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At least 1,207 records · Page 67

Intricate short-range order in GeSn alloys revealed by atomistic simulations with highly accurate and efficient machine-learning potentials

GeSn alloys hold promise for silicon-compatible integrated applications in electronics, photonics, and topological quantum devices. However, understanding their intricate structures using density functional theory (DFT) calculations is hindered by spatiotemporal constraints. To overcome this limitation, we develop highly accurate and efficient machine-learning interatomic potentials based on a neuroevolution potential approach with farthest point sampling on a comprehensive DFT data set. The application of the developed machine-learning potential in large-scale atomistic simulations bridges the spatiotemporal gap between modeling and advanced characterizations, and facilitates the discovery of structural intricacies in GeSn alloys. Through extensive statistical sampling, we identify a type of short-range order (SRO) that is distinguished by both its structural signature and electronic band gap from the SRO structure previously predicted. Modeling based on a large simulation cell reveals the coexistence of nano SRO domains with various degrees of ordering, demonstrating a complex spatial heterogeneity of SRO structure. Finally, our study not only reinforces the significance of fine-level structural information in alloys, but it also constitutes an effective framework for exploring SRO in a broad range of complex alloys based on highly accurate and effective machine-learning potentials.

36 MATERIALS SCIENCE↗

Wave Events: Climatology, Trends, and Relationship to Northern Hemisphere Winter Blocking and Weather Extremes

Diagnostics of finite-amplitude local wave activity (LWA) are applied to the 500-hPa geopotential height field to diagnose persistent synoptic weather events of anomalously large wave activity in the Northern Hemisphere. By considering the cyclonic and anticyclonic components of LWA separately, persistent weather systems associated with large-amplitude troughs and ridges are detected. While anticyclonic wave events are predominantly found over Europe and Alaska, cyclonic wave events usually occur over East Asia and northeastern Canada. Those preferred regions correspond to the location of planetary-scale ridges and troughs, which contribute, together with transient anomalies, to the formation of wave events. Although wave events are not blocking events per definition, they are typically associated with increased blocking in their vicinity. Their spatial relationship to blocking, however, varies depending on their cyclonic or anticyclonic nature and the type of wave-breaking signatures. Wave events are also shown to be accompanied by warm or cold temperature extremes, whose spatial pattern depends on the type of events, cyclonic or anticyclonic, and the sector affected. Trends in the frequency of wave events indicate that cyclonic wave events and the associated cold extremes affecting East Asia have become more frequent in recent decades and could be linked to recent trends toward La Niña–like conditions in the Pacific and trends toward the negative phase of Arctic Oscillation.

54 ENVIRONMENTAL SCIENCES↗

Identification of Porphyrin-Silica Composite Nanoparticles using Atmospheric Solids Analysis Probe Mass Spectrometry

Porphyrins are critical pigments involved in biological energy transduction processes. Their abilities to absorb light, then convert it to energy, have raised the interest of using porphyrin nanoparticles as photosensitizers in photodynamic therapy. A current study showed that self- assembled porphyrin-silica composite nanoparticles can selectively destroy tumor cells, but detection of the cellular uptake of porphyrin-silica composite nanoparticles was limited to imaging microscopy. In this work, we developed a novel method to rapidly identify porphyrin-silica composite nanoparticles using Atmospheric Solids Analysis Probe-Mass Spectrometry (ASAP-MS). ASAP-MS can directly analyze complex mixtures without the need for sample preparation. Porphyrin-silica composite nanoparticles were vaporized using heated nitrogen desolvation gas, and their thermo-profiles were examined to identify distinct mass- to-charge (M/Z) signatures. HeLa cells were incubated in growth media containing the nanoparticles, and after sufficient washing to remove residual nanoparticles, the cell suspension was loaded onto the end of ASAP glass capillary probe. Upon heating, HeLa cells were degraded and porphyrin-silica composite nanoparticles were released. Vaporized nanoparticles were ionized and detected by MS. Furthermore, the cellular uptake of porphyrin-silica composite nanoparticles was identified using this ASAP-MS method.

