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At least 1,639 records · Page 91

Overlap Concentration in Salt-Free Polyelectrolyte Solutions

For strongly charged polyelectrolytes in salt-free solutions, we use molecular dynamics simulations of a coarse-grained bead-spring model to calculate overlap concentrations c* and chain structure for polymers containing N = 10 to 1600 monomers. Over much of this range, we find that the end-to-end distance R* at c* increases faster than linearly with increasing N, as chains at the overlap concentration approach strongly extended conformations. This trend results in the overlap concentration c* decreasing as a stronger function of N than the classical prediction c* ~ N –2 . Finally, this stronger dependence can be fit either by a logarithmic correction to scaling or by an apparent scaling c* ~ N –m , with m > 2.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Polyoxometalate-Assisted Crystallization: A General Strategy Enabling Structural Characterization of Molecular Radium Complexes

A fundamental understanding of radium (Ra) coordination chemistry has been hindered by the scarcity and radiological hazards of 226 Ra, leaving the structural characterization of molecular Ra complexes almost entirely unexplored. Here, we introduce a polyoxometalate (POM)-assisted crystallization strategy that enables single-crystal X-ray diffraction analysis of Ra–chelator complexes from microgram-scale samples. Employing the plenary Keggin anion [SiW 12 O 40 ] 4– , we isolated and structurally characterized Ra 2+ complexes of 18-crown-6 and the bis-picolinate macrocycle macropa, together with their Sr 2+ and Ba 2+ analogues. The resulting structures reveal systematic, size-dependent trends in coordination number and metal-donor distances across the alkaline earth series and provide the first direct experimental measurements of Ra–N and Ra–OCOO bond distances. Together, these results establish POM-assisted crystallization as a robust approach for obtaining solid-state structural information on Ra 2+ complexes of organic chelators, opening new opportunities to advance the coordination chemistry needed to fully realize radium’s potential in isotope production and targeted radiotherapy. More broadly, this approach expands the experimental toolkit available for studying scarce, highly radioactive elements accessible only in microgram quantities.

Anions↗

Forest tree growth is linked to mycorrhizal fungal composition and function across Europe

Most trees form symbioses with ectomycorrhizal fungi (EMF) which influence access to growth-limiting soil resources. Mesocosm experiments repeatedly show that EMF species differentially affect plant development, yet whether these effects ripple up to influence the growth of entire forests remains unknown. Here we tested the effects of EMF composition and functional genes relative to variation in well-known drivers of tree growth by combining paired molecular EMF surveys with high-resolution forest inventory data across 15 European countries. We show that EMF composition was linked to a three-fold difference in tree growth rate even when controlling for the primary abiotic drivers of tree growth. Fast tree growth was associated with EMF communities harboring high inorganic but low organic nitrogen acquisition gene proportions and EMF which form contact versus medium-distance fringe exploration types. These findings suggest that EMF composition is a strong bio-indicator of underlying drivers of tree growth and/or that variation of forest EMF communities causes differences in tree growth. While it may be too early to assign causality or directionality, our study is one of the first to link fine-scale variation within a key component of the forest microbiome to ecosystem functioning at a continental scale.

54 ENVIRONMENTAL SCIENCES↗

The origin of the Stokes–Einstein relation in simple dense liquids

Here, we investigate the origin of the universal relation between structural relaxation and diffusion in simple dense liquids, known as the Stokes–Einstein (SE) relation. The fact that this relation, originally derived from a hydrodynamic model of a macroscopic particle in a viscous medium, can describe the microscopic-scale liquid dynamics still eludes understanding. We introduce a new universal measure of structural relaxation in a system of N identical particles based on an explicit decomposition of the configuration space into N! congruent convex polyhedra. This measure makes it possible to quantify the correlation between two distinct particle configurations in terms of their minimal Euclidean distance, optimized with respect to particle permutations. Using this measure alongside a model of independent random walkers under the single-occupancy constraint, we derive a master equation that quantifies the SE relation. It allows us to demonstrate that the universal relation between structural relaxation and diffusion in simple dense liquids is caused by two conditions: (a) the confinement of the dominant density fluctuations to the first coordination shell, manifested by de Gennes narrowing, and (b) Gaussianity of the diffusion process; the former is shown to be violated in low-density fluids, and the latter is known to be violated in supercooled liquids.

