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At least 1,585 records · Page 88

Understanding the Reaction Mechanism of Lithium–Sulfur Batteries by In Situ/Operando X-ray Absorption Spectroscopy

Because of the high theoretical energy density of 2600Whkg -1 , lithium–sulfur (Li–S) batteries are regarded as one of the most promising energy storage technologies to meet the increasing requirement from personal devices to automobiles. However, the practical application of Li–S batteries is still challenging due to technical obstacles, such as low sulfur utilization and poor lifetime. Therefore, understanding the electrode reaction mechanism is of critical importance to further improve the battery performance and lifetime. Here, we review recent progress in the application of in situ and operando X-ray absorption spectroscopy in characterizing Li–S batteries. In this paper, we discuss in detail how this advanced technique helps researchers understand the redox process of the electrode materials as well as the influence of polymer binder and electrolyte additive on the polysulfide shuttle effect, which provide valuable information for designing better Li–S batteries. A general conclusion and critical further research directions are also provided at the end.

25 ENERGY STORAGE↗

A critical review of principal traffic noise models: Strategies and implications

The paper presents an exhaustive comparison of principal traffic noise models adopted in recent years in developed nations. The comparison is drawn on the basis of technical attributes including source modelling and sound propagation algorithms. Although the characterization of source in terms of rolling and propulsion noise in conjunction with advanced numerical methods for sound propagation has significantly reduced the uncertainty in traffic noise predictions, the approach followed is quite complex and requires specialized mathematical skills for predictions which is sometimes quite cumbersome for town planners. Also, it is sometimes difficult to follow the best approach when a variety of solutions have been proposed. This paper critically reviews all these aspects pertaining to the recent models developed and adapted in some countries and also discusses the strategies followed and implications of these models. - Highlights: • Principal traffic noise models developed are reviewed. • Sound propagation algorithms used in traffic noise models are compared. • Implications of models are discussed.

54 ENVIRONMENTAL SCIENCES↗

A short review of defect superlattice formation in metals and alloys under irradiation

Irradiation damage drives complex and coupled phenomena in materials at far-from-equilibrium conditions. The self-organization of nanoscale defects in materials under irradiation shows great potential to tailor the physical properties of materials by controlling nanopatterned microstructures. Irradiation-induced gas bubble and void superlattices are two important ordered nanostructures of great scientific interest. Although both types of superlattices have been investigated extensively, a consensus has yet to be reached on their formation mechanisms. In this review article, the current research status of gas bubble and void superlattices in metals and alloys and their characterization, structural stability, and mechanistic modeling are summarized. The fundamental research goals to advance the mechanistic understanding of gas bubble and void superlattices are outlined.

36 MATERIALS SCIENCE↗

Solid solution barium–strontium chlorides with tunable ammonia desorption properties and superior storage capacity

Metal halide ammines are very attractive materials for ammonia absorption and storage—applications where the practically accessible or usable gravimetric and volumetric storage densities are of critical importance. Here we present, that by combining advanced computational materials prediction with spray drying and in situ thermogravimetric and structural characterization, we synthesize a range of new, stable barium-strontium chloride solid solutions with superior ammonia storage densities. By tuning the barium/strontium ratio, different crystallographic phases and compositions can be obtained with different ammonia ab- and desorption properties. In particular it is shown, that in the molar range of 35–50% barium and 65–50% strontium, stable materials can be produced with a practically usable ammonia density (both volumetric and gravimetric) that is higher than any of the pure metal halides, and with a practically accessible volumetric ammonia densities in excess of 99% of liquid ammonia. - Graphical abstract: Thermal desorption curves of ammonia from Ba{sub x}Sr{sub (1−x)}Cl{sub 2} mixtures with x equal to 0.125, 0.25 and 0.5 and atomic structure of Sr(NH{sub 3}){sub 8}Cl{sub 2}. - Highlights: • Solid solutions of strontium and barium chloride were synthesized by spray drying. • Adjusting molar ratios led to different crystallographic phases and compositions. • Different molar ratios led to different ammonia ab-/desorption properties. • 35–50 mol% BaCl{sub 2} in SrCl{sub 2} yields higher ammonia density than any other metal halide. • DFT calculations can be used to predict properties of the mixtures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Modeling and characterizing the elastodynamic response of octet-truss lattice structures using resonance techniques

