Molecular entrapment via homopolymer self-assembly
The present invention provides novel nanostructures comprising solution of PPSU 20 . Methods of preparing the novel PPSU nanostructures, and applications of such nanostructures are also provided.
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The present invention provides novel nanostructures comprising solution of PPSU 20 . Methods of preparing the novel PPSU nanostructures, and applications of such nanostructures are also provided.
We applied elastic thermobarometry on garnet-bearing migmatites along two transects through the crustal section at Sierra Valle Fértil-La Huerta, Argentina. We performed quartz-in-garnet barometry and zircon-in-garnet thermometry on metapelites from different paleo-depths across the crustal section. Our work recovers entrapment pressures ranging from 240 to 1330 MPa and entrapment temperatures between 691 and 1574 °C. The entrapment conditions are broadly consistent with anticipated pressures and temperatures along the crustal section derived previously using conventional, thermodynamic thermobarometers. The quartz-in-garnet barometer reproduces those conventionally established entrapment conditions when samples only experienced conditions within the alpha-quartz stability field. Raman-derived pressures for samples that experienced beta-quartz reference conditions are commonly much higher than those established by conventional barometry. Samples that preserve compressive (positive) residual pressures best reproduce reference entrapment pressures. Entrapment temperatures show high variability and overestimation of temperature conditions compared to conventional results. These results indicate elastic thermobarometry over- or under-estimates crystallization conditions in rocks crystallized at high temperatures, as is common in the Famatinian Arc deep-crust. We suggest that modeling quartz behavior across the alpha–beta transition may present challenges, as does shape maturation, viscous deformation, and radiation damage in zircon.
A technique based on matching the refractive index of an invading liquid to that of a fiber mat was used to study entrapment of air ('voids') that occurs during forced in-plane radial flow into nonwoven multifilament glass networks. The usefulness of this technique is demonstrated in quantifying and mapping the air pockets. Experiments with a series of fluids with surface tensions varying from 28 x 10(exp -3) to 36 x 10(exp -3) N/m, viscosities from 45 x 10(exp -3) to 290 x 10(exp -3) Pa.s, and inlet flow rates from 0.15 x 10(exp -6) to 0.75 x 10(exp -6) m(exp 3)/s, showed that void content is a function of the capillary number characterizing the flow process. A critical value of capillary number, Ca = 2.5 x 10(exp -3), identifies a zone below which void content increases exponentially with decreasing capillary number. Above this critical value, negligible entrapment of voids is observed. Similar experiments carried out on surface treated nonwoven mats spanning a range of equilibrium contact angles from 20 deg to 78 deg showed that there is a critical contact angle above which negligible entrapment is observed. Below this value, there is no apparent effect of contact angle on the void fraction - capillary number relationship described earlier. Studies on the effect of filament wettability, and fluid velocity and viscosity on the size of the entrapment (voids) were also carried out. These indicate that larger sized entrapments which envelop more than one pore are favored by a low capillary number in comparison to smaller, pore level bubbles. Experiments were carried out on deformed mats - imposing high permeability spots at regular intervals on a background of low permeability. The effect of these spatial fluctuations in heterogeneity of the mat on entrapment is currently being studied.
Abstract Jeffbenite (Mg 3 Al 2 Si 3 O 12 ) is a tetragonal phase found in so far only in superdeep diamonds, and its thermoelastic parameters are a prerequisite for determining entrapment pressures as it is regarded as a potential indicator for superdeep diamonds. In this study, the thermoelastic properties of synthetic Fe 3+ ‐jeffbenite were measured up to 33.7 GPa and 750 K. High‐temperature static compression data were fitted, giving ( ∂K T 0 / ∂ T ) P = −0.0107 (4) GPa/K and α T = 3.50 (3) × 10 −5 K −1 . The thermoelastic properties and phase stability are applied to modeling isomekes, or P‐T paths intersecting possible conditions of entrapment in diamond. We calculate that under ideal exhumation, jeffbenite entrapped at mantle transition zone conditions will exhibit a high remnant pressure at 300 K ( P inc ) of ∼5.0 GPa. Elastic geobarometry on future finds of jeffbenite inclusions can use the new equation of state to estimate entrapment pressures for this phase with still highly uncertain stability field in the mantle.