36 MATERIALS SCIENCE↗

Missions to Near-Earth Asteroids: Implications for Exploration, Science, Resource Utilization, and Planetary Defense

Introduction: In 2009 the Augustine Commission identified near-Earth asteroids (NEAs) as high profile destinations for human exploration missions beyond the Earth-Moon system as part of the Flexible Path. More recently the U.S. presidential administration directed NASA to include NEAs as destinations for future human exploration with the goal of sending astronauts to a NEA in the mid to late 2020s. This directive became part of the official National Space Policy of the United States of America as of June 28, 2010. NEA Space-Based Survey and Robotic Precursor Missions: The most suitable targets for human missions are NEAs in Earth-like orbits with long synodic periods. However, these mission candidates are often not observable from Earth until the timeframe of their most favorable human mission opportunities, which does not provide an appropriate amount of time for mission development. A space-based survey telescope could more efficiently find these targets in a timely, affordable manner. Such a system is not only able to discover new objects, but also track and characterize objects of interest for human space flight consideration. Those objects with characteristic signatures representative of volatile-rich or metallic materials will be considered as top candidates for further investigation due to their potential for resource utilization and scientific discovery. Once suitable candidates have been identified, precursor spacecraft are required to perform basic reconnaissance of a few NEAs under consideration for the human-led mission. Robotic spacecraft will assess targets for potential hazards that may pose a risk to the deep space transportation vehicle, its deployable assets, and the crew. Additionally, the information obtained about the NEA's basic physical characteristics will be crucial for planning operational activities, designing in-depth scientific/engineering investigations, and identifying sites on the NEA for sample collection. Human Exploration Considerations: These missions would be the first human expeditions to interplanetary bodies beyond the Earth-Moon system and would prove useful for testing technologies required for human missions to Mars, Phobos and Deimos, and other Solar System destinations. Current analyses of operational concepts suggest that stay times of 15 to 30 days may be possible at a NEA with total mission duration limits of 180 days or less. Hence, these missions would undoubtedly provide a great deal of technical and engineering data on spacecraft operations for future human space exploration while simultaneously conducting detailed investigations of these primitive objects with instruments and equipment that exceed the mass and power capabilities delivered by robotic spacecraft. All of these activities will be vital for refinement of resource characterization/identification and development of extraction/utilization technologies to be used on airless bodies under low- or micro-gravity conditions. In addition, gaining enhanced understanding of a NEA s geotechnical properties and its gross internal structure will assist the development of hazard mitigation techniques for planetary defense. Conclusions: The scientific, resource utilization, and hazard mitigation benefits, along with the programmatic and operational benefits of a human venture beyond the Earth-Moon system, make a piloted sample return mission to a NEA using NASA s proposed human exploration systems a compelling endeavor.

Abell, P. A.↗

Microstructural and Rheological Transitions in Bacterial Biofilms

Biofilms are aggregated bacterial communities structured within an extracellular matrix (ECM). ECM controls biofilm architecture and confers mechanical resistance against shear forces. From a physical perspective, biofilms can be described as colloidal gels, where bacterial cells are analogous to colloidal particles distributed in the polymeric ECM. However, the influence of the ECM in altering the cellular packing fraction (Φ) and the resulting viscoelastic behavior of biofilm remains unexplored. Using biofilms of Pantoea sp. (WT) and its mutant (ΔUDP), the correlation between biofilm structure and its viscoelastic response is investigated. Experiments show that the reduction of exopolysaccharide production in ΔUDP biofilms corresponds with a seven-fold increase in Φ, resulting in a colloidal glass-like structure. Consequently, the rheological signatures become altered, with the WT behaving like a weak gel, whilst the ΔUDP displayed a glass-like rheological signature. By co-culturing the two strains, biofilm Φ is modulated which allows us to explore the structural changes and capture a change in viscoelastic response from a weak to a strong gel, and to a colloidal glass-like state. The results reveal the role of exopolysaccharide in mediating a structural transition in biofilms and demonstrate a correlation between biofilm structure and viscoelastic response.

viscoelasticity↗

Exploring parasite heterogeneity using single-cell RNA-seq reveals a gene signature among sexual stage Plasmodium falciparum parasites