Characterization of additively manufactured materials and structures is an ongoing effort for the advanced manufacturing community. This article will investigate an approach using resonant spectral ultrasound (RUS) to measure the effective elastic constants of an Octet Truss lattice and apply the results to continuum bases models representing the lattice regions in different structures. The study is focused on simple lattices structures fabricated from Ti5553 using a laser powder bed fusion process (LBPF). Solid and lattice samples are measured to determine RUS estimates for the elastic properties of the bulk material and the effective elastic properties of the lattice structure. The estimated elastic properties are then incorporated into 3d finite element models using a continuum approximation of the physical AM parts. Comparisons show good agreement between the experimentally measured eigen frequencies of the Ti5553 LBPF parts and the eigen frequencies calculated using the continuum approximations based on the effective RUS elastic properties. The current results suggest there is additional physics and geometrical effects that are accounted for in the RUS continuum approximation of the lattice that are not captured in the full 3d finite element model of the parts utilizing only the base material properties.

36 MATERIALS SCIENCE↗

IsoForma: An R Package for Quantifying and Visualizing Positional Isomers in Top-Down LC-MS/MS Data

Proteoforms, the different forms of a protein with sequence variations including post-translational modifications (PTMs), execute vital functions in biological systems such as cell signaling and epigenetic regulation. Precisely defining the stoichiometry of PTMs has been challenging because, in the widely used bottom-up proteomics methods, the detection occurs at the peptide level and thus the link between peptides and their specific modification site is lost, resulting in proteoform ambiguity. Advances in top-down mass spectrometry (MS) technology have permitted the direct characterization of intact proteoforms and their exact number of modification sites, allowing for the relative quantification of positional isomers (PI). Proteins with positional isomers refers to proteoforms with identical total mass and set of modifications but varying PTM site combinations. The relative abundance of PI can be estimated by matching proteoform-specific fragment ions to top-down tandem MS (MS2) data to localize and quantify modifications. However, current approaches heavily rely on manual annotation. Here, we present IsoForma, an open-source R package for relative quantification of PI within a single tool. We benchmarked IsoForma’s performance against two existing workflows and highlight the similarity of the results and improvements in speed. Overall, IsoForma provides a streamlined process, reduces the time of conducting isoform-based analyses, and offers an essential framework for developing customized proteoform analysis workflows. Finally, the software is open source and available at https://github.com/EMSL-Computing/isoforma-lib.

59 BASIC BIOLOGICAL SCIENCES↗

Rapidly Assessing the Quality of Targeted Proteomics Experiments through Monitoring Stable-Isotope Labeled Standards

