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Isotope separation methods and systems

Methods and systems for the separation of isotopes from an aqueous stream are described as can be utilized in one embodiment to remove and recover tritium from contaminated water. Methods include counter-current flow of an aqueous stream on either side of a separation membrane. The separation membrane includes an isotope selective layer (e.g., graphene) and an ion conductive supporting layer (e.g., Nafion®). An electronic driving force encourages passage of isotopes selectively across the membrane to enrich the flow in the isotopes.

07 ISOTOPE AND RADIATION SOURCES↗

Tuning Molecular Interactions between Peptoids and Substrates to Achieve Surface-Agnostic Coating

Achieving programmable and robust coatings that maintain functionality while adhering to various surface types with molecular-level tunability and programmable features remains challenging. In this study, we develop adaptable and stable surface-agnostic coatings (SACs) based on crystalline peptoid membranes by tuning interpeptoid and peptoid-substrate interactions. We utilize two complementary methods: (1) surfaceinduced assembly, where peptoid membranes form directly on substrates, and (2) depositing preformed peptoid crystalline membranes via an aqueous layer-by-layer (LbL) assembly technique. These strategies are applied to substrates with diverse surface chemistries and topographies, including mica, highly ordered pyrolytic graphite (HOPG), MoS 2 , sapphire, and porous membranes like porous alumina and polysulfide. Atomic force microscopy confirms the formation of peptoid coatings and reveals differences in assembly behavior across surfaces. Moisture vapor transport measurements serve as a proof-of-concept test for membrane continuity and tunable permeance. Together, these findings demonstrate the adaptability and programmability of peptoid-based SACs, enabling rational coating design on surfaces with diverse chemical and topographical features. Furthermore, this work opens pathways for using peptoid membranes as programmable surface modifiers in functional interfaces, protective coatings, and membrane platforms.

biomimetic polymers↗

Meeting the Grand Challenge of Protecting Astronauts Health: Electrostatic Active Space Radiation Shielding for Deep Space Missions

This report describes the research completed during 2011 for the NASA Innovative Advanced Concepts (NIAC) project. The research is motivated by the desire to safely send humans in deep space missions and to keep radiation exposures within permitted limits. To this end current material shielding, developed for low earth orbit missions, is not a viable option due to payload and cost penalties. The active radiation shielding is the path forward for such missions. To achieve active space radiation shielding innovative large lightweight gossamer space structures are used. The goal is to deflect enough positive ions without attracting negatively charged plasma and to investigate if a charged Gossamer structure can perform charge deflections without significant structural instabilities occurring. In this study different innovative configurations are explored to design an optimum active shielding. In addition, to establish technological feasibility experiments are performed with up to 10kV of membrane charging, and an electron flux source with up to 5keV of energy and 5mA of current. While these charge flux energy levels are much less than those encountered in space, the fundamental coupled interaction of charged Gossamer structures with the ambient charge flux can be experimentally investigated. Of interest are, will the EIMS remain inflated during the charge deflections, and are there visible charge flux interactions. Aluminum coated Mylar membrane prototype structures are created to test their inflation capability using electrostatic charging. To simulate the charge flux, a 5keV electron emitter is utilized. The remaining charge flux at the end of the test chamber is measured with a Faraday cup mounted on a movable boom. A range of experiments with this electron emitter and detector were performed within a 30x60cm vacuum chamber with vacuum environment capability of 10-7 Torr. Experiments are performed with the charge flux aimed at the electrostatically inflated membrane structure (EIMS) in both charged and uncharged configurations. The amount of charge shielding behind and around the EIMS was studied for different combinations of membrane structure voltages and electron energies. Both passive and active shielding were observed, with active shielding capable of deflecting nearly all incoming electrons. The pattern of charge distribution around the structure was studied as well as the stability of the structures in the charge flow. The charge deflection experiments illustrate that the EIMS remain inflated during charge deflection, but will experience small amplitude oscillations. Investigations were performed to determine a potential cause of the vibrations. It is postulated these vibrations are due to the charge flux causing local membrane charge distribution changes. As the membrane structure inflation pressure is changed, the shape responds, and causes the observed sustained vibration. Having identified this phenomenon is important when considering electrostatically inflated membrane structures (EIMS) in a space environment. Additionally, this project included a study of membrane material impacts, specifically the impact of membrane thickness. Extremely thin materials presented new challenges with vacuum preparation techniques and rapid charging. The thinner and lighter membrane materials were successfully inflated using electrostatic forces in a vacuum chamber. However, care must be taken when varying the potentials of such lighter structures as the currents can cause local heating and melting of the very thin membranes. Lastly, a preliminary analysis is performed to study rough order of magnitude power requirements for using EIMS for radiation shielding. The EIMS power requirement becomes increasingly more challenging as the spacecraft voltage is increased. As a result, the emphasis is on the deflection of charges away from the spacecraft rather than totally stopping them. This significantly alleviates the initial power requirements. With modest technological development(s) active shielding is emerging to be a viable option.