The malaria parasite has a complex lifecycle, including several events of differentiation and stage progression, while actively evading immunity in both its mosquito and human hosts. Important parasite gene expression and regulation during these events remain hidden in rare populations of cells. Here, we combine a capillary-based platform for cell isolation with single-cell RNA-sequencing to transcriptionally profile 165 single infected red blood cells (iRBCs) during the intra-erythrocytic developmental cycle (IDC). Unbiased analyses of single-cell data grouped the cells into eight transcriptional states during IDC. Interestingly, we uncovered a gene signature from the single iRBC analyses that can successfully discriminate between developing asexual and sexual stage parasites at cellular resolution, and we verify five, previously undefined, gametocyte stage specific genes. Moreover, we show the capacity of detecting expressed genes from the variable gene families in single parasites, despite the sparse nature of data. In total, the single parasite transcriptomics holds promise for molecular dissection of rare parasite phenotypes throughout the malaria lifecycle.

60 APPLIED LIFE SCIENCES↗

Charge Delocalization and Vibronic Couplings in Quadrupolar Squaraine Dyes

Squaraines are prototypical quadrupolar charge-transfer chromophores that have recently attracted much attention as building blocks for solution-processed photovoltaics, fluorescent probes with large two-photon absorption cross sections, and aggregates with large circular dichroism. Their optical properties are often rationalized in terms of phenomenological essential state models, considering the coupling of two zwitterionic excited states to a neutral ground state. As a result, optical transitions to the lowest S 1 excited state are one-photon allowed, whereas the next higher S 2 state can only be accessed by two-photon transitions. A further implication of these models is a substantial reduction of vibronic coupling to the ubiquitous high-frequency vinyl-stretching modes of organic materials. Here, in this study, we combine time-resolved vibrational spectroscopy, two-dimensional electronic spectroscopy, and quantum-chemical simulations to test and rationalize these predictions for nonaggregated molecules. We find small Huang–Rhys factors below 0.01 for the high-frequency, 1500 cm –1 modes in particular, as well as a noticeable reduction for those of lower frequency modes in general for the electronic S 0 → S 1 transition. The two-photon allowed state S 2 is well separated energetically from S 1 and has weak vibronic signatures as well. Thus, the resulting pronounced concentration of the oscillator strength in a narrow region relevant to the lowest electronic transition makes squaraines and their aggregates exceptionally interesting for strong and ultrastrong coupling of excitons to localized light modes in external resonators with chiral properties that can largely be controlled by the molecular architecture.

36 MATERIALS SCIENCE↗

n -Type PbSe Quantum Dots via Post-Synthetic Indium Doping

We developed a postsynthetic treatment to produce impurity n-type doped PbSe QDs with In 3+ as the substitutional dopant. Increasing the incorporated In content is accompanied by a gradual bleaching of the interband first-exciton transition and concurrently the appearance of a size-dependent, intraband absorption, suggesting the controlled introduction of delocalized electrons into the QD band edge states under equilibrium conditions. We compare the optical properties of our In-doped PbSe QDs to cobaltocene treated QDs, where the n -type dopant arises from remote reduction of the PbSe QDs and observe similar behavior. Spectroelectrochemical measurements also demonstrate characteristic n -type signatures, including both an induced absorption within the electrochemical bandgap and a shift of the Fermi-level toward the conduction band. Finally, we demonstrate that the In 3+ dopants can be reversibly removed from the PbSe QDs, whereupon the first exciton bleach is recovered. Our results demonstrate that PbSe QDs can be controllably n -type doped via impurity aliovalent substitutional doping.

36 MATERIALS SCIENCE↗

Single reconstructed Fermi surface pocket in an underdoped single-layer cuprate superconductor

The observation of a reconstructed Fermi surface via quantum oscillations in hole-doped cuprates opened a path towards identifying broken symmetry states in the pseudogap regime. However, such an identification has remained inconclusive due to the multi-frequency quantum oscillation spectra and complications accounting for bilayer effects in most studies. We overcome these impediments with high-resolution measurements on the structurally simpler cuprate HgBa2CuO4+δ (Hg1201), which features one CuO2 plane per primitive unit cell. We find only a single oscillatory component with no signatures of magnetic breakdown tunnelling to additional orbits. Therefore, the Fermi surface comprises a single quasi-two-dimensional pocket. Quantitative modelling of these results indicates that a biaxial charge density wave within each CuO2 plane is responsible for the reconstruction and rules out criss-crossed charge stripes between layers as a viable alternative in Hg1201. Lastly, we determine that the characteristic gap between reconstructed pockets is a significant fraction of the pseudogap energy