Selected reaction monitoring (SRM), also known as multiple reaction monitoring (MRM), is a data acquisition technique used in targeted analysis of molecules, including targeted proteomic studies. It exploits the unique capability of triple-quadrupole (QQQ) mass spectrometers to monitor the predefined precursor and fragment ion pairs of specific molecules of interest throughout a liquid chromatography (LC) elution profile. Compared to shotgun proteomics, targeted proteomics using SRM has high selectivity, high sensitivity, and a wide linear dynamic range,(1-3) which makes it especially useful in the accurate and reproducible quantification of low-abundance proteins in highly complex biological samples. SRM has been widely used in the fields of biomarker discovery,(4-7) analysis of protein post-translational modifications(8) and characterization of biological protein networks.(4,9) In the recent years, multiple technical advances have greatly improved the throughput of SRM analyses, allowing for the quantification of hundreds of peptides in a single analysis.(6,7,10) For example, a single 800-plex SRM assay (e.g., 400 unlabeled and heavy-labeled peptide pairs and 2400 transitions with retention time scheduling) using ultrahigh-performance liquid chromatography (UHPLC) has been developed to quantify proteins in plasma.(11) Advanced labeling techniques utilizing in vitro proteome-assisted MRM for protein absolute quantification (iMPAQT) demonstrated the capability of SRM in genome-wide protein quantification of over 18?000 human proteins.(12) Moreover, the scan speed of QQQ instrumentation has been greatly improved in recent releases of commercial instrumentation. The newly developed TSQ Altis (released in 2017) can scan more than 600 transitions per second, which is 6 times more than a traditional QQQ scan speed of 100 transitions per second. The breadth of measurement enabled by these technological improvements to QQQ mass spectrometry has increased the feasibility and popularity of large scale targeted proteomics studies,(13) a major application of which will be in clinical studies in which up to hundreds of protein candidates need to be quantified in hundreds of clinical specimens.(14) Quantitative accuracy is a primary motivating factor for utilizing a targeted proteomics protocol. The precise and reproducible absolute quantification produced by SRM assays is essential to many clinical and laboratory experiments.(15,16) Because the abundance of an endogenous peptide is calculated from the measurement of the spiked-in reference standard, it is essential to assess the data quality of these references.(17) In early applications of targeted proteomics, when instrument speed greatly limited the number of transitions that could be monitored, much of this quality assessment was done manually. However, recent improvements in instrument performance and experimental design have enabled a dramatic increase in the number of target peptides and associated SRM transitions, which makes manual quality assessment an untenable and laborious task. A variety of computational tools assist in SRM experiment design and data analysis. The first task in creating an SRM experiment is the choice of proteins and representative peptides to monitor. Achieving a reliable protein abundance requires appropriately choosing peptides that have a strong signal and are free from interferences in the biological matrix. Numerous computational tools exist to facilitate assay design by identifying peptides and refining SRM transitions.(18-21) To help share these assays and eliminate time spent designing the same transitions at multiple institutions, community portals have begun to host well-designed and vetted assays.(22-24) Analyzing the experimental data requires significant computational effort to align files across replicates and experimental conditions, pick peaks and produce quantitative values, normalize data and perform statistical tests, etc.(25-27)

Gibbons, Bryson C.↗

Three-Dimensional Mapping of Resistivity and Microstructure of Composite Electrodes for Lithium-Ion Batteries

Nanoparticle silicon–graphite composite electrodes are a viable way to advance the cycle life and energy density of lithium-ion batteries. However, characterization of composite electrode architectures is complicated by the heterogeneous mixture of electrode components and nanoscale diameter of particles, which falls beneath the lateral and depth resolution of most laboratory-based instruments. In this work, we report an original laboratory-based scanning probe microscopy approach to investigate composite electrode microstructures with nanometer-scale resolution via contrast in the electronic properties of electrode components. Applying this technique to silicon-based composite anodes demonstrates that graphite, SiOx nanoparticles, carbon black, and LiPAA binder are all readily distinguished by their intrinsic electronic properties, with measured electronic resistivity closely matching their known material properties. Resolution is demonstrated by identification of individual nanoparticles as small as ~20 nm. Our technique presents future utility in multiscale characterization to better understand particle dispersion, localized lithiation, and degradation processes in composite electrodes for lithium-ion batteries.

25 ENERGY STORAGE↗

Two Experimental Protocols for Accurate Measurement of Gas Component Uptake and Production Rates in Bioconversion Processes

Abstract Bioconversion processes offer many economic, environmental, and societal advantages for production of fuels and chemicals. Successful commercialization of any biotechnology usually requires accurate characterization of cell growth dynamics, substrate conversion and production excretion rates. Despite recent advancements in analytical equipment, obtaining accurate measurement of gas component uptake or production rates remains challenging due to their high sensitivity to system pressure or volume changes. Specifically, the consumption and production of various gases will result in changes in system pressure (for batch operations) or off-gas flow rate (for continuous operations). These changes would cause significant errors in the estimated gas component uptake and production rates if they were not accounted for. In this work, we propose two easy-to-implement experimental protocols and associated calculation procedures to obtain accurate measurements of gas component consumption and production rates; one is for batch operation and one is for continuous operation. For depressurized ( i . e ., system pressure below 1 atm) batch cultures, nitrogen (or other inert gases) is used to repressurize the system to 1 atm before taking sample; while for continuous cultures, He (or other inert gases) is used as an internal tracer to accurately measure off-gas flow rate. The effectiveness and accuracy of the two protocols and associated calculation procedures are demonstrated using several case studies with both abiotic and biotic systems.

