 h, and the composition was confirmed by energy-dispersive X-ray spectroscopy. IrGe 4 adopts a chiral crystal structure (space group P3 1 21) instead of a polar crystal structure (P3 1 ), which was corroborated by the convergent-beam electron diffraction and Rietveld refinements using synchrotron powder X-ray diffraction data. The crystal structure features layers of IrGe 8 polyhedra along the b axis, and the layers are connected by edge- and corner-sharing. Each layer consists of corner-shared [Ir 3 Ge 20 ] trimers, which are formed by three IrGe 8 polyhedra connected by edge-sharing. Temperature-dependent resistivity indicates metallic behavior. The magnetoresistance increases with increasing applied magnetic field, and the nonsaturating magnetoresistance reaches 11.5% at 9 T and 10 K. The Hall resistivity suggests that holes are the majority carrier type, with a carrier concentration of 4.02 × 10 21 cm –3 at 300 K. In conclusion, electronic band structures calculated by density functional theory reveal a Weyl point with a chiral charge of +3 above the Fermi level.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Does size matter? An evaluation of length and proportion of information in environmental impact statements

Highlights: • Empirical analysis of length and proportion of information in EISs is presented. • Current EISs, in Brazil, are significantly longer than the early ones. • Baseline information is the most common element in EISs. • EIS length is affected by many variables, including project sector and size. • While relevant to decision-making, EIS length should be carefully regulated. - Abstract: For decades, authors and institutions have argued that the quality of Environmental Impact Statements (EISs) is somehow affected by the volume of information they contain. Both too little and too much information can be a problem. However, very few academic studies have addressed the issue of EIS length in detail. The objective of this article was to systematically analyze the volume of information presented in EISs, using Brazil as the empirical context. More specifically, this study evaluated the volume and proportion of information disclosed in 49 Brazilian EISs. This study also tried to identify sectorial variations and whether variables such as project size and number of pages in Terms of References are likely determinants of information volume. >146 thousand pages of EIS information were scrutinized in two rounds of content analysis. Data were organized in spreadsheets and then coded and analyzed through various descriptive and inferential statistical techniques. Overall, findings corroborate the fact that EISs are now significantly longer than the early ones, and still heavily loaded with baseline information. The average number of pages in EISs and in Non-technical Summaries was found to be 2993 and 94, respectively. Kruskal-Wallis and linear regression tests indicated that EIS length is likely affected by a combination of variables, including project size, territorial and sectorial characteristics. Such findings suggest that the historical approach of setting page limits to EISs through regulations and Terms of References is no longer appropriate for EIA practice in connection with large enterprises in Brazil, and arguably elsewhere. The article discusses its practical and academic implications, and highlights the need to further investigate the actual impacts of EIS length on decision-making.

54 ENVIRONMENTAL SCIENCES↗

The Arctic Ocean as a dead end for floating plastics in the North Atlantic branch of the Thermohaline Circulation

The subtropical ocean gyres are recognized as great marine accumulation zones of floating plastic debris; however, the possibility of plastic accumulation at polar latitudes has been overlooked because of the lack of nearby pollution sources. In the present study, the Arctic Ocean was extensively sampled for floating plastic debris from the Tara Oceans circumpolar expedition. Although plastic debris was scarce or absent in most of the Arctic waters, it reached high concentrations (hundreds of thousands of pieces per square kilometer) in the northernmost and easternmost areas of the Greenland and Barents seas. The fragmentation and typology of the plastic suggested an abundant presence of aged debris that originated from distant sources. This hypothesis was corroborated by the relatively high ratios of marine surface plastic to local pollution sources. Surface circulation models and field data showed that the poleward branch of the Thermohaline Circulation transfers floating debris from the North Atlantic to the Greenland and Barents seas, which would be a dead end for this plastic conveyor belt. Given the limited surface transport of the plastic that accumulated here and the mechanisms acting for the downward transport, the seafloor beneath this Arctic sector is hypothesized as an important sink of plastic debris.