Physics - Condensed matter physics↗

Effectiveness and predictability of in-network storage cache for Scientific Workflows

Large scientific collaborations often have multiple scientists accessing the same set of files while doing different analyses, which create repeated accesses to the large amounts of shared data located far away. These data accesses have long latency due to distance and occupy the limited bandwidth available over the wide-area network. To reduce the wide-area network traffic and the data access latency, regional data storage caches have been installed as a new networking service. To study the effectiveness of such a cache system in scientific applications, we examine the Southern California Petabyte Scale Cache for a high-energy physics experiment. By examining about 3TB of operational logs, we show that this cache removed 67.6% of file requests from the wide-area network and reduced the traffic volume on wide-area network by 12. 3TB (or 35.4%) an average day. The reduction in the traffic volume (35.4%) is less than the reduction in file counts (67.6%) because the larger files are less likely to be reused. Due to this difference in data access patterns, the cache system has implemented a policy to avoid evicting smaller files when processing larger files. We also build a machine learning model to study the predictability of the cache behavior. Tests show that this model is able to accurately predict the cache accesses, cache misses, and network throughput, making the model useful for future studies on resource provisioning and planning.

Sim, Caitlin↗

Seasonality regulates the structure and biogeochemical impact of ectomycorrhizal fungal communities across environmentally divergent neotropical dry forests

Abstract Ectomycorrhizal (ECM) symbioses support forest functioning globally, yet both the structure and function of ECM fungal communities in seasonally dry neotropical forests (SDTFs), known for extreme heterogeneity in vegetation and edaphic properties, remain under characterized. Here, we evaluated the relative influences of seasonal versus spatial variation in ECM fungal community structure in soils from four environmentally divergent SDTFs. We also assessed the importance of biotic and abiotic drivers of SDTF ECM fungal community structure at regional scales, as well as ECM impacts on soil carbon (C) and nitrogen (N) cycling. ECM fungal frequency, relative abundance and richness all increased in the wet season, but spatial rather than seasonal effects explained more variation in community composition. Across the four SDTFs investigated, differences in tree communities drove ECM fungal community turnover more than geographic distances, site abiotic conditions or soil chemistry. Although soil moisture and ECM tree basal area were stronger predictors of soil biogeochemistry, incorporating ECM fungal community composition and relative abundance added explanatory power to models of soil C and N cycling in the wet season. Synthesis : Our results highlight the importance of seasonality and plant community composition in shaping different aspects of SDTF ECM fungal community structure and diversity as well as the potential for both the plant and fungal components of ECM symbioses to impact soil functioning across heterogenous SDTFs. Furthermore, our findings suggest that alterations in SDTF plant community composition due to climate or land‐use change will have important consequences for ECM fungal diversity and associated effects on soil biogeochemical cycling.

54 ENVIRONMENTAL SCIENCES↗

Mimicking Natural Photosynthesis: Designing Ultrafast Photosensitized Electron Transfer into Multiheme Cytochrome Protein Nanowires

Efficient nanomaterials for artificial photosynthesis require fast and robust unidirectional electron transfer (ET) from photosensitizers through charge-separation and accumulation units to redox-active catalytic sites. We explored the ultrafast time-scale limits of photo-induced charge transfer between a Ru(II)tris(bipyridine) derivative photosensitizer and PpcA, a 3-heme c-type cytochrome serving as a nanoscale biological wire. Four covalent attachment sites (K28C, K29C, K52C, and G53C) were engineered in PpcA enabling site-specific covalent labeling with expected donor-acceptor (DA) distances of 4–8 Å. X-ray scattering results demonstrated that mutations and chemical labeling did not disrupt the structure of the proteins. Time-resolved spectroscopy revealed three orders of magnitude difference in charge transfer rates for the systems with otherwise similar DA distances and the same number of covalent bonds separating donors and acceptors. All-atom molecular dynamics simulations provided additional insight into the structure-function requirements for ultrafast charge transfer and the requirement of van der Waals contact between aromatic atoms of photosensitizers and hemes in order to observe sub-nanosecond ET. This work demonstrates opportunities to utilize multi-heme c-cytochromes as frameworks for designing ultrafast light-driven ET into charge-accumulating biohybrid model systems, and ultimately for mimicking the photosynthetic paradigm of efficiently coupling ultrafast, light-driven electron transfer chemistry to multi-step catalysis within small, experimentally versatile photosynthetic biohybrid assemblies.