Illuminating past hydrological and climatological conditions in arid regions may provide insights into future trends in groundwater availability. The main objective of this study is to explore paleorecharge processes in the deep regional Nubian Sandstone Aquifer (NSA), which stretches below the hyperarid deserts of the Sinai Peninsula (Egypt) and the Negev (Israel), using dissolved noble gas data. Extremely high amounts of dissolved excess air (Ne concentrations up to 4 × solubility equilibrium) were observed in the ancient ( 81 Kr-depleted) groundwater that was recharged during past pluvial epochs in the basin. Here, the observed unique excess air signal and the clear spatiotemporal structure of the noble gas compositions in the aquifer are hypothesized to reflect two major characteristics of the groundwater system: (a) large-scale, long-term rises in the water table that facilitate the entrapment and dissolution of air bubbles under increased hydrostatic pressure, and (b) the geological settings in the southern recharge area in Sinai, including an almost horizontal position of the layers and intercalation of low-permeability rock formations within the aquifer, which inefficiently reject air bubbles from groundwater, thereby allowing for substantial entrapment of bubbles that dissolve as the water table rises. Enhanced dissolution of entrapped air was also observed in other paleo-groundwater-containing regional sandstone aquifers across North Africa, which, together with the recent findings from the NSA, suggest that largescale water table fluctuations have likely extensively occurred during past pluvial periods over these (and possibly other) arid regions. A preliminary assessment of noble gas recharge temperatures (NGTs) indicates an apparent decoupling of surface and water table temperatures in the case of deep aquifers with a thick (hundreds of m) unsaturated zone. This observed decoupling calls for a re-evaluation of previously obtained NGT records and a need for future work to consider the modification of NGTs due to soil air fractionation and geothermal heating of the underlying deep unsaturated zones.
Transcriptional regulators play key roles in plant growth, development and environmental responses; however, understanding how their regulatory activity is encoded at the protein level has been hindered by a lack of multiplexed large-scale methods to characterize protein libraries in planta. Here we present enrichment of nuclear trans-elements reporter assay in plants with sequencing (ENTRAP-seq), a high-throughput method that introduces protein-coding libraries into plant cells to drive a nuclear magnetic sorting-based reporter, enabling multiplexed measurement of regulatory activity from thousands of protein variants. Using ENTRAP-seq and machine learning, we screen 1,495 plant viruses and identify hundreds of putative transcriptional regulatory domains found in structural proteins and enzymes not associated with gene regulation. In addition, we combine ENTRAP-seq with machine-guided design to engineer the activity of a plant transcription factor in a semirational fashion. Our findings demonstrate how scalable protein function assays deployed in planta will enable the characterization of natural and synthetic coding diversity in plants.
Laser damage-prone precursors in high index materials such as hafnia are believed to be the primary limiter in the performance of dielectric multilayer films to advance ultra-high power and energy laser applications. Removing or suppressing these precursors is the key to fabricating laser damage resistant thin films for the enabling technologies. Early work has revealed that nanobubbles formed by entrapped argon (Ar) working gas in ion beam sputtering (IBS) produced hafnia films are primarily responsible for the onset of laser damage upon exposure to UV, ns-laser pulses. In this study, we demonstrate that the UV ns-laser damage onset of IBS produced hafnia films can be improved to 3.1 +/- 0.2 J/cm 2 by substituting the conventional Ar working gas with xenon (Xe), a nearly 1 J/cm 2 increase from that of the Ar produced hafnia films. In addition to the suppression of the overall point-defect density of the hafnia films, the reduction of the Xe entrapment eliminates the nanobubbles and the generation of plasmas that initiates the laser damage. The defect suppression and its correlation to the increase in laser damage threshold is revealed by the combined analysis of Rutherford backscattering spectroscopy, electron paramagnetic resonance spectroscopy, transmission electron microscopy, and laser damage testing. Monte Carlo simulations suggest a much smaller entrapment of Xe gas by comparison to Ar, which is attributed to the significant difference in the energy of the reflected neutrals (3X) which are likely to be implanted. These results provide an effective process route with a fundamental understanding for producing high laser damage resistant dielectric films for high power and high energy laser applications.