54 ENVIRONMENTAL SCIENCES↗

Systematic mapping of the conformational landscape and dynamism of soluble fibrinogen

Background: Fibrinogen is a soluble, multisubunit, and multidomain dimeric protein, which, upon its proteolytic cleavage by thrombin, is converted to insoluble fibrin, initiating polymerization that substantially contributes to clot growth. Fibrinogen contains numerous, transiently accessible “cryptic” epitopes for hemostatic and immunologic proteins, suggesting that fibrinogen exhibits conformational flexibility, which may play functional roles in its temporal and spatial interactions. Hitherto, there have been limited integrative approaches characterizing the solution structure and internal flexibility of fibrinogen. Methods: Here, utilizing a multipronged, biophysical approach involving 2 solution-based techniques, temperature-dependent hydrogen-deuterium exchange mass spectrometry and small angle X-ray scattering, corroborated by negative stain electron microscopy, we present a holistic, conformationally dynamic model of human fibrinogen in solution. Results: Our data reveal 4 major and distinct conformations of fibrinogen accommodated by a high degree of internal protein flexibility along its central scaffold. We propose that the fibrinogen structure in the solution consists of a complex, conformational landscape with multiple local minima. This is further supported by the location of numerous point mutations that are linked to dysfibrinogenemia and posttranslational modifications, residing near the identified fibrinogen flexions. Conclusion: Further, this work provides a molecular basis for the structural “dynamism” of fibrinogen that is expected to influence the broad swath of its functionally diverse macromolecular interactions and fine-tune the structural and mechanical properties of blood clots.

59 BASIC BIOLOGICAL SCIENCES↗

HIGH-RESOLUTION LABORATORY SPECTRA ON THE λ131 CHANNEL OF THE AIA INSTRUMENT ON BOARD THE SOLAR DYNAMICS OBSERVATORY

Extreme ultraviolet spectra of C, O, F, Ne, Si, S, Ar, Ca, Fe, and Ni have been excited in an electron beam ion trap and studied with much higher resolution than available on Solar Dynamics Observatory (SDO) in order to ascertain the spectral composition of the SDO observations. We presently show our findings in the wavelength range 124-134 Å, which encompasses the λ131 observation channel of the Atmospheric Imaging Assembly (AIA). While the general interpretation of the spectral composition of the λ131 Fe channel is being corroborated, a number of new lines have been observed that might help to improve the diagnostic value of the SDO/AIA data.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

High-Temperature Gas Sensor Materials with Properties Predicted via First-Principles Calculations with Machine Learning Modeling and Experimental Corroboration

Understanding the temperature dependence of functional properties of sensing materials is vital for their applications in combustion environments. The electron-phonon coupling that derives the electronic structure change with temperatures is a key property of interest as it affects other sensing responses. Herein, we first assess the temperature dependence of band gap renormalization in sensing materials by employing Allen-Heine-Cardona (AHC) theory with density functional theory (DFT) simulations corroborated with experimental observation. As the AHC calculations are impractical for high-throughput screening of materials, we employ data-driven Gaussian process regression to predict the parameters employed in the O’Donnell empirical model from a set of physical features. To mitigate the reliability issues arising from the small size of the dataset, we apply a Bayesian technique to improve the generalizability of the data-driven models as well as to quantify the uncertainty associated with theoretical predictions. These models capture well the overall trend of the O’Donnell parameters with respect to a reduced feature set obtained by transforming the available physical features. Quantifying the associated uncertainty helps us understand the reliability of the predictions and, therefore, the variation of bandgap as a function of temperature for other novel materials. The predicted candidates from machine learning models are further validated by experiments and DFT calculations.

