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At least 1,081 records · Page 60

Ultraviolet Photooxidation of Smectite-Bound Fe(II) and Implications for the Origin of Martian Nontronites

Clay minerals detected with orbital and in situ instruments in ancient Martian terrains constrain Mars' climate and aqueous alteration history. Early in its history, Mars experienced an atmospheric redox change and iron-bearing clay minerals may preserve the effects of that transition. Ferrous smectites, the thermodynamically predicted product of chemical weathering of basalts under anoxic conditions, may have undergone oxidation by exposure to chemical oxidants in the atmosphere or regolith, or by direct photooxidation at the surface. To assess these potential oxidation pathways, ferrous trioctahedral smectites of varying initial iron content were synthesized and subjected to oxidation by ultraviolet (UV) irradiation. Experimental UV irradiation under an anoxic atmosphere equivalent to approximately 7 years of flux on the Martian surface caused partial oxidation of smectite-bound Fe (Fe3+/ΣFe = 16–18%) and octahedral sheet contraction. Metal-OH vibrational bands in visible/near infrared (VNIR) reflectance spectra of oxidized smectites changed in band depth and asymmetry with higher iron content. X-ray diffraction patterns of UV irradiated samples indicate the formation of a mixed di- and trioctahedral smectite or a secondary nontronite phase, possibly on the surfaces of higher iron content smectites. These experiments suggest that UV irradiation is able to oxidize structurally bound iron in smectites without the presence of other chemical oxidants. Photooxidation may have influenced the mineralogy, both syndepositionally and postdepositionally, of Martian alteration assemblages formed near the surface and this process needs not be limited to one part of their formation history. Plain Language Summary: Martian mineral assemblages observed with orbiters and rover instruments allow us to understand the planet's past climate and aqueous activity. Hydrated minerals that contain Fe(II) are of particular interest as they would have been affected by the early atmosphere becoming more oxidizing overtime, changing the structural iron into Fe(III). In this study, we synthesized Fe(II) smectites with varying iron content and irradiated them with an ultraviolet (UV) light source to test whether they could be photooxidized. Iron in the smectite minerals was incompletely oxidized by UV radiation after being exposed for the equivalent of approximately 7 years of exposure on the early Mars surface. The smectites with higher iron content showed more changes with photooxidation in their visible/near infrared spectra as well as in their X-ray diffraction patterns, two datasets collected by instruments on currently active Martian missions. These results suggest that UV photooxidation is a plausible contributor to the mineralogy and redox state of clay mineral assemblages observed at the Martian surface.

V. B. Rivera Banuchi↗

Synthesis of a laterally displaced cluster feed for a reflector antenna with application to multiple beams and contoured patterns

Two methods are described for efficiently synthesizing the excitation coefficients of a laterally displaced cluster feed in a reflector antenna subject to beam distortion. Applications are presented for rotationally symmetric paraboloids excited by an equilateral triangular array of feed elements. The basic cluster is a central element surrounded by a hexagonal ring. The first method - termed the sequential current method - determines a set of excitation coefficients which minimizes the phase distortion in the 'effective' aperture distribution of the reflector. The second method - termed the gradient optimization method - is such that the distortion in the secondary power pattern is directly minimized in a min-L2 form by a gradient optimization algorithm regarded as a systematic computer iteration procedure. Application to the synthesis of contour patterns is included.

Galindo-Israel, V.↗

Asymmetric oligomerization state and sequence patterning can tune multiphase condensate miscibility

Endogenous biomolecular condensates, composed of a multitude of proteins and RNAs, can organize into multiphasic structures with compositionally distinct phases. This multiphasic organization is generally understood to be critical for facilitating their proper biological function. However, the biophysical principles driving multiphase formation are not completely understood. Here we use in vivo condensate reconstitution experiments and coarse-grained molecular simulations to investigate how oligomerization and sequence interactions modulate multiphase organization in biomolecular condensates. We demonstrate that increasing the oligomerization state of an intrinsically disordered protein results in enhanced immiscibility and multiphase formation. Interestingly, we find that oligomerization tunes the miscibility of intrinsically disordered proteins in an asymmetric manner, with the effect being more pronounced when the intrinsically disordered protein, exhibiting stronger homotypic interactions, is oligomerized. Our findings suggest that oligomerization is a flexible biophysical mechanism that cells can exploit to tune the internal organization of biomolecular condensates and their associated biological functions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Optical strain measurement system development, phase 1

A laser speckle, differential strain measurement system was built and tested for future applications in hostile environments. One dimensional electronic correlation of speckle pattern movement allows a quasi-real time measure of strain. The system was used successfully to measure uniaxial strain reaching into plastic deformation of a test specimen, at temperatures ranging to 450 C. A resolution of 16 microstrain is given by the photodiode array sensor pitch and the specimen to sensor separation. The strain measurement limit of the gauge is determined by air density perturbations causing decorrelation of the reference and shifted speckle patterns, and may be improved by limiting convective flow in the immediate vicinity of the test specimen.