36 MATERIALS SCIENCE↗

Impact of Alloy-Disorder-Induced Localization on Hole Diffusion in Highly Excited c -Plane and m -Plane (In, Ga) N Quantum Wells

The diffusion coefficient of holes can provide knowledge about carrier localization in (In, Ga)N, where the carrier dynamics are altered by randomly fluctuating potential landscape. In group-III nitrides, the diffusivity of holes is difficult to measure by electrical methods but it can be studied using optical techniques. Here, we investigate the dependence of the hole diffusion coefficient on direction and carrier density in c-plane and m-plane (In, Ga)N structures by employing the light-induced transient-grating technique. We show that the hole diffusion coefficient is anisotropic in the m-plane structure, where it is several times larger along the a crystallographic direction than along the c direction. Such anisotropy is observed within the broad range of carrier densities from 10 18 to 10 20 cm –3 . The diffusivity changes nonmonotonously with increasing photoexcitation, this dependence being different in thick and thin layers. We argue that an unexpectedly high diffusion coefficient at low carrier densities in thick quantum wells can be a signature of efficient hole transport via percolative paths occurring due to compositional disorder. In turn, a decrease of diffusivity with the excitation can reflect the effect of Coulomb blockade of these paths. Lastly, we demonstrate that disorder impacts carrier diffusivity even at carrier densities above 10 19 cm –3 , where the overflow of localized states must be included to explain the observed increase of the diffusion coefficient with the carrier density.

36 MATERIALS SCIENCE↗

Signatures of distinct impurity configurations in atomic-resolution valence electron-energy-loss spectroscopy: Application to graphene

The detection and identification of impurities and other point defects in materials is a challenging task. Signatures for point defects are typically obtained using spectroscopies without spatial resolution. Here in this paper, we demonstrate the power of valence electron-energy-loss spectroscopy (VEELS) in an aberration-corrected scanning transmission-electron microscope (STEM) to provide energy-resolved and atomically resolved maps of electronic excitations of individual impurities which, combined with theoretical simulations, yield unique signatures of distinct bonding configurations of impurities. We report VEELS maps for isolated Si impurities in graphene, which are known to exist in two distinct configurations. We also report simulations of the maps, based on density functional theory and dynamical scattering theory, which agree with and provide direct interpretation of observed features. We show that theoretical VEELS maps exhibit distinct and unambiguous signatures for the threefold- and fourfold-coordinated configurations of Si impurities in different energy-loss windows, corresponding to impurity-induced bound states, resonances, and antiresonances. With the advent of new monochromators and detectors with high energy resolution and low signal-to-noise ratio, the present work ushers an atomically resolved STEM-based spectroscopy of individual impurities as an alternative to conventional spectroscopies for probing impurities and defects.

36 MATERIALS SCIENCE↗

Reflectance Spectroscopy and Lunar Sample Science: Finally a Marriage After Far Too Long an Engagement

Inferences about the igneous and impact evolution of planetary bodies are based upon spectral remote sensing of their surfaces. However, it is not the rocks of a body that are seen by the remote sensing, but rather the regolith, that may contain small pieces of rock but also many other phases as well. Indeed, recent flybys of objects even as small as asteroid Ida have shown that these objects are covered by a regolith. Thus, spectral properties cannot be directly converted into information about the igneous history of the object. It is imperative to fully understand the nature of the regolith, particularly its finer fraction termed "soil," to appreciate the possible effects of "space weathering" on the reflectance spectra. We have initiated a study of our nearest, regolith-bearing body, the Moon, as "ground truth" for further probes of planetary and asteroidal surfaces. the foundation for remote chemical and mineralogical analyses lies in the physics underlying optical absorption and the linking of spectral properties of materials measured in the laboratory to well understood mineral species and their mixtures. From this statement, it is obvious that there should be a thorough integration of the material science of lunar rocks and soils with the remote-sensing observations. That is, the lunar samples returned by the Apollo missions provide a direct means for evaluation of spectral characteristics of the Moon. However, this marriage of the remote-sensing and lunar sample communities has suffered from a prolonged unconsummated betrothal, nurtured by an obvious complacency by both parties. To make more direct and quantitative links between soil chemistry/mineralogy and spectral properties, we have initiated a program to (1) obtain accurate characterization of the petrography of lunar soils (in terms relevant to remote analyses), coupled with (2) measurement of precise reflectance spectra, with testing and use of appropriate analytical tools that identify and characterize individual mineral and glass components. It is the finest-sized fractions of the bulk lunar soil that dominate the observed spectral signatures.

