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At least 19 records

Protocol for Engineered Compositional Asymmetry Within Nanodiscs

Membrane proteins remain the most challenging targets for structural characterization, yet their elucidation provides valuable insights into protein function, disease mechanisms, and drug specificity. Structural biology platforms have advanced rapidly in recent years, notably through the development and implementation of nanodiscs—discoidal lipid–protein complexes that encapsulate and solubilize membrane proteins within a controlled, native-like environment. While nanodiscs have become powerful tools for studying membrane proteins, faithfully reconstituting the compositional asymmetry intrinsic to nearly all biological membranes has not yet been achieved. Proper membrane leaflet lipid distribution is critical for accurate protein folding, stability, and insertion. Here, we share a protocol for reconstituting tailored compositional asymmetry within nanodiscs through membrane extraction from giant unilamellar vesicles (GUVs) treated with a leaflet-specific methyl-β-cyclodextrin (mβCD) lipid exchange. Nanodisc asymmetry is verified through a geometric approach: biotin-DPPE-preloaded mβCD engages in lipid exchange with the outer leaflet of POPC GUVs solubilized by the lipid-free membrane scaffold protein (MSP) Δ49ApoA-I to form nanodisc structures. Once isolated, nanodiscs are introduced to the biotin-binding bacterial protein streptavidin. High-speed atomic force microscopy imaging depicts nanodisc–dimer complexes, indicating that biotin-DPPE was successfully reconstituted into a single leaflet of the nanodiscs. This finding outlines the first step toward engineering tailored nanodisc asymmetry and mimicking the native environment of integral proteins—a potentially powerful tool for accurately reconstituting and structurally analyzing integral membrane proteins whose functions are modulated by lipid asymmetry.

Biological and medical sciences↗

Contribution of the mantle to the lunar asymmetry

Evidence of three kinds indicates a lunar compositional asymmetry: mare basalts are much more abundant on the near side; the incompatible rich KREEP component is mainly observed in near-side soils; and materials on the far side are less dense than those of the near side, as indicated by the 2-km offset between the center of mass and center of figure. Recent models to explain the 2-km offset are based on near side-far side differences in the thickness of crustal units. The most widely discussed model calls for a thickness of anorthosite of about 24 km greater on the far side than on the near side, but no satisfactory method of generating such a large difference has been proposed. It is suggested that much of the offset reflects longitudinal differences in mantle composition, primarily resulting from earlier (or more rapid) crystallization of the magma ocean on what is not the far-side hemisphere. As a result, the far-side mantle would be more magnesian and thus less dense than the near-side mantle.

Wasson, J. T.↗

Stable nanovesicles formed by intrinsically planar bilayers

Quatsome nanovesicles, formed through the self-assembly of cholesterol (CHOL) and cetyltrimethylammonium bromide (CTAB) in water, have shown long-term stability in terms of size and morphology, while at the same time exhibiting high CHOL-CTAB intermolecular binding energies. We hypothesize that CHOL/CTAB quatsomes are indeed thermodynamically stable nanovesicles, and investigate the mechanism underlying their formation. A systematic study was performed to determine whether CHOL/CTAB quatsomes satisfy the experimental requisites of thermodynamically stable vesicles. Coarse-grain molecular dynamics simulations were used to investigate the molecular organization in the vesicle membrane, and the characteristics of the simulated vesicle were corroborated with experimental data obtained by cryo–electron microscopy, small- and wide-angle X-ray scattering, and multi-angle static light scattering. CHOL/CTAB quatsomes fulfill the requisites of thermodynamically stable nanovesicles, but they do not exhibit the classical membrane curvature induced by a composition asymmetry between the bilayer leaflets, like catanionic nanovesicles. Instead, CHOL/CTAB quatsomes are formed through the association of intrinsically planar bilayers in a faceted vesicle with defects, indicating that distortions in the organization and orientation of molecules can play a major role in the formation of thermodynamically stable nanovesicles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Lunar asymmetry and palaeomagnetism