The Lab-On-a-Chip Application Development (LOCAD) team at NASA s Marshall Space Flight Center is utilizing Lab-On-a-Chip to support technology development specifically for Space Exploration. In this paper, we investigate the transient two-phase flow patterns in an optic well configuration with an entrapped bubble through numerical simulation. Specifically, the filling processes of a liquid inside an expanded chamber that has bubbles entrapped. Due to the back flow created by channel expansion, the entrapped bubbles tend to stay stationary at the immediate downstream of the expansion. Due to the huge difference between the gas and liquid densities, mass conservation issues associated with numerical diffusion need to be specially addressed. The results are presented in terms of the movement of the bubble through the optic well. Bubble removal strategies are developed that involve only pressure gradients across the optic well. Results show that for the bubble to be moved through the well, pressure pulsations must be utilized in order to create pressure gradients across the bubble itself.
Coating spallation events have been observed along the slip-side joggle region of the Space Shuttle Orbiter wing-leading-edge panels. One potential contributor to the spallation event is a pressure build up within subsurface voids or defects due to volatiles or water vapor entrapped during fabrication, refurbishment, or normal operational use. The influence of entrapped pressure on the thermo-mechanical fracture-mechanics response of reinforced carbon-carbon with subsurface defects is studied. Plane-strain simulations with embedded subsurface defects are performed to characterize the fracture mechanics response for a given defect length when subjected to combined elevated-temperature and subsurface-defect pressure loadings to simulate the unvented defect condition. Various subsurface defect locations of a fixed-length substrate defect are examined for elevated temperature conditions. Fracture mechanics results suggest that entrapped pressure combined with local elevated temperatures have the potential to cause subsurface defect growth and possibly contribute to further material separation or even spallation. For this anomaly to occur, several unusual circumstances would be required making such an outcome unlikely but plausible.
Previous oil containment booms have an open top that allows natural gas to escape, and have significant oil leakage due to wave action. Also, a subsea pyramid oil trap exists, but cannot move relative to moving oil plumes from deepsea oil leaks. The solution is to have large, moveable oil traps. One version floats on the sea surface and has a flexible tarp cover and a lower weighted skirt to completely entrap the floating oil and natural gas. The device must have at least three sides with boats pulling at each apex, and sonar or other system to track the slowly moving oil plume, so that the boats can properly locate the booms. The oil trap device must also have a means for removal of the oil and the natural gas. A second design version has a flexible pyramid cover that is attached by lines to ballast on the ocean floor. This is similar to fixed, metal pyramid oil capture devices in the Santa Barbara Channel off the coast of California. The ballast lines for the improved design, however, would have winches that can move the pyramid to always be located above the oil and gas plume. A third design is a combination of the first two. It uses a submerged pyramid to trap oil, but has no anchor and uses boats to locate the trap. It has ballast weights located along the bottom of the tarp and/or at the corners of the trap. The improved floating oil-spill containment device has a large floating boom and weighted skirt surrounding the oil and gas entrapment area. The device is triangular (or more than three sides) and has a flexible tarp cover with a raised gas vent area. Boats pull on the apex of the triangles to maintain tension and to allow the device to move to optimum locations to trap oil and gas. The gas is retrieved from a higher buoyant part of the tarp, and oil is retrieved from the floating oil layer contained in the device. These devices can be operated in relatively severe weather, since waves will break over the devices without causing oil leaking. Also, natural gas is entrapped and can be retrieved. All designs can use sonar to locate the moving oil plume, and then be relocated by using boats or winches to move the oil trapping devices. These devices can be constructed of treated, non-permeable DuPont Kevlar cloth (or similar material).
For applications in which unmanned vehicles must traverse unfamiliar terrain, there often exists the risk of vehicle entrapment. Typically, this risk can be reduced by using feedback from on-board sensors that assess the terrain. This work addressed the situations where a vehicle has already become immobilized or the desired route cannot be traversed using conventional rolling. Specifically, the focus was on using push-pull locomotion in high sinkage granular material. Push-pull locomotion is an alternative mode of travel that generates thrust through articulated motion, using vehicle components as anchors to push or pull against. It has been revealed through previous research that push-pull locomotion has the capacity for generating higher net traction forces than rolling, and a unique optical flow technique indicated that this is the result of a more efficient soil shearing method. It has now been found that pushpull locomotion results in less sinkage, lower travel reduction, and better power efficiency in high sinkage material as compared to rolling. Even when starting from an "entrapped" condition, push-pull locomotion was able to extricate the test vehicle. It is the authors' recommendation that push-pull locomotion be considered as a reliable back-up mode of travel for applications where terrain entrapment is a possibility.