bandgap renormalization↗

Subterahertz collective dynamics of polar vortices

The collective dynamics of topological structures are of interest from both fundamental and applied perspectives. For example, studies of dynamical properties of magnetic vortices and skyrmions have not only deepened our understanding of many-body physics but also offered potential applications in data processing and storage. Topological structures constructed from electrical polarization, rather than electron spin, have recently been realized in ferroelectric superlattices, and these are promising for ultrafast electric-field control of topological orders. However, little is known about the dynamics underlying the functionality of such complex extended nanostructures. In this study, using terahertz-field excitation and femtosecond X-ray diffraction measurements, we observe ultrafast collective polarization dynamics that are unique to polar vortices, with orders-of-magnitude higher frequencies and smaller lateral size than those of experimentally realized magnetic vortices. A previously unseen tunable mode, hereafter referred to as a vortexon, emerges in the form of transient arrays of nanoscale circular patterns of atomic displacements, which reverse their vorticity on picosecond timescales. Its frequency is considerably reduced (softened) at a critical strain, indicating a condensation (freezing) of structural dynamics. We use first-principles-based atomistic calculations and phase-field modelling to reveal the microscopic atomic arrangements and corroborate the frequencies of the vortex modes. The discovery of subterahertz collective dynamics in polar vortices opens opportunities for electric-field-driven data processing in topological structures with ultrahigh speed and density.

36 MATERIALS SCIENCE↗

Full-flow-regime storage-streamflow correlation patterns provide insights into hydrologic functioning over the continental US

Interannual changes in low, median, and high regimes of streamflow have important implications for flood control, irrigation, and ecologic and human health. The Gravity Recovery and Climate Experiment (GRACE) satellites record global terrestrial water storage anomalies (TWSA), providing an opportunity to observe, interpret, and potentially utilize the complex relationships between storage and full-flow-regime streamflow. Here we show that utilizable storage-streamflow correlations exist throughout vastly different climates in the continental US (CONUS) across low- to high-flow regimes. A panoramic framework, the storage-streamflow correlation spectrum (SSCS), is proposed to examine macroscopic gradients in these relationships. SSCS helps form, corroborate or reject hypotheses about basin hydrologic behaviors. SSCS patterns vary greatly over CONUS with climate, land surface, and geologic conditions. Data mining analysis suggests that for catchments with hydrologic settings that favor storage over runoff, e.g., a large fraction of precipitation as snow, thick and highly-permeable permeable soil, SSCS values tend to be high. Based on our results, we form the hypotheses that groundwater flow dominates streamflows in South-eastern CONUS and Great Plains, while thin soils in a belt along the Appalachian Plateau impose a limit on water storage. SSCS also suggests shallow water table caused by high-bulk density soil and flat terrain induces rapid runoff in several regions. Our results highlight the importance of subsurface properties and groundwater flow in capturing flood and drought. Finally, we propose that SSCS can be used as a fundamental hydrologic signature to constrain models and to provide insights that lead us to better understand hydrologic functioning.

54 ENVIRONMENTAL SCIENCES↗

Nonadiabatic Derivative Couplings through Multiple Franck–Condon Modes Dictate the Energy Gap Law for Near and Short-Wave Infrared Dye Molecules

Near infrared (NIR, 700–1000 nm) and short-wave infrared (SWIR, 1000–2000 nm) dye molecules exhibit significant nonradiative decay rates from the first singlet excited state to the ground state. While these trends can be empirically explained by a simple energy gap law, detailed mechanisms of nearly universal behavior have remained unsettled for many cases. Theoretical and experimental results for two representative NIR/SWIR dye molecules reported here clarify the key mechanism for the observed energy gap law behavior. It is shown that the first derivative nonadiabatic coupling terms serve as major coupling pathways for nonadiabatic decay processes from the first excited singlet state to the ground state for these NIR and SWIR dye molecules and that vibrational modes other than the highest frequency modes also make significant contributions to the rate. Finally, this assessment is corroborated by further theoretical comparison with possible alternative mechanisms of intersystem crossing to triplet states and also by comparison with experimental data for deuterated molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Active site plasticity and possible modes of chemical inhibition of the human DNA deaminase APOBEC3B

The single-stranded DNA cytosine deaminase APOBEC3B (A3B) functions in innate immunity against viruses, but it is also strongly implicated in eliciting mutations in cancer genomes. Because of the critical role of A3B in promoting virus and tumor evolution, small molecule inhibitors are desirable. However, there is no reported structure for any of the APOBEC3-family enzymes in complex with a small molecule bound in the active site, which hampers the development of small molecules targeting A3B. Here we report high-resolution structures of an active A3B catalytic domain chimera with loop 7 residues exchanged with those from the corresponding region of APOBEC3G (A3G). The structures reveal novel open conformations lacking the catalytically essential zinc ion, with the highly conserved active site residues extensively rearranged. These inactive conformations are stabilized by 2-pyrimidone or an iodide ion bound in the active site. Molecular dynamics simulations corroborate the remarkable plasticity of the engineered active site and identify key interactions that stabilize the native A3B active site. These data provide insights into A3B active site dynamics and suggest possible modes of its inhibition by small molecules, which would aid in rational design of selective A3B inhibitors for constraining virus and tumor evolution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