Radiation↗

Hydrogen isotope separation methods and systems

Methods and systems for the separation of hydrogen isotopes from one another are described. Methods include utilization of a hydrogen isotope selective separation membrane that includes a hydrogen isotope selective layer (e.g., graphene) and a hydrogen ion conductive supporting layer. An electronic driving force encourages passage of isotopes selectively across the membrane at an elevated separation temperature to enrich the product in a selected hydrogen isotope.

07 ISOTOPE AND RADIATION SOURCES↗

Amyloplast sedimentation dynamics in maize columella cells support a new model for the gravity-sensing apparatus of roots

Quantitative analysis of statolith sedimentation behavior was accomplished using videomicroscopy of living columella cells of corn (Zea mays) roots, which displayed no systematic cytoplasmic streaming. Following 90 degrees rotation of the root, the statoliths moved downward along the distal wall and then spread out along the bottom with an average velocity of 1.7 microm min(-1). When statolith trajectories traversed the complete width or length of the cell, they initially moved horizontally toward channel-initiation sites and then moved vertically through the channels to the lower side of the reoriented cell where they again dispersed. These statoliths exhibited a significantly lower average velocity than those sedimenting on distal-to-side trajectories. In addition, although statoliths undergoing distal-to-side sedimentation began at their highest velocity and slowed monotonically as they approached the lower cell membrane, statoliths crossing the cell's central region remained slow initially and accelerated to maximum speed once they reached a channel. The statoliths accelerated sooner, and the channeling effect was less pronounced in roots treated with cytochalasin D. Parallel ultrastructural studies of high-pressure frozen-freeze-substituted columella cells suggest that the low-resistance statolith pathway in the cell periphery corresponds to the sharp interface between the endoplasmic reticulum (ER)-rich cortical and the ER-devoid central region of these cells. The central region is also shown to contain an actin-based cytoskeletal network in which the individual, straight, actin-like filaments are randomly distributed. To explain these findings as well as the results of physical simulation experiments, we have formulated a new, tensegrity-based model of gravity sensing in columella cells. This model envisages the cytoplasm as pervaded by an actin-based cytoskeletal network that is denser in the ER-devoid central region than in the ER-rich cell cortex and is linked to stretch receptors in the plasma membrane. Sedimenting statoliths are postulated to produce a directional signal by locally disrupting the network and thereby altering the balance of forces acting on the receptors in different plasma membrane regions.

NASA Program Fundamental Space Biology↗

Uniaxial and biaxial tensioning effects on thin membrane materials

Thin laminated membranes are being considered for various surface applications on future large space structural systems. Some of the thin membranes would be stretched across or between structural members with the requirement that the membrane be maintained within specified limits of smoothness which would be dictated by the particular applications such as antenna reflector requirements. The multiaxial tensile force required to maintain the smoothness in the membrane needs to be determined for use in the structure design. Therefore, several types of thicknesses of thin membrane materials have been subjected to varied levels of uniaxial and biaxial tensile loads. During the biaxial tests, deviations of the material surface smoothness were measured by a noncontacting capacitance probe. Basic materials consisted of composites of vacuum deposited aluminum on Mylar and Kapton ranging in thickness from 0.00025 in (0.000635 cm) to 0.002 in (0.00508 cm). Some of the material was reinforced with Kevlar and Nomex scrim. The uniaxial tests determined the material elongation and tensile forces up to ultimate conditions. Biaxial tests indicated that a relatively smooth material surface could be achieved with tensile force of approximately 1 to 15 Newtons per centimeter, depending upon the material thickness and/or reinforcement.