Lant, Christian T.↗

Optical generation of a circular harmonic filter for rotation and translation invariant optical pattern recognition

A new method to generate a circular harmonic filter with both rotation and translation invariance is described, which is based on a phase-shifted double-exposure (PSDE) technique. An expression for the peak correlation intensity at the origin for the correlation plane as a function of target orientation for the PSDE filter is derived. Experimental results confirming the theoretical predictions are provided.

Cheng, Yeou-Yen↗

Adaptively coupled phase retrieval in multi-peak Bragg coherent diffraction imaging

Recent advances in Bragg coherent diffraction imaging (BCDI) experimental techniques permit routine measurement of multiple Bragg peaks from a single crystalline grain. The resulting images contain the full lattice distortion vector field which can be differentiated to provide lattice strain and rotation. With the advent of fourth-generation synchrotron light sources, such multi-peak datasets are produced at high rates, facilitating the need for rapid phase retrieval of the multiple peaks and subsequent image analysis. Here we describe and demonstrate a new implementation of a coupled phase retrieval technique for multi-peak BCDI which simultaneously treats each Bragg peak of the dataset and produces a three-dimensional image of the crystal's morphology and lattice distortion field. In addition, this method uses the redundant information contained in the various Bragg diffraction patterns to detect and suppress spurious signal appearing on the detector in a subset of the measurements. Compared with manual data editing, adaptive coupling produces a more consistent phase profile in reciprocal space and sharper surfaces in direct space, with no significant difference in computational cost. These improvements reduce the need for manual preprocessing and enable robust high-throughput analysis of multi-peak BCDI data, supporting near-real-time strain microscopy at modern synchrotron facilities.

36 MATERIALS SCIENCE↗

Evolution of the Space Station Freedom module pattern

A reanalysis of the evolution configuration module pattern for Space Station Freedom is presented. The module pattern is to consist of one habitation module, one airlock, one cupola, two Space Shuttle Orbiter pressurized docking adapters, one assured crew return vehicle, and one pressurized logistics module. Three laboratory modules are also included. A phased plan has been developed on the basis of utilization analysis being performed and derived through actual and projected user mission requirements for the growth of pressurized elements. The evolution requirement impacts to the module pattern are outlined. Application of the growth philosophy and the physical limitations resulted in a number of core element ground rules for module pattern growth. Nodes and modules are to be grown symmetrically in order to optimize poor flight control characteristics and maximize the capability for crew dual egress between elements. Core module pattern elements are not to be grown along Y-Y axis from nodes 1 or 2 due to physical clearance problems with the thermal control system radiators operational envelope.

Gould, Marston↗

Remote Influence of Andean Convection on Amazonian Rainfall and Its Mechanisms

Models from Coupled Model Intercomparison Project Phase 6 produce too much precipitation over the Andes but too little over the Amazon or the Wet Andes-Dry Amazon (WADA) bias pattern. Unlike the conventional view that convection parameterization and land model deficiencies can contribute to Amazonian rainfall biases, we approach this long-standing biased model behavior through the lens of Andean convection. Using Community Earth System Model v1.1 and focusing on the wet season, our mechanism-denial experiments demonstrate that Andean convection notably reduces precipitation over the Amazon during austral summer. The Andean forced Amazonian response operates on weather timescale. Furthermore, the reduction of Amazonian rainfall is detectable within a few hours after initial Andean forcing. The precipitation response is primarily driven by variations in the moisture budget and is moderated by changes in convective available potential energy over the Amazon. Changes in the total advection of moisture over the Amazon are dominated by the vertical advection term and can be attributed to discrepancies in the dynamic omega field. In the experiments, the Andean east flank region is scrutinized where the vertical velocity and moisture fields play an intermediary role for the Andean driven WADA connection. The Andean forcing induces descending anomalies on the Andean east flank. The disturbances of wind and geopotential fields over the Andean east flank propagate eastward via Kelvin waves. Over the Amazon, descending anomalies and advective drying lead to reduction of mid-to-high level cloud, increase of shortwave cloud forcing and surface net radiation, and enhancement of themodynamic stability and rainfall reduction.