A model is proposed for the early lunar evolution which accounts for the compositional asymmetry between the nearside and farside of the moon and the natural remanent magnetism of lunar rocks. According to the model, the preferred gravitational energy state consisted of an asymmetric accumulation of a liquid iron alloy (Fe-Ni and a small amount of sulfur) which displaces upwards the cold primordial undifferentiated core. The resulting depth asymmetry of the outer partially molten zone leads eventually to the subcrustal accumulation of light magnesium-rich pyroxenes and olivine, preferentially in one hemisphere, sufficient to explain the offset and also indirectly providing a possible explanation for the nearside concentration of KREEP and mass basalt. Slow downward migration of iron releases gravitational energy sufficient for convection and dynamo generation in an iron layer for about a billion years.

Stevenson, D. J.↗

Thorium Enrichment within the Procellarum KREEP Terrane: The Record in Surface Deposits and Significance for Thermal Evolution

The nearside-farside structural and compositional asymmetry of the Moon was recognized during the early days of Apollo and the suggestion was made that the migration of mantle melts to the nearside would have been favored by early Earth-Moon orbital dynamics and nonuniform planetesimal bombardment. Recent global geochemical mapping by Lunar Prospector has provided additional data, particularly in the Th distribution, that strongly supports the notion of global, preferential melt migration, which led in part to the development of the Procellarum KREEP Terrane (PKT) [2-5]. The surface distribution of Th was then reshaped by basin-forming impacts into the PKT, especially the Imbrium impact, which was the last and largest to strike in that region. The Imbrium event probably excavated material from a partially molten zone deep in the crust and delivered Th-rich ejecta Moon-wide. A fundamentally important but poorly understood aspect of the global Th distribution is the concentration of Th in the subsurface rocks of the PKT crustal section. For example, depending on what assumptions are made, the PKT crustal section, which is about 12% of the crust and only about 1.2% of the whole Moon, may contain as much as 40% of the Moon's entire Th budget. Such a distribution of Th and related heat-producing elements would have had a profound effect on melting, mixing, and the thermal evolution of the PKT and the underlying mantle. In this abstract, we examine the compositions of terra formations within the PKT and relate them to some of the Th-bearing rock types known from the Apollo samples. It appears that the existence of the PKT may be a unifying concept for a number of petrologic and geochemical observations. From the initial Lunar Prospector gamma-ray spectrometer data(-about 5 deg. resolution) and from the preliminary low-orbit data, there appears to be a number of relatively hotter "spots" within the PKT in terms of Th concentration. Some of the hotter spots correspond to intermediate-sized craters that penetrated volcanic flows and excavated Th-rich, submare material, such as Aristarchus, Aristillus, and Kepler. Other spots, however, correspond to surficial formations that constitute mainly rough topography associated with Imbrium ejecta or circum-Imbrium ring mountains and do not necessarily imply the presence of exposed KREEP basalts. The Fra Mauro Formation south of Copernicus toward the Apollo 14 site and regions of the Alpes Formation southwest of Copernicus in the vicinity of Reinhold lie within the most prominent hotspot; here them concentration is consistent with that found in the Apollo 14 soils (about 12-13 ppm) when the proportions of Fra Mauro Formation and mare basalt are considered. The area between Copernicus and Kepler and northwest of Copernicus in terra extending to the Carpathians is similarly enriched in Th. The Apennines from Eratosthenes toward the Apollo 15 site contain elevated Th concentrations, as does the northwestern quadrant of circum-Imbrium terra, especially between (but not including) La Condamine and Plato, and in the region northwest of the Jura mountains extending southward past Mairan to the Gruithuisen-Domes region. Within the main topographic rim of Imbrium, the Apennine Bench formation south of Archimedes appears to have relatively elevated Th concentration. Comparing the map of Th distribution to a digital-elevation map derived from Clementine altimetry, it appears that most of the areas richest in Th occur where the surface is elevated relative to the majority of PKT volcanic plains. Not all rough topography within the PKT has such elevated Th, however. Based on an analysis of the 5 deg. data, and using the calibration of, the mean Th concentrations for mainly volcanic-resurfaced terrain and rugged terrain are similar (about 5.5 ppm). This occurs in part because craters that penetrated mare basalt excavated Th-rich material. Even so, there appear to be extensive areas of volcanic resurfacing that have no obvious extrinsic source of Th-rich material, suggesting that the basalts, themselves, may contain as much as 5-6 ppm Th. High-FeO concentrations (18 to >20 wt%) indicate that these are not KREEP basalts but mare basalts. If so, this is surprising because most of the Apollo-sampled mare basalts have very low-Th (typically <2 ppm). A variety of Th-rich materials occur in the sample collection, particularly in the samples from the Apollo 12,14, and 15 sites. The most abundant Th-rich rock types are the mafic impact-melt breccias, which although found at all sites, are most abundant at Apollo 14, where they dominate the rock samples and make up some 40% of the rock particles in the soil. These have Th concentrations ranging up to about 30 ppm and averaging about 18 ppm. The Apollo 14 soils contain about 13 ppm Th, reflecting the high abundance of this melt-breccia component. At the nearby Apollo 12 site, the rocks consist mainly of mare basalts, and these have low-Th concentrations, mostly <1 ppm. Among the nonmare rocks, however, a few such as complex breccia 12013 contain a variety of evolved lithologies and represent potential sources of Th-rich components ranging from 17 to 50 ppm. A single fragment of KREEP basalt from the Apollo 12 soil contains about 50 ppm Th. Despite the identification of highly Th-enriched lithologic components at the Apollo 12 site, the soils there vary linearly in composition so as to extrapolate to a moderate Th KREEP-basalt component or a composition like that of the Fra Mauro formation as reflected by Apollo 14 soil (14 ppm Th at 10 wt% FeO). The nearby Lansberg Crater (39-km diameter) is a likely candidate to have delivered submare material such as buried Fra Mauro or Alpes material to the Apollo 12 site. Additional information contained in the original.