Hinson, W. F.↗

pH Homeostasis and Sodium Ion Pumping by Multiple Resistance and pH Antiporters in Pyrococcus furiosus

Multiple Resistance and pH (Mrp) antiporters are seven-subunit complexes that couple transport of ions across the membrane in response to a proton motive force (PMF) and have various physiological roles, including sodium ion sensing and pH homeostasis. The hyperthermophilic archaeon Pyrococcus furiosus contains three copies of Mrp encoding genes in its genome. Two are found as integral components of two respiratory complexes, membrane bound hydrogenase (MBH) and the membrane bound sulfane sulfur reductase (MBS) that couple redox activity to sodium translocation, while the third copy is a stand-alone Mrp. Sequence alignments show that this Mrp does not contain an energy-input (PMF) module but contains all other predicted functional Mrp domains. The P. furiosus Mrp deletion strain exhibits no significant changes in optimal pH or sodium ion concentration for growth but is more sensitive to medium acidification during growth. Cell suspension hydrogen gas production assays using the deletion strain show that this Mrp uses sodium as the coupling ion. Mrp likely maintains cytoplasmic pH by exchanging protons inside the cell for extracellular sodium ions. Deletion of the MBH sodium-translocating module demonstrates that hydrogen gas production is uncoupled from ion pumping and provides insights into the evolution of this Mrp-containing respiratory complex.

59 BASIC BIOLOGICAL SCIENCES↗

Conceptual design of electrostatic antenna

The concept of using electrostatic forces to tension a thin, conducting membrane and maintain it in a precision antenna shape is discussed. This electrostatically controlled membrane mirror is an adpative structure which maintains surface quality despite errors in construction, irregularities of materials, solar heating, and on board disturbances.

Coyner, J. V.↗

Zeolite Membrane Reactor for Pre-Combustion Carbon Dioxide Capture (Final Scientific/Technical Report)

Water-gas shift (WGS) reaction followed by carbon dioxide (CO 2 ) separation is a critical step in the integrated gasification combined cycle (IGCC) process for fossil-fuel-fired electrical power generation with CO 2 capture. To intensify the IGCC process hydrogen-permselective zeolite membrane reactor offers promise to replace the conventional energy-intensive fixed-bed reactors and solvent-based CO 2 capture units. The objectives of this project were to develop a bench-scale zeolite membrane reactor (total membrane area: 932 cm 2 for a 21-tube membrane bundle) for the water-gas-shift reaction of raw syngas from an oxygen-blown coal-gasifier for H 2 production with simultaneous CO 2 separation at the capability of about 2 kilograms H 2 per day (equivalent to 2 kW IGCC power plant) and to demonstrate significant progress toward achieving overall performance goal of 90% CO 2 capture rate with 95% CO 2 purity at the cost of electricity 30% less than the baseline carbon capture approaches. This report summarizes results obtained in this project on scaling up the zeolite membrane reactor by a factor of 200 in membrane area, tests of the bench-scale zeolite membrane reactor for the water-gas-shift reaction at high temperature and high-pressure, and techno-economic analysis of the integration of the zeolite membrane reactor in IGCC power plant for the electrical generation with CO 2 capture. With effective pore modification by catalytic cracking deposition of MDES (methyldiethoxysilane), fabrication of MFI-type zeolite membranes was successfully scaled-up from a lab-scale disk type to bench-scale multiple-tube bundles on low-cost alumina supports. A Co-Mo based sour shift catalyst was evaluated and used in the zeolite membrane reactors for water-gas-shift reaction. The reaction kinetic and gas-permeation equations were developed and employed in mathematic models to guide/predict experiments/performance of zeolite membrane reactors for water-gas shift reaction. Multiple-tube zeolite membrane bundles and reactors were designed, fabricated and tested for gas separation and water-gas-shift reactions with real raw syngas from a coal-fired gasifier operated at high temperature and pressure. The zeolite membrane reactors demonstrated good long-term thermal and chemical stability and constant H 2 permeance (>300 GPU) together with a Knudsen selectivity (~4.7) for H 2 over CO 2 in the field test (cumulative time >28 hours) with high-sulfur coal-derived syngas. The zeolite-membrane-reactor integrated IGCC process was designed using the performance experimentally measured by the University of Cincinnati team with a single-tube zeolite membrane reactor that offers a CO conversion >98% with more than 90% of CO 2 and H 2 captured. With the above integrative approaches, a techno-economic analysis for a cost-benefit comparison was performed to uncover features that determine the power output, capital expenditure, operating expenditure, cost of electricity and cost of CO 2 capture in a 550-MW zeolite-membrane-reactor integrated IGCC process. The integration of the zeolite membrane reactor in IGCC could provide a significant reduction of 80% and 27% in the power consumption for Selexol™ Acid Gas Removal and CO 2 compression, respectively, which lowers the total auxiliary power consumption by 12.5%. However, the low pressure required at permeate stream for maintaining the driving force of hydrogen permeation through the zeolite membrane costs a huge power in permeate compressor, compensating the power consumption reduction achieved with the membrane reactor. Thus, for coal-fired IGCC for electricity generation with 90% CO 2 captured, the integration of the membrane reactor could provide a CO conversion ~99% and a significant drop in cost-of-electricity using zeolite membrane with H 2 permeance >600 GPU and the H 2 /CO 2 selectivity over 70.