58 GEOSCIENCES↗

Analysis of the Amplitude Response of a Two-Point and a Two-Line/Multi-Point Focused Laser Differential Interferometer

Experiments were performed with two different focused laser differential interferometer (FLDI) instruments to assess the amplitude response of each instrument to a traveling shock-wave generated by a laser spark. The first FLDI instrument generated two measurement points, with each measurement point providing sensitivity to density fluctuations induced by the shockwave. By performing a cross-correlation between the signals obtained from each measurement point, the phase velocity of density fluctuations can be obtained. The second FLDI instrument generated two measurement lines that are oriented either parallel or orthogonal to the shockwave direction of travel with the resulting interference pattern sampled at multiple equally-spaced points along each line. As a result, this instrument provides density fluctuation measurement capability at multiple points simultaneously. When the measurement lines are oriented parallel to the shockwave direction of travel, the phase velocity, rate of change of the phase velocity, and acceleration of density fluctuations traveling along each line can be obtained by performing a cross-correlation between points along a single line. When the measurement lines are oriented orthogonal to the shockwave direction of travel, the spatially-varying phase velocity can be obtained by performing a cross-correlation between points at the same relative location on each measurement line. Computations of the shockwave generated by the laser spark are used to simulate the response of each instrument and are compared to the experimental results. High-speed Schlieren imaging has also been performed and is compared with the FLDI measurements and computational results.

Focused Laser Differential Interferometer↗

A regional comparison of sub-daily flow variability in regulated and unregulated rivers in the United States

Regulating rivers for hydropower or other purposes can dramatically alter river flow patterns, including creating substantial changes in flow over short, minutes-to-hours-long timespans known as sub-daily flow variability (SDFV). The impacts of flexible hydropower production on flow and aquatic organisms are increasingly documented in research. However, the degree to which flow alteration relates to different hydropower operational modes in distinct geographical regions and seasons is not well understood. This study offers a methodology for regional- and species-appropriate evaluations of potential impacts of flow on fish based on sub-daily flow characteristics of hydropower operational modes. We analyzed 15-min discharge data between 2018 and 2021 from 69 USGS stream gages to compare SDFV in hydropeaking, run-of-river, and unregulated systems in the US Southeast and Pacific Northwest. Regulated systems exhibited significant SDFV downstream from hydropower facilities relative to unregulated systems, but specific impacts differed between regions. Regulated systems in the Southeast were characterized by high flow coefficients of variation and ratios (hydropeaking only) and extended durations of daily upramping flow phases. Regulated systems in the Pacific Northwest were characterized by many short flow phases per day and large portions of the day spent upramping. Pacific Northwest unregulated systems displayed the strongest seasonal flow patterns while Southeastern hydropeaking systems displayed the greatest SDFV. Given that SDFV impacts multiple dimensions of fish ecology, region-specific sub-daily flow signatures have important implications for understanding and mitigating potential community-, species-, and age-specific effects on fish in different parts of the country.

Fish↗

Simulation of the Indian Summer Monsoon Using Comprehensive Atmosphere-land Interactions, in the Absence of Two-way Air-sea Interactions

Community Land Model version 2 (CLM2) as a comprehensive land surface model and a simple land surface model (SLM) were coupled to an atmospheric climate model to investigate the role of land surface processes in the development and the persistence of the South Asian summer monsoon. Two-way air-sea interactions were not considered in order to identify the reproducibility of the monsoon evolution by the comprehensive land model, which includes more realistic vertical soil moisture structures, vegetation and 2-way atmosphere-land interactions at hourly intervals. In the monsoon development phase (May and June). comprehensive land-surface treatment improves the representation of atmospheric circulations and the resulting convergence/divergence through the improvements in differential heating patterns and surface energy fluxes. Coupling with CLM2 also improves the timing and spatial distribution of rainfall maxima, reducing the seasonal rainfall overestimation by approx.60 % (1.8 mm/d for SLM, 0.7 mm/dI for CLM2). As for the interannual variation of the simulated rainfall, correlation coefficients of the Indian seasonal rainfall with observation increased from 0.21 (SLM) to 0.45 (CLM2). However, in the mature monsoon phase (July to September), coupling with the CLM2 does not exhibit a clear improvement. In contrast to the development phase, latent heat flux is underestimated and sensible heat flux and surface temperature over India are markedly overestimated. In addition, the moisture fluxes do not correlate well with lower-level atmospheric convergence, yielding correlation coefficients and root mean square errors worse than those produced by coupling with the SLM. A more realistic representation of the surface temperature and energy fluxes is needed to achieve an improved simulation for the mature monsoon period.