Jolliff, B. L.↗

Phase coexistence implications of violating Newton’s third law

Newton’s third law, action = reaction, is a foundational statement of classical mechanics. However, in natural and living systems, this law appears to be routinely violated for constituents interacting in a nonequilibrium environment. Here, we use computer simulations to explore the macroscopic phase behavior implications of breaking microscopic interaction reciprocity for a simple model system. We consider a binary mixture of attractive particles and introduce a parameter that is a continuous measure of the degree to which interaction reciprocity is broken. In the reciprocal limit, the species are indistinguishable, and the system phase separates into domains with distinct densities and identical compositions. Furthermore, increasing nonreciprocity is found to drive the system to explore a rich assortment of phases, including phases with strong composition asymmetries and three-phase coexistence. Many of the states induced by these forces, including traveling crystals and liquids, have no equilibrium analogs. By mapping the complete phase diagram for this model system and characterizing these unique phases, our findings offer a concrete path forward toward understanding how nonreciprocity shapes the structures found in living systems and how this might be leveraged in the design of synthetic materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Double Diffusive Convection in Materials Processing

A great number of crystals grown in space are plagued by convective motions which contribute to structural flaws. The character of these instabilities is not well understood but is associated with density variations in the presence of residual gravity (g-jitter). As a specific example, past HgCdTe crystal growth space experiments by Lehoczky and co-workers indicate radial compositional asymmetry in the grown crystals. In the case of HgCdTe the rejected component into the melt upon solidification is HgTe which is denser than the melt. The space grown crystals indicate the presence of three dimensional flow with the heavier HgTe-rich material clearly aligned with the residual gravity (0.55-1.55 micro g) vector. This flow stems from double-diffusive convection, namely, thermal and solutal buoyancy driven flow in the melt. The study of double-diffusive convection is multi-faceted and rather vast. In our investigation, we seek to focus on one specific aspect of this discipline that is of direct relevance to materials processing especially crystal growth, namely, the side ways heating regime. This problem has been widely studied, both experimentally and numerically, in the context of solar ponds wherein the system is characterized by a linear salt (solutal) gradient with an imposed lateral temperature gradient. The induced flow instabilities arise from the wide disparity between the fluid thermal diffusivity and the solute diffusivity. The extension of the analysis to practical crystal growth applications has however not been rigorously made and understood. One subtle but important difference in crystal growth systems is the fact that die system solute gradient is non-linear (typically exponential). Besides, the crystal growth problem has the added complexities of solidification, both lateral and longitudinal thermal gradients and segregation phenomena in systems where binary and ternary compounds are being grown. This paper treats the side ways heating problem alone in a model fluid system. Results from detailed numerical calculations, mainly two dimensional are provided. The interactions between a non-linear solute gradient and an imposed transverse thermal gradient are investigated. The buoyancy effects are treated in the traditional Boussinesq approximation and also in a more complete density formulation to address recent concerns of the first approach especially in simulations of the system response in a reduced gravity environment. Detailed flow, temperature and solute field plots along with heat and mass transfer results are presented in the paper. Implications to practical crystal growth systems as discerned from the modeling results are also explored and reported.