Shergottites, the largest martian meteorite group, come from at least two geochemically different source reservoirs i.e. incompatible trace element (ITE)-depleted and enriched. The depleted shergottites are thought to be derived from an ITE-depleted mantle reservoir, while enriched shergottites are thought to be derived from an ITE-enriched mantle reservoir that represents late stage residual melt from a magma ocean or interaction with martian crust. Moreover, the martian crust is distinct from shergottites, by being highly oxidized, distinctly ITE-enriched, and older. The link between the crust and shergottite compositions is poorly understood. Here we model shergottite differentiation to resolve the origin of enriched shergottites and why the bulk martian crust is compositionally distinct from shergottites. Early formed olivine-hosted melt inclusions can provide primary melt composition from which the parental magma had crystallized and also information at different stages of crystallization during parent magma differentiation that leads to shergottite magma evolution as well as crustal contribution assessment. We analyzed olivine-hosted melt inclusions of two enriched poikilitic shergottites for their major, minor and trace element concentrations using electron microprobe and laser ablation ICP-MS. We corrected the melt inclusion compositions for post-entrapment re-equilibration with their host olivine. To comprehend the crystallization sequence of these rocks and whether the melt entrapment is consistent with the crystallization, we use MELTS models for equilibrium and fractional crystallization. The results of these models suggest that all the melts were trapped in a closed system progressive crystallization at 1150-1210 ⁰C within 1 kbar to 1 bar pressure that is equivalent to <8.5 km, implying melt entrapment without any additional exogenous materials.
The 2018 Lower East Rift Zone (LERZ) eruption of Kīlauea Volcano and the accompanying collapse of the summit caldera marked the most destructive phase of activity on Hawai’i in the last 200 years. The integration of petrological data extracted from lava samples collected throughout the eruption with geodetic data examining the caldera collapse event, and estimates of the co-erupted flux of SO2 from the main eruptive fissure (Fissure 8), provides an exceptional opportunity to determine the reservoir geometry and magma transport paths supplying Kīlauea’s LERZ. The forsterite contents of erupted olivines and the degree of disequilibrium with their carrier melts indicate that two distinct olivine populations were erupted from Fissure 8. Melt inclusion entrapment pressures reveal that more evolved olivines (Fo<81.5) crystallized at ~2 km depth within the shallower Halema’uma’u reservoir, while more primitive olivines (Fo>81.5)crystallized within the deeper South Caldera reservoir at ~3–5 km depth. Crucially, primitive olivines experienced extensive post-entrapment crystallization, driving the growth of a vapor bubble. Raman spectroscopy reveals that this bubble contains up to 99% of the total inclusionCO2 budget (median=93%). Measurements of CO2 in only the glass phase would have underestimated entrapment depths by up to 60× (median=11×), and the importance of the SC reservoir as a source of magma to Fissure 8 would have been overlooked. Overall, we demonstrate that Raman measurements of bubbles, along with careful choice of suitably-calibrated H2O-CO2 solubility model, is vital to place accurate constraints on the depths of magma storage regions supplying volcanic eruptions.
Gas-liquid flows through packed bed reactors (PBRs) are challenging to predict due to the tortuous flow paths that fluid interfaces must traverse. Experiments at the International Space Station showed that bubble and pulse flows are predominately observed under microgravity conditions, while the trickle and spray flows observed under terrestrial conditions are not present in microgravity. To understand the physics behind the former experiments, we simulate bubble flow through a PBR for different packing-particle-diameter-based Weber numbers and under different gravity conditions. We demonstrate different pore-scale mechanisms, such as capillary entrapment, buoyancy entrapment, and inertia-induced bubble displacement. Then, we perform a quantitative analysis by introducing new dynamic scales, dependent upon the evolving gas-liquid interfacial area, to understand the dynamic trade-offs between the inertia, capillary, and buoyancy forces on a bubble passing through a PBR. This analysis leads us to define new dimensionless Weber-like numbers that delineate bubble entrapment from bubble displacement.