Monsoon Precipitation↗

Discovery Of A Rossby Wave In Jupiter's South Equatorial Region

A detailed study of the chevron-shaped dark spots on the strong southern equatorial wind jet near 7.5 deg S planetographic latitude shows variations in velocity with longitude and time. The chevrons move with velocities near the maximum wind jet velocity of approx.140 m/s, as deduced by the history of velocities at this latitude and the magnitude of the symmetric wind jet near 7 deg N latitude. Their repetitive nature is consistent with an inertia-gravity wave (n = 75-100) with phase speed up to 25 m/s, relative to the local flow, but the identity of this wave mode is not well constrained. However, high spatial resolution movies from Cassini images show that the chevrons oscillate in latitude with a approx.7-day period. This oscillating motion has a wavelength of approx.20 deg and a speed of approx.100 m/s, following a pattern similar to that seen in the Rossby wave plumes of the North Equatorial Zone, and possibly reinforced by it, though they are not perfectly in phase. The transient anticyclonic South Equatorial Disturbance (SED) may be a similar wave feature, but moves at slower velocity. All data show chevron latitude variability, but it is unclear if this Rossby wave is present during other epochs, without time series movies that fully delineate it. In the presence of multiple wave modes, the difference in dominant cloud appearance between 7 deg N and 7.5 deg S may be due to the presence of the Great Red Spot, either through changes in stratification and stability or by acting as a wave boundary.

Simon-Miller, Amy A.↗

The decay of HIV under anti-retroviral therapy is biphasic even in humanized mice with just T cells

HIV-1 plasma viral load decays in a biphasic manner during antiretroviral therapy (ART). It was hypothesized that this is due to infection of different cell types, namely CD4+ T cells and macrophages. We studied this possibility directly by modeling the decay of HIV-1 in humanized mice. We utilized previously published data from humanized T-cell only mice (TOM) and myeloid-only mice (MOM) infected with HIV-1 and treated with a potent ART regimen. Viral load decay dynamics were modeled using either a single or a biexponential decay fitted using nonlinear mixed effects techniques. Fits were compared using the corrected Bayesian information criterion (BICc). In TOM, the biphasic model was significantly better than a single-phase decay model (ΔBICc ≈ 16) despite additional parameters. In MOM, the biphasic decay was statistically better, but there was substantial uncertainty because the virus goes below detection very fast. The first-phase half-life was consistent between groups (1.2 days in MOM and 1.3 days in TOM) and similar to the half-life estimated in human infection. The second-phase decay in these mice was minimal likely due to low initial viral loads. Additional analyses with mice containing both CD4+ T cells and macrophages or X4-tropic virus-infected MOM mice confirmed the biphasic pattern, demonstrating the robustness of this result. The biphasic decline in HIV-1 occurs, even with only CD4+ T cells, refuting the hypothesis that distinct cell populations (CD4+ T cells and macrophages) drive each decay phase. These findings support an alternative model in which the observed dynamics arise from intrinsic properties of the viral infection lifecycle rather than from cellular compartmentalization.

59 BASIC BIOLOGICAL SCIENCES↗

Unidirectional Sidechain Engineering to Construct Dual‐Asymmetric Acceptors for 19.23 % Efficiency Organic Solar Cells with Low Energy Loss and Efficient Charge Transfer

Abstract Achieving both high open‐circuit voltage ( V oc ) and short‐circuit current density ( J sc ) to boost power‐conversion efficiency (PCE) is a major challenge for organic solar cells (OSCs), wherein high energy loss ( E loss ) and inefficient charge transfer usually take place. Here, three new Y‐series acceptors of mono‐asymmetric asy‐YC11 and dual‐asymmetric bi‐asy‐YC9 and bi‐asy‐YC12 are developed. They share the same asymmetric D 1 AD 2 (D 1 =thieno[3,2‐ b ]thiophene and D 2 =selenopheno[3,2‐ b ]thiophene) fused‐core but have different unidirectional sidechain on D 1 side, allowing fine‐tuned molecular properties, such as intermolecular interaction, packing pattern, and crystallinity. Among the binary blends, the PM6 : bi‐asy‐YC12 one has better morphology with appropriate phase separation and higher order packing than the PM6 : asy‐YC9 and PM6 : bi‐asy‐YC11 ones. Therefore, the PM6 : bi‐asy‐YC12‐based OSCs offer a higher PCE of 17.16 % with both high V oc and J sc , due to the reduced E loss and efficient charge transfer properties. Inspired by the high V oc and strong NIR‐absorption, bi‐asy‐YC12 is introduced into efficient binary PM6 : L8‐BO to construct ternary OSCs. Thanks to the broadened absorption, optimized morphology, and furtherly minimized E loss , the PM6 : L8‐BO : bi‐asy‐YC12‐based OSCs achieve a champion PCE of 19.23 %, which is one of the highest efficiencies among these annealing‐free devices. Our developed unidirectional sidechain engineering for constructing bi‐asymmetric Y‐series acceptors provides an approach to boost PCE of OSCs.