SU-D-BRA-02: Motion Assessment During Open Face Mask SRS Using CBCT and Surface Monitoring

Purpose: To assess the robustness of immobilization using open-face mask technology for linac-based stereotactic radiosurgery (SRS) with multiple non-coplanar arcs via repeated CBCT acquisition, with comparison to contemporaneous optical surface tracking data. Methods: 25 patients were treated in open faced masks with cranial SRS using 3–4 non-coplanar arcs. Repeated CBCT imaging was performed to verify the maintenance of proper patient positioning during treatment. Initial patient positioning was performed based on prescribed shifts and optical surface tracking. Positioning refinements employed rigid 3D-matching of the planning CT and CBCT images and were implemented via automated 6DOF couch control. CBCT imaging was repeated following the treatment of all non-transverse beams with associated couch kicks. Detected patient translations and rotations were recorded and automatically corrected. Optical surface tracking was applied throughout the treatments to monitor motion, and this contemporaneous patient positioning data was recorded to compare against CBCT data and 6DOF couch adjustments. Results: Initial patient positions were refined on average by translations of 3±1mm and rotations of ±0.9-degrees. Optical surface tracking corroborated couch corrections to within 1±1mm and ±0.4-degrees. Following treatment of the transverse and subsequent superior-oblique beam, average translations of 0.6±0.4mm and rotations of ±0.4-degrees were reported via CBCT, with optical surface tracking in agreement to within 1.1±0.6mm and ±0.6-degrees. Following treatment of the third beam, CBCT indicated additional translations of 0.4±0.2mm and rotations of ±0.3-degrees. Cumulative couch corrections resulted in 0.7 ± 0.4mm average magnitude translations and rotations of ±0.4-degrees. Conclusion: Based on CBCT measurements of patients during SRS, the open face mask maintained patient positioning to within 1.5mm and 1-degree with >95% confidence. Patient positioning determined by optical surface tracking agreed with CBCT assessment to within 1±1mm and ±0.6-degree rotations. These data support the use of 1–2mm PTV margins and repeated CBCT to maintain stereotactic positioning tolerances.

60 APPLIED LIFE SCIENCES↗

Li2[SeC2Se] · 2 NH3: A Crystalline Ammoniate with a-Se-C=C-Se- Dianion

Reaction of Li2C2 with elemental selenium in a molar ratio of 1:2 in liquid ammonia led to the formation of the ammoniate Li2[SeC2Se] ? 2 NH3. Its crystal structure was solved and refined from high-resolution synchrotron powder diffraction data (P21/c, Z = 4). It contains the ?Se-C?C-Se? anion, unprecedented in a crystalline material, whose existence was corroborated by IR/Raman spectra and electronic-structure theory, showing an almost perfect agreement with calculated spectra. Elaborated magnetic-bottle and velocity-map imaging photoelectron spectroscopic investigations show that the ?Se-C?C-Se? radical anion can be transferred to the gas phase, where it was analyzed by NIPE (Negative Ion Photoelectron) and VMI (Velocity-Map Imaging) spectra, which correlate nicely with simulated spectra based on 2?u ? 3Sg – and 2?u ?1Sg + transitions including spin-orbit couplings

Hetzert, Marc↗

Layered inorganic/organic mercaptopropyl pendant chain hybrid for chelating heavy cations