01 COAL, LIGNITE, AND PEAT↗

Histopathology of the Chimpanzee Ear

Four female and two male chimpanzees were secured in various positions on a Daisy Decelerator and subjected to forces ranging from 54 to 180 G. It was found that forces in excess of 54 G may rupture the tympanic membranes and cause subepithelial hemorrhages in the middle ear. The majority of cases showed proteinaceous material, with or without cells in the petrous air spaces. When exposed to forces above 119 G, there was engorgement and often rupture of the pericarotid venous plexus. When supine, distortion of both superior and posterior semicircular canals was found. With forces in excess of 54 G, the cupulae of the cristae ampullaris were either elevated or destroyed. The hair processes were also often broken off. The otolithic membranes, especially of the maculae utriculi were also elevated or otherwise distorted and the saccule was often partially collapsed. In several instances, there was an overabundance of a proteinaceous substance in the lumina of the vestibular apparatus and in the cochlear ducts with their associated scalae. In half the cases, the cochlear duct was narrowed by the depression of the vestibular membrane. Although there seems to be considerable individual variation in ability to withstand these forces, neither age, sex nor weight appear to directly influence the results. The possible sources for the materials found both in the air cells and labyrinth are discussed.

ACCELERATION TOLERANCE↗

Gravity Responsive NADH Oxidase of the Plasma Membrane

A method and apparatus for sensing gravity using an NADH oxidase of the plasma membrane which has been found to respond to unit gravity and low centrifugal g forces. The oxidation rate of NADH supplied to the NADH oxidase is measured and translated to represent the relative gravitational force exerted on the protein. The NADH oxidase of the plasma membrane may be obtained from plant or animal sources or may be produced recombinantly.

Morre, D. James↗

Data appendix: F-number=1.0 EMR with a flexible back electrode

A 12.5 micron Tedlar low f-number electrostatic membrane reflector was tested. The antenna reflector was designed to achieve a spherical reflector surface with a focal length to diameter ratio f(sub n) of one and a potential accuracy of 1.0 over its 4.88 m diameter. The configuration required the cutting and joining of twelve pie-shaped panels to form the reflector surface. Electrostatic forces are used to tension this preformed membrane reflector. The test data is spare-only three sets of measurements were taken due to lack of funds.