59 BASIC BIOLOGICAL SCIENCES↗

Calibration of proton dispersion for the NIF electron positron proton spectrometer (NEPPS) for short-pulse laser experiments on the NIF ARC

Experiments using the Advanced Radiographic Capability (ARC) laser at the National Ignition Facility (NIF) aim to characterize short-pulse-driven proton beams for use as both probes and drivers for high-energy-density physics experiments. Measurements of ARC-driven proton beam characteristics, such as energy spectrum and conversion efficiency, rely on the NIF Electron Positron Proton Spectrometer (NEPPS). The NEPPS diagnostic is a version of an existing particle spectrometer which is used for detecting MeV electron and positron spectra via permanent magnetic field dispersion. These spectrometers have not yet been calibrated for protons and instead use an analytical calculation to estimate the dispersion. Small variations in the field uniformity can affect the proton dispersion due to the relatively small resolving power (E/dE) for this diagnostic. A broadband energy, laser-accelerated proton source was produced at the Titan laser to experimentally calibrate the proton dispersion. These experimental data were used to test the theoretical dispersion. Numerical simulations using measurements of the magnetic field variation within the diagnostic were used to obtain a realistic proton dispersion curve for the new NEPPS units. In conclusion, this procedure for obtaining each independent dispersion is applicable to all EPPS and NEPPS diagnostics, given the axial magnetic field profile.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

High-Throughput Computing on High-Performance Platforms: A Case Study

The computing systems used by LHC experiments has historically consisted of the federation of hundreds to thousands of distributed resources, ranging from small to mid-size resource. In spite of the impressive scale of the existing distributed computing solutions, the federation of small to mid-size resources will be insufficient to meet projected future demands. This paper is a case study of how the ATLAS experiment has embraced Titan -- a DOE leadership facility in conjunction with traditional distributed high- throughput computing to reach sustained production scales of approximately 52M core-hours a years. The three main contributions of this paper are: (i) a critical evaluation of design and operational considerations to support the sustained, scalable and production usage of Titan; (ii) a preliminary characterization of a next generation executor for PanDA to support new workloads and advanced execution modes; and (iii) early lessons for how current and future experimental and observational systems can be integrated with production supercomputers and other platforms in a general and extensible manner.

Oleynik, D↗

Cryo-EM analysis of S. aureus TarL, a polymerase in wall teichoic acid biogenesis central to virulence and antibiotic resistance

Wall teichoic acid (WTA), a covalent adduct of Gram-positive bacterial cell wall peptidoglycan, contributes directly to virulence and antibiotic resistance in pathogenic species. Polymerization of the Staphylococcus aureus WTA ribitol-phosphate chain is catalyzed by TarL, a member of the largely uncharacterized TagF-like family of membrane-associated enzymes. We report the cryo–electron microscopy structure of TarL, showing a tetramer that forms an extensive membrane-binding platform of monotopic helices. TarL is composed of an amino-terminal immunoglobulin-like domain and a carboxyl-terminal glycosyltransferase-B domain for ribitol-phosphate polymerization. The active site of the latter is complexed to donor substrate cytidine diphosphate–ribitol, providing mechanistic insights into the catalyzed phosphotransfer reaction. Furthermore, the active site is surrounded by electropositive residues that serve to retain the lipid-linked acceptor for polymerization. Our data advance general insight into the architecture and membrane association of the still poorly characterized monotopic membrane protein class and present molecular details of ribitol-phosphate polymerization that may aid in the design of new antimicrobials.