Chemistry↗

High Pressure X-ray Diffraction and Equation of State of Hydrazine

Synchrotron X-ray diffraction has been used to investigate the structure and equation of state (EOS) of hydrazine (N 2 H 4 ) up to 54.3 GPa at 298 K. The diffraction patterns could be fit to a monoclinic unit-cell structure and put strong constraints on previously reported phase transitions documented by vibrational spectroscopy over this pressure range. Pressure–volume ( P–V ) data were fit using a Vinet EOS, yielding parameters: V 0 = 45.2 Å 3 /molecule (fixed), K 0 = 11.8(7) GPa, and K 0 ′ = 6.5(2). Previously measured high-pressure vibrational frequency shifts were used to estimate the vibrational free energy and model P–V–T isotherms from 0 to 1200 K. The results of the P–V–T isotherms are compared to existing shock Hugoniot data on hydrazine and 298 K isotherms for assemblages of possible decomposition products. This comparison suggests dissociation at high density under shock loading. Good correspondence was found between the static lattice EOS as calculated by the model and the previously reported EOS as calculated by density functional theory. Finally, these results resolve existing uncertainties about the EOS and crystal symmetry of hydrazine at high pressure and provide valuable baseline information on this important energetic material.

diffraction↗

Control over Banded Morphologies and Circular Dichroism in Chiral Halide Perovskites

Chiral halide perovskites (c-HPs) merge the chirality of organic cations with the semiconducting properties of metal halide frameworks, creating a family of chiral semiconductors with tunable chiroptoelectronic behavior. Here, we describe the impact of periodic banded morphologies of textured c-HP ( R/S -NEA) 2 PbBr 4 films (NEA = 1- (1-naphthyl)ethylammonium) on their chiroptical behavior. Due to the interplay between the crystalline and glassy phases, the c-HP film growth is driven by rhythmic precipitation, producing a distinctive controllable radial banded pattern with the ( R/S -NEA) 2 PbBr 4 inorganic planes oriented parallel to the substrate. The banded morphology can be controlled, as evidenced by the growth temperature dictating the ridge-to-ridge spacing as well as the density of banded regions. The resulting circular dichroism (CD) spectral shape, intensity, and polarity vary in a seemingly random manner across processing conditions. However, these spectral features can be explained by considering key features of the banded morphology, such as refraction of the incident light due to surface morphology, birefringence, and stacked, rotated crystallites. These effects cannot be canceled by averaging front and back CD spectra of c-HP films, and our model incorporating these effects reproduces all observed CD spectra remarkably well. The control over the c-HP morphology and prediction capabilities of our CD modeling leads to further understanding of this class of semiconductors and the possibility of exploiting structural features for light polarization control akin to enhanced metamaterials.

14 SOLAR ENERGY↗

Control of structure and spin texture in the van der Waals layered magnet CrSBr

Controlling magnetism at nanometer length scales is essential for realizing high-performance spintronic, magneto-electric and topological devices and creating on-demand spin Hamiltonians probing fundamental concepts in physics. Van der Waals (vdW)-bonded layered magnets offer exceptional opportunities for such spin texture engineering. Here, we demonstrate nanoscale structural control in the layered magnet CrSBr with the potential to create spin patterns without the environmental sensitivity that has hindered such manipulations in other vdW magnets. We drive a local phase transformation using an electron beam that moves atoms and exchanges bond directions, effectively creating regions that have vertical vdW layers embedded within the initial horizontally vdW bonded exfoliated flakes. We calculate that the newly formed two-dimensional structure is ferromagnetically ordered in-plane with an energy gap in the visible spectrum, and weak antiferromagnetism between the planes, suggesting possibilities for creating spin textures and quantum magnetic phases.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

A magnon scattering platform

Significance This work describes a general scattering platform that uses magnons to explore the underlying properties of target materials. In this work we show how both phase and amplitude of magnons can be imaged using a nitrogen vacancy center magnetometer and how the scattered pattern of waves can be used to infer geometric and magnetic properties of a target material. To demonstrate this new experimental methodology we use a permalloy disk as our target and show that even with such a simple target unexpected behavior is observed. In addition, we provide a theoretical framework to reconstruct the properties of the target.

36 MATERIALS SCIENCE↗