Mihora, D. J.↗

Mechanosensory calcium-selective cation channels in epidermal cells

This paper explores the properties and likely functions of an epidermal Ca(2+)-selective cation channel complex activated by tension. As many as eight or nine linked or linkable equivalent conductance units or co-channels can open together. Open time for co-channel quadruplets and quintuplets tends to be relatively long with millimolar Mg2+ (but not millimolar Ca2+) at the cytosolic face of excised plasma membrane. Sensitivity to tension is regulated by transmembrane voltage and temperature. Under some circumstances channel activity is sychronized in rhythmic pulses. Certain lanthanides and a cytoskeleton-disturbing herbicide that inhibit gravitropic reception act on the channel system at low concentrations. Specifically, ethyl-N-phenylcarbamate promotes tension-dependent activity at micromolar levels. With moderate suction, Gd3+ provided at about 0.5 micromole at the extracellular face of the membrane promotes for several seconds but may then become inhibitory. Provision at 1-2 micromoles promotes and subsequently inhibits more vigorously (often abruptly and totally), and at high levels inhibits immediately. La3+, a poor gravitropic inhibitor, acts similarly but much more gradually and only at much higher concentrations. These properties, particularly these susceptibilities to modulation, indicate that in vivo the mechanosensitive channel must be mechanosensory and mechanoregulatory. It could serve to transduce the shear forces generated in the integrated wall-membrane-cytoskeleton system during turgor changes and cell expansion as well as transducing the stresses induced by gravity, touch and flexure. In so far as such transduction is modulated by voltage and temperature, the channels would also be sensors for these modalities as long as the wall-membrane-cytoskeleton system experiences mechanical stress.

NASA Discipline Number 40-50↗

Carbon nanotube porin diffusion in mixed composition supported lipid bilayers

Carbon nanotube porins (CNTPs), short pieces of carbon nanotubes capable of self-inserting into a lipid bilayer, represent a simplified model of biological membrane channels. We have used high-speed atomic force microscopy (HS-AFM) and all-atom molecular dynamics (MD) simulations to study the behavior of CNTPs in a mixed lipid membrane consisting of DOPC lipid with a variable percentage of DMPC lipid added to it. HS-AFM data reveal that the CNTPs undergo diffusive motion in the bilayer plane. Motion trajectories extracted from the HS-AFM movies indicate that CNTPs exhibit diffusion coefficient values broadly similar to values reported for membrane proteins in supported lipid bilayers. The data also indicate that increasing the percentage of DMPC leads to a marked slowing of CNTP diffusion. MD simulations reveal a CNTP-lipid assembly that diffuses in the membrane and show trends that are consistent with the experimental observations.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Salinity and hydraulic retention time induce membrane phospholipid acyl chain remodeling in Halanaerobium congolense WG10 and mixed cultures from hydraulically fractured shale wells

Bacteria remodel their plasma membrane lipidome to maintain key biophysical attributes in response to ecological disturbances. For Halanaerobium and other anaerobic halotolerant taxa that persist in hydraulically fractured deep subsurface shale reservoirs, salinity, and hydraulic retention time (HRT) are important perturbants of cell membrane structure, yet their effects remain poorly understood. Membrane-linked activities underlie in situ microbial growth kinetics and physiologies which drive biogeochemical reactions in engineered subsurface systems. Hence, we used gas chromatography–mass spectrometry (GC–MS) to investigate the effects of salinity and HRT on the phospholipid fatty acid composition of H. congolense WG10 and mixed enrichment cultures from hydraulically fractured shale wells. We also coupled acyl chain remodeling to membrane mechanics by measuring bilayer elasticity using atomic force microscopy (AFM). For these experiments, cultures were grown in a chemostat vessel operated in continuous flow mode under strict anoxia and constant stirring. Our findings show that salinity and HRT induce significant changes in membrane fatty acid chemistry of H. congolense WG10 in distinct and complementary ways. Notably, under nonoptimal salt concentrations (7% and 20% NaCl), H. congolense WG10 elevates the portion of polyunsaturated fatty acids (PUFAs) in its membrane, and this results in an apparent increase in fluidity (homeoviscous adaptation principle) and thickness. Double bond index (DBI) and mean chain length (MCL) were used as proxies for membrane fluidity and thickness, respectively. These results provide new insight into our understanding of how environmental and engineered factors might disrupt the physical and biogeochemical equilibria of fractured shale by inducing physiologically relevant changes in the membrane fatty acid chemistry of persistent microbial taxa. GRAPHICAL ABSTRACT Salinity significantly alters membrane bilayer fluidity and thickness in Halanaerobium congolense WG10.