59 BASIC BIOLOGICAL SCIENCES↗

Beyond Arms-Control Monitoring

Expanded monitoring of the environment, everywhere and at all times, can advance arms control around the world, enhancing transparency among nations. In particular, improved characterization of the atmosphere now offers powerful opportunities for global monitoring, with multiple societal benefits. It may be useful to think of environmental monitoring as a long-term objective of arms-control verification.

arms-control monitoring↗

Topological grain boundary segregation transitions

Engineering the structure of grain boundaries (GBs) by solute segregation is a promising strategy to tailor the properties of polycrystalline materials. Solute segregation triggering phase transitions at GBs has been suggested theoretically to offer different pathways to design interfaces, but an understanding of their intrinsic atomistic nature is missing. Here, we combined atomic resolution electron microscopy and atomistic simulations to discover that iron segregation to GBs in titanium stabilizes icosahedral units (“cages”) that form robust building blocks of distinct GB phases. Owing to their five-fold symmetry, the iron cages cluster and assemble into hierarchical GB phases characterized by a different number and arrangement of the constituent icosahedral units. Our advanced GB structure prediction algorithms and atomistic simulations validate the stability of these observed phases and the high excess of iron at the GB that is accommodated by the phase transitions.

36 MATERIALS SCIENCE↗

Pharmacological Profiling of a Brugia malayi Muscarinic Acetylcholine Receptor as a Putative Antiparasitic Target

The diversification of anthelmintic targets and mechanisms of action will help ensure the sustainable control of nematode infections in response to the growing threat of drug resistance. G protein-coupled receptors (GPCRs) are established drug targets in human medicine but remain unexploited as anthelmintic substrates despite their important roles in nematode neuromuscular and physiological processes. Bottlenecks in exploring the druggability of parasitic nematode GPCRs include a limited helminth genetic toolkit and difficulties establishing functional heterologous expression. In an effort to address some of these challenges, we profile the function and pharmacology of muscarinic acetylcholine receptors in the human parasite Brugia malayi, an etiological agent of human lymphatic filariasis. While acetylcholine-gated ion channels are intensely studied as targets of existing anthelmintics, comparatively little is known about metabotropic receptor contributions to parasite cholinergic signaling. Using multivariate phenotypic assays in microfilariae and adults, we show that nicotinic and muscarinic compounds disparately affect parasite fitness traits. We identify a putative G protein-linked acetylcholine receptor of B. malayi (Bma-GAR-3) that is highly expressed across intramammalian life stages and adapt spatial RNA in situ hybridization to map receptor transcripts to critical parasite tissues. Tissue-specific expression of Bma-gar-3 in Caenorhabditis elegans (body wall muscle, sensory neurons, and pharynx) enabled receptor deorphanization and pharmacological profiling in a nematode physiological context. Finally, we developed an image-based feeding assay as a reporter of pharyngeal activity to facilitate GPCR screening in parasitized strains. We expect that these receptor characterization approaches and improved knowledge of GARs as putative drug targets will further advance the study of GPCR biology across medically important nematodes.

60 APPLIED LIFE SCIENCES↗

Model Catalysts: Simulating the Complexities of Heterogeneous Catalysts

Surface-science investigations have contributed significantly to heterogeneous catalysis in the past several decades. Fundamental studies of reactive systems on metal single crystals have aided researchers in understanding the effect of surface structure on catalyst reactivity and selectivity for a number of important reactions. Recently, model systems, consisting of metal clusters deposited on planar oxide surfaces, have facilitated the study of metal particle-size and support effects. These model systems not only are useful for carrying out kinetic investigations, but are also amenable to surface spectroscopic techniques, thus enabling investigations under realistic pressures and at working temperatures. By combining surface-science characterization methods with kinetic measurements under realistic working conditions, researchers are continuing to advance the molecular-level understanding of heterogeneous catalysis and are narrowing he pressure and material gap between model and real-world catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Spherical nanoindentation stress-strain analysis, Version 1