Taylor, Lawrence A.↗

The Primordial Inflation Explorer (PIXIE)

The Primordial Inflation Explorer is an Explorer-class mission to open new windows on the early universe through measurements of the polarization and absolute frequency spectrum of the cosmic microwave background. PIXIE will measure the gravitational-wave signature of primordial inflation through its distinctive imprint in linear polarization, and characterize the thermal history of the universe through precision measurements of distortions in the blackbody spectrum. PIXIE uses an innovative optical design to achieve background-limited sensitivity in 400 spectral channels spanning over 7 octaves in frequency from 30 GHz to 6 THz (1 cm to 50 micron wavelength). Multi-moded non-imaging optics feed a polarizing Fourier Transform Spectrometer to produce a set of interference fringes, proportional to the difference spectrum between orthogonal linear polarizations from the two input beams. Multiple levels of symmetry and signal modulation combine to reduce systematic errors to negligible levels. PIXIE will map the full sky in Stokes I, Q, and U parameters with angular resolution 2.6 degrees and sensitivity 70 nK per 1degree square pixel. The principal science goal is the detection and characterization of linear polarization from an inflationary epoch in the early universe, with tensor-to-scalar ratio r < 10(exp. -3) at 5 standard deviations. The PIXIE mission complements anticipated ground-based polarization measurements such as CMBS4, providing a cosmic-variance-limited determination of the large-scale E-mode signal to measure the optical depth, constrain models of reionization, and provide a firm detection of the neutrino mass (the last unknown parameter in the Standard Model of particle physics). In addition, PIXIE will measure the absolute frequency spectrum to characterize deviations from a blackbody with sensitivity 3 orders of magnitude beyond the seminal COBE/FIRAS limits. The sky cannot be black at this level; the expected results will constrain physical processes ranging from inflation to the nature of the first stars and the physical conditions within the interstellar medium of the Galaxy. We describe the PIXIE instrument and mission architecture required to measure the CMB to the limits imposed by astrophysical foregrounds.

Kogut, Alan↗

Hijacking a rapid and scalable metagenomic method reveals subgenome dynamics and evolution in polyploid plants

Premise: The genomes of polyploid plants archive the evolutionary events leading to their present forms. However, plant polyploid genomes present numerous hurdles to the genome comparison algorithms for classification of polyploid types and exploring genome dynamics. Methods: Here, the problem of intra- and inter-genome comparison for examining polyploid genomes is reframed as a metagenomic problem, enabling the use of the rapid and scalable MinHashing approach. To determine how types of polyploidy are described by this metagenomic approach, plant genomes were examined from across the polyploid spectrum for both k-mer composition and frequency with a range of k-mer sizes. In this approach, no subgenome-specific k-mers are identified; rather, whole-chromosome k-mer subspaces were utilized. Results: Given chromosome-scale genome assemblies with sufficient subgenome-specific repetitive element content, literature-verified subgenomic and genomic evolutionary relationships were revealed, including distinguishing auto- from allopolyploidy and putative progenitor genome assignment. The sequences responsible were the rapidly evolving landscape of transposable elements. An investigation into the MinHashing parameters revealed that the downsampled k-mer space (genomic signatures) produced excellent approximations of sequence similarity. Furthermore, the clustering approach used for comparison of the genomic signatures is scrutinized to ensure applicability of the metagenomics-based method. Discussion: The easily implementable and highly computationally efficient MinHashing-based sequence comparison strategy enables comparative subgenomics and genomics for large and complex polyploid plant genomes. Such comparisons provide evidence for polyploidy-type subgenomic assignments. In cases where subgenome-specific repeat signal may not be adequate given a chromosomes' global k-mer profile, alternative methods that are more specific but more computationally complex outperform this approach.