03 NATURAL GAS↗

Hybrid MBE Route to Adsorption-Controlled Growth of BaTiO 3 Membranes with Robust Polarization Switching

Freestanding ferroelectric membranes are promising for flexible electronics, nonvolatile memory, photonics, and spintronics, but their synthesis is challenged by the need for reproducibility with precise stoichiometric control. Here, we demonstrate the adsorption-controlled growth of single-crystalline, epitaxial BaTiO 3 films by hybrid molecular beam epitaxy (MBE) on a binary oxide sacrificial layer. Using a simple water-droplet lift-off method, we obtained submillimeter- to millimeter-sized membranes that retained crystallinity, as confirmed by high-resolution X-ray diffraction, and exhibited robust tetragonal symmetry, as verified by Raman spectroscopy. Impedance spectroscopy confirmed a high dielectric constant of ∼1340, reflecting the robust dielectric response of the membranes. Ferroelectric functionality was revealed by piezoresponse force microscopy (PFM) and further verified by polarization-electric field (P-E) loop measurements with Positive-Up-Negative-Down (PUND). The P-E loops exhibited a remnant polarization of ∼5 μC cm –2 and a coercive field of ∼63 kV cm –1 . Furthermore, these results were interpreted in relation to c- and a-domain configurations.

Raman spectroscopy↗

Characterization of Polyamide Thin Films by Atomic Force Microscopy

This study directly compares the mechanical behavior of novel molecular layer deposition (MLD) and analogous interfacial polymerization (IP) polyamide thin films in environments relevant to reverse osmosis (RO) membrane operation. The elastic modulus of the films was determined using atomic force microscopy (AFM) in dry, hydrated, and chlorinated states. Surface roughness characteristics were also obtained given their potential influence on AFM modulus measurements. The much smoother MLD films demonstrated a statistically higher modulus in all states as compared to their IP counterparts. The MLD films maintained a modulus ~3X and ~5X greater than that of IP films after hydration and chlorination, respectively. Such differences in behavior may be due to the higher density and correspondingly lower void content of the MLD films. Results from this study provide a rationale for future development of MLD for fabrication of polyamide films for incorporation in RO membranes.

atomic force microscopy↗

X-ray Scattering Studies of Reverse Osmosis Materials

Scarcity of freshwater is becoming a world crisis. In a recent annual risk report, the World Economic Forum lists it in their greatest global risk category. Currently, about four billion people live under conditions of severe water scarcity for at least one month out of the year [1]. Increasing water use efficiency is thus essential. However, this alone will not be able to provide adequate drinking water to meet the world’s needs. The process of preparing drinking water from seawater and brackish water involves many stages, the final and most expensive of which is typically reverse osmosis (RO). Reverse osmosis processes operate by forcing water across a semi-permeable membrane by applying a pressure greater than the osmotic pressure of the feed solution (seawater, Π ≈ 28 bar = 400 psi), thereby separating the water from any dissolved ions and impurities (rejection > 99%). The flux of water through the membrane is directly proportional to the amount of pressure applied above the osmotic pressure; however, the energy consumption is related to the total pressure. According to the American Membrane Technology Association, the amount of energy required to desalinate seawater with current technologies is 2.5 to 3.5 kWh/m 3 of water. RO materials have been tuned, modified, and optimized extensively since their initial discovery through an Edisonian approach. Despite immense technological progress [2, 3], many basic scientific questions remain on the molecular structure of RO membranes. Overall, in this report, we demonstrate that synchrotron X-ray scattering methods offer the possibility of improving our fundamental understanding of RO materials.

36 MATERIALS SCIENCE↗