Ramachandra, Narayanan↗

Hemispheric Asymmetry of the Annual and Semiannual Variation of Thermospheric Composition

We examine hemispheric asymmetry of the annual and semiannual variation of the ratio of O and N 2 concentrations ( O/N 2 ) using observations by the Global Ultraviolet Imager (GUVI) instrument onboard the Thermosphere Ionosphere Mesosphere Energetics and Dynamics satellite and compare them with Whole Atmosphere Community Climate Model with thermosphere-ionosphere eXtension (WACCM-X) model simulations. We found that in the equatorial region, the “equinox peaks” of the observed O/N 2 are near the end of March and October, and the two annual lows are near the beginning of July and January. Compared to the equatorial region, in the northern hemisphere (NH) low latitudes, the first “equinox peak” clearly shifts toward the December solstice, whereas in the southern hemisphere (SH) low latitudes, the “equinox peaks” shift toward the June solstice (JS), forming the hemispheric asymmetry characteristics of the annual and semiannual variation. Seasonal variation of O/N 2 shows no apparent phase variation with altitude, and the annual and semiannual pattern is consistent from year to year. WACCM-X reproduces the observed annual and semiannual pattern in NH but in SH, it simulates an annual variation instead of the observed annual and semiannual variation. The largest discrepancy occurs near JS in the lower and middle thermosphere: the simulated O density has an annual high near JS in SH; the simulated N 2 density has an annual high near JS in NH but a predominant annual low near JS in SH. These are not in the GUVI data. A weaker thermospheric meridional circulation in the winter hemisphere, or a reduced summer-to-winter latitudinal gradient of neutral temperature in WACCM-X simulations would make model-data comparisons more consistent.

thermosphere composition↗

Superhydrophobic composite asymmetric electrospun membrane for sustainable vacuum assisted air gap membrane distillation

Membrane distillation (MD) relies on superhydrophobic membranes that must achieve the competing goals of high liquid entry pressure (LEP) and high permeability. Here, in this study, we developed the first superhydrophobic composite electrospun asymmetric membrane using fluorinated graphite (FG). We also provided among the first comparisons of the relative benefits of membrane asymmetry and composite coatings via 3D electrospinning and spraying. FG particles increased the roughness and reduced the zeta potential of the membranes. Superhydrophobic composite membranes had a contact angle of 157° (sliding angle of 7°) and an LEP of 327 kPa. Long-term MD testing revealed that FG particles could increase MD's sustainability while decreasing membrane wetting. Vacuum-assisted air gap membrane distillation (V-AGMD) showed that the composite asymmetric membrane outperformed the non-asymmetric version (composite nanofiber) membrane by 21 % in average water flux and 25 % in average thermal efficiency because of the asymmetric structure of the membrane. The numerical model developed for the V-AGMD system also successfully predicted the water flux generated experimentally from the composite nanofiber and composite asymmetric membranes. Our results confirmed that electrospun asymmetric FG membranes with high contact angle, low sliding angle, high permeability, and high gained output ratio (GOR) would be promising candidates for sustainable MD.