Nanoindentation is a tool that allows the mechanical response of a variety of materials at the nano to micron length scale to be measured. Recent advances in spherical nanoindentation techniques have allowed for a more reliable and meaningful characterization of the mechanical response from nanoindentation experiments in the form on an indentation stress-strain curve. This code base, Spin, is written in MATLAB (The Mathworks, Inc.) and based on the analysis protocols developed by S.R. Kalidindi and S. Pathak [1, 2]. The inputs include the displacement, load, harmonic contact stiffness, harmonic displacement, and harmonic load from spherical nanoindentation tests in the form of an Excel (Microsoft) spreadsheet. The outputs include indentation stress-strain curves and indentation properties as well their variance due to the uncertainty of the zero-point correction in the form of MATLAB data (.mat) and figures (.png). [1] S. Pathak, S.R. Kalidindi. Spherical nanoindentation stress–strain curves, Mater. Sci. Eng R-Rep 91 (2015). [2] S.R. Kalidindi, S. Pathak. Determination of the effective zero-point and the extraction of spherical nanoindentation stress-strain curves, Acta Materialia 56 (2008) 3523-3532.

Weaver, JordanS.↗

SLH Timing Belt Powertrain (Final Technical Report)

The main goal of this proposal was to develop and test a novel powertrain solution for the SLH hydroEngine, a low-cost, efficient low-head hydropower technology. Nearly two-thirds of U.S. renewable electricity is produced by hydropower (EIA 2010). According to the U.S. Department of Energy; this amount could be increased by 50% with small hydropower plants, often using already-existing dams (Hall 2004). There are more than 80,000 existing dams, and of these, less than 4% generate power (Blankinship 2009). In addition, there are over 800 irrigation districts in the U.S., many with multiple, non-power, low-head drops. These existing, non-power dams and irrigation drops could be retrofitted to produce distributed, baseload, renewable energy with appropriate technology. The problem is that most existing dams are low-head, or less than 30 feet in height (Ragon 2009). Only about 2% of the available low-head hydropower resource in the U.S. has been developed, leaving more than 70 GW of annual mean potential low-head capacity untapped (Hall 2004). Natel Energy, Inc. is developing a low-head hydropower turbine that operates efficiently at heads less than 6 meters and is cost-effective for deployment across multiple low-head structures. Because of the unique racetrack-like path taken by the prime-movers in the SLH, a flexible powertrain is required. Historically, the only viable technological solution was roller chain. Despite the having the ability to easily attach blades, roller chain is characterized by significant drawbacks, including high cost, wear, and vibration from chordal action. Advanced carbon- fiber-reinforced timing belts have been recently developed which, coupled with a novel belt attachment system developed by Natel Energy, result in a large reduction in moving parts, reduced mass and cost, and elimination of chordal action for increased fatigue life. The work done in this project affirmatively addressed each of the following 3 major uncertainties concerning a timing-belt based hydroEngine powertrain: 1. Can a belt handle the high torques and power loads demanded by the SLH? (Yes.) 2. Can the SLH blades be mounted to belt with a connection that can withstand the loads encountered in operation? (Yes.) 3. Can the belt, with blade attachments, live through the required cyclic loading? (Yes.) The research adds to the general understanding of sustainable small hydropower systems by using innovative system testing to develop and demonstrate performance of a novel powertrain solution, enabling a new type of hydroelectric turbine to be commercially developed. The technical effectiveness of the methods investigated has been shown to be positive through an extensive design and testing process accommodating many constraints and goals, with a major emphasis on high cycle fatigue life. Economic feasibility of the innovations has been demonstrated through many iterations of design for manufacturability and cost reduction. The project is of benefit to the public because it has helped to develop a solution to a major problem -- despite the large available potential for new low-head hydropower, high capital costs and high levelized cost of electricity (LCOE) continue to be major barriers to project development. The hydroEngine represents a significant innovation, leveraging novel fluid mechanics and mechanical configuration to allow lower-cost turbine manufacture and development of low head hydropower resources.

13 HYDRO ENERGY↗