59 BASIC BIOLOGICAL SCIENCES↗

Strain Tuning in Complex Oxide Epitaxial Films Using an Ultrathin Strontium Aluminate Buffer Layer

A reliable method to apply biaxial strain over a wide range of values with minimal dislocation generation is critical for the study of strain dependent physical properties in oxide thin films and heterostructures. In this study, we systematically controlled the strain state in a perovskite manganite thin film by as much as 1% using a new ultrathin strain-releasing buffer layer Sr 3 Al 2 O 6 , and observed signatures of accompanying magnetic and metal–insulator transitions. The near-zero strain state is achieved within five nanometers of buffer layer thickness, substantially thinner than any oxide epitaxial buffer layers that can continuously tune the film strain states. Furthermore, the majority of misfit dislocations were confined to the Sr 3 Al 2 O 6 layer, structurally decoupling defects in the film from the substrate.

36 MATERIALS SCIENCE↗

Cell type-resolved human lung lipidome reveals cellular cooperation in lung function

Cell type-resolved proteome analyses of the brain, heart and liver have been reported, however a similar effort on the lipidome is currently lacking. Here we applied liquid chromatography-tandem mass spectrometry to characterize the lipidome of major lung cell types isolated from human donors, representing the first lipidome map of any organ. We coupled this with cell type-resolved proteomics of the same samples (available at Lungmap.net). Complementary proteomics analyses substantiated the functional identity of the isolated cells. Lipidomics analyses showed significant variations in the lipidome across major human lung cell types, with differences most evident at the subclass and intra-subclass (i.e. total carbon length of the fatty acid chains) level. Further, lipidomic signatures revealed an overarching posture of high cellular cooperation within the human lung to support critical functions. Our complementary cell type-resolved lipid and protein datasets serve as a rich resource for analyses of human lung function.

Kyle, Jennifer E.↗

Mapping wave packet bifurcation at a conical intersection in CH 3 I by attosecond XUV transient absorption spectroscopy

Extreme ultraviolet (XUV) transient absorption spectroscopy has emerged as a sensitive tool for mapping the real-time structural and electronic evolution of molecules. Here, attosecond XUV transient absorption is used to track dynamics in the A-band of methyl iodide (CH 3 I). Gaseous CH 3 I molecules are excited to the A-band by a UV pump (277 nm, ~20 fs) and probed by attosecond XUV pulses targeting iodine I(4d) core-to-valence transitions. Owing to the excellent temporal resolution of the technique, passage through a conical intersection is mapped through spectral signatures of nonadiabatic wave packet bifurcation observed to occur at 15 ± 4 fs following UV photoexcitation. The observed XUV signatures and time dynamics are in agreement with previous simulations [H. Wang, M. Odelius, and D. Prendergast, J. Chem. Phys. 151, 124106 (2019)]. Furthermore, due to the short duration of the UV pump pulse, coherent vibrational motion in the CH 3 I ground state along the C-I stretch mode (538 ± 7 cm -1 ) launched by resonant impulsive stimulated Raman scattering and dynamics in multiphoton excited states of CH 3 I are also detected.

36 MATERIALS SCIENCE↗

Hybridization effect on the x-ray absorption spectra for actinide materials: Application to PuB 4

Studying the local moment and 5 f -electron occupations sheds insight into the electronic behavior in actinide materials. X-ray absorption spectroscopy (XAS) has been a powerful tool to reveal the valence electronic structure when assisted with theoretical calculations. However, the analysis currently taken in the community on the branching ratio of the XAS spectra generally does not account for the hybridization effects between local f orbitals and conduction states. In this paper, we discuss an approach which employs the density functional theory plus Gutzwiller rotationally invariant slave boson method to obtain a local Hamiltonian for the single-impurity Anderson model, and calculates the XAS spectra by the exact diagonalization (ED) method. A customized numerical routine was implemented for the ED XAS part of the calculation. By applying this technique to the recently discovered 5 f -electron topological Kondo insulator Pu B 4 , we determined the signature of 5 f -electronic correlation effects in the theoretical x-ray spectra. Furthermore, we found that the Pu 5 f - 6 d hybridization effect provides an extra channel to mix the j = 5 / 2 and 7 / 2 orbitals in the 5 f valence. As a consequence, the resulting electron occupation number and spin-orbit coupling strength deviate from the intermediate-coupling regime.

36 MATERIALS SCIENCE↗