36 MATERIALS SCIENCE↗

Interstellar bullets - H2O masers and Herbig-Haro objects

The paper considers the energy input to H2O masers in a dense molecular cloud and analyzes the response time scales for both collisional and radiative pump models. Specific mechanisms for magnetic energy input are given. The evolution of dense H2O maser clouds is studied in the environment of a young pre-main-sequence star that has developed an appreciable supersonic wind. It is shown that compact clouds can be ejected at high velocity to distances of order 1 pc. It is suggested that these clouds (referred to as interstellar bullets) might explain the phenomena of Herbig-Haro objects and high-velocity gas motions observed near compact infrared objects.

Norman, C.↗

Optical radiation associated with gamma-ray bursts

Calculations are made of the approximate characteristics of the reprocessed optical radiation resulting from the absorption of a gamma-ray burst by a nearby star. The overall reprocessing time scale, including contributions from gamma-ray transfer and diffusion of the optical radiation, is estimated. It is noted that diffusive cooling occurs by either a 'self-similar' or a 'transparency' wave of postabsorption stellar surface temperatures greater or less than 10,000 K, respectively. Depending on the combination of stellar and gamma-ray burst properties, the reprocessing time scale can vary from the duration of the gamma-ray burst (approximately 1 s) to the maximum calculated cooling time (approximately 1000 s). Calculations for close binary systems are made of the number of optical photons per square centimeter expected at earth as a function of the observed gamma-ray burst fluences and likely distances. It is predicted that, if all gamma-ray bursters are in close binaries, the number of detections per year by an all sky monitor of 200 photons per sq cm sensitivity will be about 100.

London, R. A.↗

Correlated observations of substorm effects in the near-earth region and the deep magnetotail

Simultaneous observations of energetic particle measurements from the geosynchronous satellite 1982-019 and magnetic field, electron plasma, and energetic proton and electron measurements obtained with ISEE 3 in the deep tail are presented. The data are supplemented by ground magnetograms. A substorm occurred on March 22, 1983, close to 0300 UT as identified in the ground magnetograms and by a particle injection at geosynchronous orbit. About 10 min later, ISEE 3 observed (at a distance of approximately 130 RE in the deep tail) magnetic field, plasma, and energetic particle signatures consistent with the passage of a plasmoid. After the passage of the plasmoid the satellite enters shortly into a lobelike environment, in which an energetic proton beam is observed. High-resolution magnetic field data are indicative of small-scale structures in the postplasmoid plasma sheet. From the plasma sheet flow speed during the plasmoid's passage it is concluded that the 0300 UT substorm is responsible for its origin. This allows an approximate timing of the plasmoid release at a near-earth neutral line and of the plasma sheet recovery after substorm onset, and it indicates a close relationship between processes in the near-earth plasma sheet and the deep tail during substorms.

Scholer, M.↗

Morphology of solar wind fluctuations and structure in the vicinity of the Sun from radio propagation measurements

Radio propagation measurements represent a powerful means for remote probing of electron density and solar wind speed in the acceleration region of the solar wind not yet explored by in situ measurements. Recent investigations based on radio propagation measurements have led to considerable progress in our knowledge of the general morphology of solar wind fluctuations and structure, especially in terms of their relationship to solar wind properties that have been observed directly by fields and particles measurements, and to coronal features observed in white-light measurements. The purpose of this paper is to present an overview of the latest results on quasi-stationary structure covering the large scale variation of solar wind speed over the streamer belt and coronal hole regions, coronal streamers (source of slow solar wind) and their associated small-scale electron density structure, plumes, density and fractional or relative density fluctuations, and the spectral characteristics of the electron density fluctuations. The radio propagation measurements not only reveal new information on the structure near the Sun, but also show that the structure appears to undergo substantial evolution on its way to 0.3 AU, the closest radial distance for which direct in situ spacecraft measurements are available.