Cell-free gene expression systems derived from bacterial lysates enable the expression of biosynthetic pathways from inexpensive and easily prepared DNA templates. These systems hold great promise for modular and on-demand bioproduction of valuable small molecules in resource-limited settings but are constrained in their long-term stability, reusability, and deployability. In this work, we demonstrate that multiple cell-free expressed enzymes can be co-immobilized in biocompatible hydrogels made from poly(ethylene glycol) diacrylate (PEGDA) with added glycerol for enhanced gel integrity. Using small-angle X-ray scattering (SAXS), we show that the mesh size of PEGDA-glycerol hydrogels is comparable to the globular sizes of many proteins and enzymes, which could be used for protein entrapment. We found that the combination between entrapment and chemical ligation of the enzymes was effective to retain proteins. By employing a method for direct fluorescence measurement from hydrogels, we found that proteins can be retained in PEGDA-glycerol for at least a week. By separating the cell-free enzyme expression from the immobilization step, we successfully fabricated enzyme-laden hydrogels with three heterologous cell-free enzymes for the bioconversion of pyruvic acid to malic acid, an industrially valuable and versatile precursor chemical. Both heterologous and endogenous enzymes from the lysate remain functional in photo-cross-linked hydrogels and can be reused for multiple biocatalytic cycles. Moreover, we also found that the immobilized enzymes exhibit up to 1.6-fold higher activity and 2-fold longer lifetimes than free enzymes in liquid reactions. Furthermore, these results could advance the deployment of cell-free synthetic biology because they show that reusable, stable, and durable multienzyme systems can be created using readily available materials and fabrication techniques.
We elucidate the evolution of the entrained air in drop impact on a wide range of liquids, using ultrafast X-ray phase-contrast imaging. We elaborate the retraction mechanism of the entrapped air film in terms of liquid viscosity. We found the criterion for deciding if the entrapped air evolves into single or double bubbles, as determined by competition among inertia, capillarity, and viscosity. Low viscosity and low surface tension induce a small daughter droplet encapsulated by a larger air shell bubble, forming an antibubble. We demonstrate a phase diagram for air evolution regarding hydrodynamics.
Directed energy deposition (DED) is increasingly valuable to many industries because of its high deposition rates relative to other metal additive manufacturing processes, but the design space of DED is limited. For instance, steep overhangs are difficult or impossible to manufacture. Polymer-based support structures could help address this challenge. The viability of DED on polymer composite substrates has begun to be explored, specifically with 316L stainless steel on carbon-fiber-reinforced ABS substrates. Monolithic metal components can be deposited on the polymer, but it was found that gas release during polymer degradation causes porosity due to gas entrapment in the metal. An interlayer cooling time was introduced to reduce polymer degradation and decrease the porosity due to gas entrapment, but this led to porosity from lack of fusion. The results of this work provide insight into process parameter selection and scan strategy development to enable the use of polymer support structures in blown-powder DED.
Atomic layer deposition (ALD) is a versatile technique for engineering the surfaces of porous polymers, imbuing the flexible, high-surface-area substrates with inorganic and hybrid material properties. Previously reported enhancements include fouling resistance, electrical conductance, thermal stability, photocatalytic activity, hydrophilicity, and oleophilicity. However, there are many poorly understood phenomena that introduce challenges in applying ALD to porous polymers. In this paper, we address five common challenges and ways to overcome them: (1) entrapped precursor, (2) embrittlement, (3) film fracture, (4) deformation, and (5) pore collapse. These challenges are often interrelated and can exacerbate one another. To investigate these phenomena, we applied various ALD chemistries to porous polymers including polyethersulfone, polysulfone, polyvinylidene fluoride, and polycarbonate track-etched membranes. Reaction-diffusion modeling revealed why certain precursors and processing conditions result in embrittling subsurface material growth, entrapment of unreacted precursors, and nongrowth. We quantify the limits of ALD processing temperatures that are dictated by thermal expansion mismatch and can lead to fractured ALD films. The results herein allow us to make recommendations to avoid, mitigate, or overcome the difficulties encountered when performing ALD and plasma-enhanced ALD on porous polymers. We intend this article to serve as a “lessons learned” guide informed by previous experience to provide a better understanding of the difficulties and limitations of ALD on porous polymers and knowledge-based guidelines for successful depositions. This knowledge can accelerate future research and help experimentalists navigate and troubleshoot as they expose porous polymers to reactive precursor vapors.