36 MATERIALS SCIENCE↗

Sm-Nd and Rb-Sr Ages for MIL 05035: Implications for Surface and Mantle Sources

The Sm-Nd and Rb-Sr ages and also the initial Nd and Sr isotopic compositions of MIL 05035 are the same as those of A-881757. Comparing the radiometric ages of these meteorites to lunar surface ages as modeled from crater size-frequency distributions as well as the TiO2 abundances and initial Sr-isotopic compositions of other basalts places their likely place of origin as within the Australe or Humboldtianum basins. If so, a fundamental west-east lunar asymmetry in compositional and isotopic parameters that likely is due to the PKT is implied.

Nyquist, L. E.↗

Equivalence of active and passive gravitational mass using the moon

Based on an asymmetry in the composition of the moon, a limit is established for the violation of the equity of passive and active gravitational mass. It is suggested that the 2-km offset between the moon's center of figure and center of mass imply an asymmetry in the distribution of Fe and Al, and that the Fe on one side and the Al on the other must attract another with equal force in order for the moon to follow the orbit predicted by classical mechanics. Based on laser ranging data and a model for the moon's interior, the ratios of active to passive mass for Fe and Al are found to be equal to a precision of 4 x 10 to the -12th.

Bartlett, D. F.↗

Brominated lipid probes expose structural asymmetries in constricted membranes

Lipids in biological membranes are thought to be functionally organized, but few experimental tools can probe nanoscale membrane structure. Using brominated lipids as contrast probes for cryo-EM and a model ESCRT-III membrane-remodeling system composed of human CHMP1B and IST1, we observed leaflet-level and protein-localized structural lipid patterns within highly constricted and thinned membrane nanotubes. These nanotubes differed markedly from protein-free, flat bilayers in leaflet thickness, lipid diffusion rates and lipid compositional and conformational asymmetries. Simulations and cryo-EM imaging of brominated stearoyl-docosahexanenoyl-phosphocholine showed how a pair of phenylalanine residues scored the outer leaflet with a helical hydrophobic defect where polyunsaturated docosahexaenoyl tails accumulated at the bilayer surface. Combining cryo-EM of halogenated lipids with molecular dynamics thus enables new characterizations of the composition and structure of membranes on molecular length scales.

59 BASIC BIOLOGICAL SCIENCES↗

Growth of organized flow coherent motions within a single-stream shear layer: 4D-PTV measurements

Abstract This study investigates the evolution of a single-stream shear layer (SSSL) originating from a wall boundary layer past a backward-facing step. Utilizing a time-resolved 3D-Particle Tracking Velocimetry (4D-PTV) technique, we track the trajectories of fluorescent particles to gain insight into the flow characteristics of the SSSL. A compact water tunnel facility ( $$\textrm{Re}_\tau =1\,240$$ Re τ = 1 240 ) is fabricated to obtain an SSSL with a perpendicular slow entrainment stream past the separation edge. A hybrid interpolation approach that combines ensemble binning and Gaussian weighting is implemented to derive minimally filtered mean and instantaneous lower- and higher-order flow field parameters. Spanwise-dominant coherent motion accompanied by finer flow scales is observed to grow due to flow entrainment through “nibbling” actions of small-scale vortices, “engulfing” by large-scale vortices, and vortex pairing events. Furthermore, the non-zero-speed stream edge grows relatively faster than the zero-speed stream edge, showing a strong asymmetry in mixing composition across a mixing layer. The SSSL reaches self-similarity at a streamwise distance of $$\approx 55\,\theta _{0}$$ ≈ 55 θ 0 , where $$\theta _0$$ θ 0 is the initial momentum thickness from the separation edge, i.e., considerably shorter than reported in previous studies. A literature comparison of growth rate parameters raises intriguing questions regarding a potential inclusive growth scaling unifying the free shear layers. A turbulent kinetic energy (TKE) budget analysis reveals a negative production region immediately downstream of the separation edge attributed to a large positive streamwise gradient of streamwise velocity. In the self-similar region, the phase-averaged flow mapping demonstrates a larger concentration of turbulence production rate around the outer edges of spanwise vortices, specifically at the intersection of braids and vortices. Furthermore, a spatial separation exists in the regions of peak production and dissipation rates within the vortex core region favoring dissipation. The braids exhibit a larger concentration of turbulence diffusion rates, indicating their function as a conduit for exchanging turbulence between neighboring coherent motions.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Spectrophotometry and organic matter on Iapetus. 1: Composition models