Graphical abstract: Crystalline lamellar silicate RUB-18 was immobilized with mercaptopropyl groups at the surface and then used as support for cadmium and lead removal from aqueous solutions. Highlights: Black-Right-Pointing-Pointer Synthetic methodology requires intercalation. Black-Right-Pointing-Pointer Organofunctionalized ilerite compound as sorbent. Black-Right-Pointing-Pointer Active mercaptopropyl groups remove cations. Black-Right-Pointing-Pointer High maximum sorption capacity for cadmium. -- Abstract: Heavy metal sorbents with uptake capacities for divalent cadmium and lead cation removal from aqueous solutions have been synthesized by grafting mercaptopropyltrimethoxysilane onto the surface of two different precursors obtained from lamellar ilerite, its acidic and the cetyltrimethylammonium exchanged forms. The organofunctionalization was carried out by two different procedures: reflux and solvent evaporation methodologies. Elemental analysis data based on carbon content gave 1.37 and 3.53 mmol of organic pendant groups per gram of hybrid by the reflux method, when starting from acidic ilerite and the surfactant form. X-ray diffraction corroborated the maintenance of the original crystallinity. Infrared spectroscopy and nuclear magnetic resonance for {sup 29}Si and {sup 13}C nuclei are in agreement with the success of the proposed method. The sulfur basic centers attached to the lamellar structure are used to coordinate both cations at the solid/liquid interface. The isotherms were obtained through the batchwise process and the experimental data were adjusted to the Freundlich model. The maximum sorption capacities of 5.55 and 5.12 mmol g{sup -1} for lead and 6.10 and 7.10 mmol g{sup -1} for cadmium were obtained for organofunctionalized ilerite and its surfactant form, synthesized by reflux methodology. This behavior suggested that these hybrids could be employed as promising sorbents with a polluted system.

36 MATERIALS SCIENCE↗

Elongational rheology and cohesive fracture of photo-oxidated LDPE

It was found recently that low-density polyethylene (LDPE) samples with different degrees of photo-oxidation represent an interesting system to study the transition from ductile to cohesive fracture and the aspects of the cohesive rupture in elongational flow. Sheets of LDPE were subjected to photo-oxidation in the presence of air using a xenon lamp to irradiate the samples for times between 1 day and 6 weeks. Characterisation methods included Fourier transform infrared spectroscopy, solvent extraction method, and rheology in shear and uniaxial extensional flows. Linear viscoelasticity was increasingly affected by increasing photo-oxidation due to crosslinking of LDPE, as corroborated by the carbonyl index, acid and aldehydes groups, and gel fraction. The molecular stress function model was used to quantify the experimental data, and the nonlinear model parameter β was found to be correlated with the gel content. The uniaxial data showed that the transition from ductile to cohesive fracture was shifted to lower elongational rates, the higher the gel content was. From 2 weeks photo-oxidation onwards, cohesive rupture occurred at every strain rate investigated. The true strain and true stress at cohesive fracture as well as the energy density applied to the sample up to fracture were analyzed. At low gel content, rupture was mainly determined by the melt fraction while at high gel content, rupture occurred predominantly in the gel structure. The strain at break was found to be independent of strain rate, contrary to the stress at break and the energy density. Thus, the true strain and not the stress at break or the energy density was found to be the relevant physical quantity to describe cohesive fracture behavior of photo-oxidated LDPE. The equilibrium modulus of the gel structures was correlated with the true strain at rupture. The stiffer the gel structure, the lower was the deformation tolerated before the sample breaks.

36 MATERIALS SCIENCE↗

EGS Collab Experiment 1: In-situ observation of pre-, co- and post-seismic shear slip preceding hydraulic fracturing

Understanding the initiation and arrest of earthquakes is one of the long-standing challenges of seismology. Here we report on direct observations of borehole displacement by a meter-sized shear rupture induced by pressurization of metamorphic rock at 1.5 km depth. We observed the acceleration of sliding, followed by fast co-seismic slip and a transient afterslip phase. Total displacements were about 7, 5.5 and 9.5 micrometers, respectively for the observed pre-slip, co-seismic slip and afterslip. The observed pre-slip lasted about 0.4 seconds. Co-seismic slip was recorded by the 1 kHz displacement recording and a 12-component array of 3-C accelerometers sampled at 100 kHz. The observed afterslip is consistent with analytical models of arrest in a velocity-strengthening region and subsequent stress relaxation. The observed slip vector agrees with the activation of a bedding plane within the phyllite, which is corroborated by relocated seismic events that were observed during the later stages of the injection experiment. This submission includes the pressure and deformation data recorded by the SIMFIP probe during the first injection at the 164 ft (50 m) notch of borehole E1-I. The injection was performed on on 05/22/2018 as part of Experiment 1 of the EGS Collab project. This data accompanies a manuscript submitted to GRL, linked in this submission.