Woo, R.↗

Functional Flight Test Report for Positive Systems' ADAR System 5500 Sensor SN8 Linear

This report describes results of the functional flight test conducted with the Positive Systems' ADAR 5500 sensor system (serial number 8, linear configuration) near Winslow, Arizona on June 30 and July 1, 1999. The in-flight test is one component of the NASA Scientific Data Purchase (SDP) Validation and Verification (V&V) process. It allows to measure characteristics of the entire sensor system affected by both performance of the sensor during a flight and post-flight image processing. The following characteristics were analyzed: changes of dark digital numbers (DN's), radiometric linearity, signal-to-noise ratio (SNR), spatial resolution, and geolocation accuracy. The measured characteristics were compared with the image product specifications defined in the Positive Systems' SDP contract. Dependence of the dark DN's on several factors was analyzed, but no significant correlation was found. However, the observed changes in dark DN's were relatively small, which justifies usage of a constant value in the dark DN subtraction procedure during post-processing. Dependence of measured at-sensor, in-band radiance (in arbitrary units) on measured in-band ground reflectance is very well described by a linear function - The sensor fulfills the linearity requirement. Measured SNR values lower than the contract specifications, but accuracy of that test was possibly affected by non-uniformity of the employed gray-scale panels. The SNR values are generally sufficiently high for most applications. SNR can also be improved during standard flights by using longer exposure times. Full width at half maximum (FWHM) of an edge response derived line spread function was used as a measure of spatial resolution. FWHM was generally smaller than twice the ground sample distance (GSD), in agreement with the contract specifications. Accuracy of the geolocation information, which is provided for the particular images in a metadata file, was found to meet contract requirements as well.

Stanley, Tom↗

Scaling device for photographic images

A scaling device projects a known optical pattern into the field of view of a camera, which can be employed as a reference scale in a resulting photograph of a remote object, for example. The device comprises an optical beam projector that projects two or more spaced, parallel optical beams onto a surface of a remotely located object to be photographed. The resulting beam spots or lines on the object are spaced from one another by a known, predetermined distance. As a result, the size of other objects or features in the photograph can be determined through comparison of their size to the known distance between the beam spots. Preferably, the device is a small, battery-powered device that can be attached to a camera and employs one or more laser light sources and associated optics to generate the parallel light beams. In a first embodiment of the invention, a single laser light source is employed, but multiple parallel beams are generated thereby through use of beam splitting optics. In another embodiment, multiple individual laser light sources are employed that are mounted in the device parallel to one another to generate the multiple parallel beams.

Rivera, Jorge E.↗

Crack Offset Measurement With the Projected Laser Target Device

The device and associated analysis methodology summarized in this report were developed for the purpose of estimating the size of discontinuities in the surface of the foam that covers the Space Shuttle External Tank. These surface offsets are thought to be due to subsurface cracks in the foam insulation. The mathematical analysis and procedure described here provide a method to quantity the dimensions of the crack offset in a direction perpendicular to the surface, making use of the projected laser target device (PLTD) tool and a laser line projector. The keys to the construction and use of the PLTD are the following geometrical design requirements: Laser dots are on a square grid: length on a side. Laser beams are perpendicular to projected surface. Beams are parallel out to the distance being projected. The PLTD can be used to (1) calibrate fixed cameras of unknown magnification and orientation (far-field solution); (2) provide equivalent calibration to multiple cameras, previously achieved only by the use of known target points, for example, in 3.D foreign-object debris tracking on a fixed launch platform; (3) compute scaling for conventional 2.D images, and depth of field for 3.D images (near-field solution); and (4) in conjunction with a laser line projector, achieve accurate measurements of surface discontinuity (cracks) in a direction perpendicular to the surface.

Source record↗

Signatures of Chemical Evolution in Protostellar Nebulae

A decade ago observers began to take serious notice of the presence of crystalline silicate grains in the dust flowing away from some comets. While crystallinity had been seen in such objects previously, starting with the recognitions by Campins and Ryan (1990) that the 10 micron feature of Comet Halley resembled that of the mineral forsterite, most such observations were either ignored or dismissed as no path to explain such crystalline grains was available in the literature. When it was first suggested that an outward flow must be present to carry annealed silicate grains from the innermost regions of the Solar Nebula out to the regions where comets could form (Nuth, 1999; 2001) this suggestion was also dismissed because no such transport mechanism was known at the time. Since then not only have new models of nebular dynamics demonstrated the reality of long distance outward transport (Ciesla, 2007; 2008; 2009) but examination of older models (Boss, 2004) showed that such transport had been present but had gone unrecognized for many years. The most unassailable evidence for outward nebular transport came with the return of the Stardust samples from Comet Wild2, a Kuiper-belt comet that contained micron-scale grains of high temperature minerals resembling the Calcium-Aluminum Inclusions found in primitive meteorites (Zolensky et aI., 2006) that formed at T > 1400K. Now that outward transport in protostellar nebulae has been firmly established, a re-examination of its consequences for nebular gas is in order that takes into account both the factors that regulate both the outward flow as well as those that likely control the chemical composition of the gas. Laboratory studies of surface catalyzed reactions suggest that a trend toward more highly reduced carbon and nitrogen compounds in the gas phase should be correlated with a general increase in the crystallinity of the dust (Nuth et aI., 2000), but is such a trend actually observable? Unlike the Fischer-Tropsch or the Haber-Bosch reactions used in industry, the surface catalyzed reactions seen in our laboratory do not produce a simple product stream of methane or ammonia, respectively. Instead, such reactions produce a wide range of both aliphatic and aromatic hydrocarbons, as well as reduced nitrogen compounds such as ammonia, amines, amides and imides, as gas phase products together with a heavy, macromolecular, kerogen-like surface coating that remains on the grains. While CO and N2 will certainly be depleted by conversion into more complex and less volatile species via reaction on grain surfaces, it may be very difficult to monitor such changes from outside the system.