Iapetus shows a greater hemispheric albedo asymmetry than any other body in the solar system. Hapke scattering theory and optical constants measured in the laboratory are used to identify possible compositions for the dark material on the leading hemisphere of Iapetus. The materials considered are poly-HCN, kerogen, Murchison organic residue, Titan tholin, ice tholin, and water ice. Three-component mixtures of these materials are modeled in intraparticle mixture of 25% poly-HCN, 10% Murchison residue, and 65% water ice is found to best fit the spectrum, albedo, and phase behavior of the dark material. The Murchison residue and/or water ice can be replaced by kerogen and ice tholin, respectively, and still produce very good fits. Areal and particle mixtures of poly-HCN, Titan tholin, and either ice tholin or Murchison residue are also possible models. Poly-HCN is a necessary component in almost all good models. The presence of poly-HCN can be further tested by high-resolution observations near 4.5 micrometers.

Wilson, Peter D.↗

Modeling the Nonlinear, Strain Rate Dependent Deformation of Woven Ceramic Matrix Composites With Hydrostatic Stress Effects Included

An analysis method based on a deformation (as opposed to damage) approach has been developed to model the strain rate dependent, nonlinear deformation of woven ceramic matrix composites with a plain weave fiber architecture. In the developed model, the differences in the tension and compression response have also been considered. State variable based viscoplastic equations originally developed for metals have been modified to analyze the ceramic matrix composites. To account for the tension/compression asymmetry in the material, the effective stress and effective inelastic strain definitions have been modified. The equations have also been modified to account for the fact that in an orthotropic composite the in-plane shear stiffness is independent of the stiffness in the normal directions. The developed equations have been implemented into a commercially available transient dynamic finite element code, LS-DYNA, through the use of user defined subroutines (UMATs). The tensile, compressive, and shear deformation of a representative plain weave woven ceramic matrix composite are computed and compared to experimental results. The computed values correlate well to the experimental data, demonstrating the ability of the model to accurately compute the deformation response of woven ceramic matrix composites.

Goldberg, Robert K.↗

Modeling the Nonlinear, Strain Rate Dependent Deformation of Shuttle Leading Edge Materials with Hydrostatic Stress Effects Included

An analysis method based on a deformation (as opposed to damage) approach has been developed to model the strain rate dependent, nonlinear deformation of woven ceramic matrix composites, such as the Reinforced Carbon Carbon (RCC) material used on the leading edges of the Space Shuttle. In the developed model, the differences in the tension and compression deformation behaviors have also been accounted for. State variable viscoplastic equations originally developed for metals have been modified to analyze the ceramic matrix composites. To account for the tension/compression asymmetry in the material, the effective stress and effective inelastic strain definitions have been modified. The equations have also been modified to account for the fact that in an orthotropic composite the in-plane shear response is independent of the stiffness in the normal directions. The developed equations have been implemented into LS-DYNA through the use of user defined subroutines (UMATs). Several sample qualitative calculations have been conducted, which demonstrate the ability of the model to qualitatively capture the features of the deformation response present in woven ceramic matrix composites.

Goldberg, Robert K.↗

Spherical asymmetry in thermospheric magnetic storms

It is suggested that spherical asymmetries in heat-input distribution during magnetic storms could be important in moving the center of thermospheric circulation toward the equator. Circumstantial evidence from neutral-composition data obtained by two satellites during a series of strong geomagnetic substorms is shown to suggest a pronounced hemispherical asymmetry in magnetic-storm-related energy deposition and to support the circulation concept. Ground-based observations of the F2 peak density in both hemispheres are used to complement the composition data and to confirm the concept of hemispherical asymmetry. The composition data are analyzed quantitatively on the basis of a linear circulation model for the cases of a zero heat source in the Northern Hemisphere, factor-of-two differences between the heat sources in the Northern and Southern Hemispheres, and identical heat sources in both hemispheres. The results are found to be in qualitative agreement with the suggestion of pronounced asymmetry in thermospheric circulation.

Mayr, H. G.↗