15 GEOTHERMAL ENERGY↗

Supported Molten Metal Membranes for Hydrogen Separation

We describe here our results on the feasibility of a novel dense metal membrane for hydrogen separation: Supported Molten Metal Membrane, or SMMM. The goal in this work was to develop these new membranes based on supporting thin films of low-melting, non- precious group metals, e.g., tin (Sn), indium (In), gallium (Ga), or their alloys, to provide a flux and selectivity of hydrogen that rivals the conventional but substantially more expensive palladium (Pd) or Pd alloy membranes, which are susceptible to poisoning by the many species in the coal-derived syngas, and further possess inadequate stability and limited operating temperature range. The novelty of the technology presented numerous challenges during the course of this project, however, mainly in the selection of appropriate supports, and in the fabrication of a stable membrane. While the wetting instability of the SMMM remains an issue, we did develop an adequate understanding of the interaction between molten metal films with porous supports that we were able to find appropriate supports. Thus, our preliminary results indicate that the Ga/SiC SMMM at 550 °C has a permeance that is an order of magnitude higher than that of Pd, and exceeds the 2015 DOE target. To make practical SMM membranes, however, further improving the stability of the molten metal membrane is the next goal. For this, it is important to better understand the change in molten metal surface tension and contact angle as a function of temperature and gas-phase composition. A thermodynamic theory was, thus, developed, that is not only able to explain this change in the liquid-gas surface tension, but also the change in the solid-liquid surface tension as well as the contact angle. This fundamental understanding has allowed us to determine design characteristics to maintain stability in the face of changing gas composition. These designs are being developed. For further progress, it is also important to understand the nature of solution and permeation process in these molten metal membranes. For this, a comprehensive microkinetic model was developed for hydrogen permeation in dense metal membranes, and tested against data for Pd membrane over a broad range of temperatures. It is planned to obtain theoretical and experimental estimates of the parameters to corroborate the model against mental results for SMMM.

08 HYDROGEN↗

Frequency, pressure and strain dependence of nonlinear elasticity in Berea Sandstone

Acoustoelasticity measurements in a sample of room dry Berea sandstone are conducted at various loading frequencies to explore the transition between the quasi-static ( f → 0) and dynamic (few kilohertz) nonlinear elastic response. We carry out these measurements at multiple confining pressures and perform a multivariate regression analysis to quantify the dependence of the harmonic content on strain amplitude, frequency, and pressure. The modulus softening (equivalent to the harmonic at 0f) increases by a factor 2–3 over 3 orders of magnitude increase in frequency. Harmonics at 2f, 4f, and 6f exhibit similar behaviors. In contrast, the harmonic at 1f appears frequency independent. This result corroborates previous studies showing that the nonlinear elasticity of rocks can be described with a minimum of two physical mechanisms. This study provides quantitative data that describes the rate dependency of nonlinear elasticity. Furthermore, these findings can be used to improve theories relating the macroscopic elastic response to microstructural features.

58 GEOSCIENCES↗

High-performance computing in water resources hydrodynamics

In this work, we present a vision of future water resources hydrodynamics codes that can fully utilize the strengths of modern high-performance computing. The advances to computing power, formerly driven by the improvement of central processing unit processors, now focus on parallel computing and, in particular, the use of graphics processing units (GPUs). However, this shift to a parallel framework requires refactoring the code to make efficient use of the data as well as changing even the nature of the algorithm that solves the system of equations. These concepts along with other features such as the precision for the computations, dry regions management, and input/output data are analyzed in this paper. A 2D multi-GPU flood code applied to a large-scale test case is used to corroborate our statements and ascertain the new challenges for the next-generation parallel water resources codes.

54 ENVIRONMENTAL SCIENCES↗