Nuth, Joseph A., III↗

Non-singlet quark helicity $\mathrm{PDF}$s of the nucleon from pseudo-distributions

The non-singlet helicity quark parton distribution functions (PDFs) of the nucleon are determined from lattice QCD, by jointly leveraging pseudo-distributions and the distillation spatial smearing paradigm. A Lorentz decomposition of appropriately isolated space-like matrix elements reveals pseudo-distributions that contain information on the leading-twist helicity PDFs, as well as an invariant amplitude that induces an additional z 2 contamination of the leading-twist signal. An analysis of the short-distance behavior of the space-like matrix elements using matching coefficients computed to next-to-leading order (NLO) exposes the desired PDF up to this additional z 2 contamination. Due to the non-conservation of the axial current, we elect to isolate the helicity PDFs normalized by the nucleon axial charge at the same scale μ 2 . The leading-twist helicity PDFs as well as several sources of systematic error, including higher-twist effects, discretization errors, and the aforementioned z 2 contaminating amplitude are jointly determined by characterizing the computed pseudo-distribution in a basis of Jacobi polynomials. The Akaike Information Criterion is exploited to effectively average over distinct model parameterizations and cuts on the pseudo-distribution. Encouraging agreement is observed with recent global analyses of each non-singlet quark helicity PDF, notably a rather small non-singlet anti-quark helicity PDF for all quark momentum fractions.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Inexact convex relaxations for AC optimal power flow: Towards AC feasibility

Convex relaxations of AC optimal power flow (AC-OPF) problems have attracted significant interest as in several instances they provably yield the global optimum to the original non-convex problem. If, however, the relaxation is inexact, the obtained solution is not AC-feasible. The quality of the obtained solution is essential for several practical applications of AC-OPF, but detailed analyses are lacking in existing literature. Here, this paper aims to cover this gap. We provide an in-depth investigation of the solution characteristics when convex relaxations are inexact, we assess the most promising AC feasibility recovery methods for large-scale systems, and we propose two new metrics that lead to a better understanding of the quality of the identified solutions. We perform a comprehensive assessment on 96 different test cases, ranging from 14 to 3120 buses, and we show the following: (i) Despite an optimality gap of less than 1%, several test cases still exhibit substantial distances to both AC feasibility and local optimality and the newly proposed metrics characterize these deviations. (ii) Penalization methods fail to recover an AC-feasible solution in 15 out of 45 test cases. (iii) The computational benefits of warm-starting non-convex solvers have significant variation, but a computational speedup exists in over 75% of cases.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Detection of voids in hydrogen embrittled iron using transmission X-ray microscopy

Hydrogen embrittlement remains a barrier to widespread adoption of hydrogen as a carbon-neutral energy source. Here, hydrogen embrittlement mechanisms are investigated across length scales in iron using transmission X-ray microscopy (TXM), digital image correlation (DIC), and notched tensile testing during in-situ electrochemical hydrogen charging. TXM reveals void size and spatial distribution ahead of a propagating crack. We find hydrogen charging leads to voids within ~10 μm of the crack tip and suppression of voids beyond this distance. Near the crack tip, voids are elongated in the direction of the crack and are smaller than voids in an uncharged sample. In the presence of hydrogen, these voids lead to quasi-cleavage fracture and a sharper crack tip. DIC shows localization and reduction of plastic strain with hydrogen charging, and tensile testing reveals a reduction in fracture energy and elongation at failure. Finally, these results are discussed in the context of hydrogen embrittlement mechanisms.

08 HYDROGEN↗