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At least 289 records · Page 16

Structural correlates of imbibitional injury in Typha pollen

The ultrastructure of Typha latifolia pollen was examined as a function of pollen moisture content and incubation temperature, in order to identify possible lesions induced by imbibitional chilling. A syndrome of structural traits was found which characterizes damaged grains. Compared to viable grains, the protoplast of damaged pollen has a higher proportion of its volume occupied by vesicles, and less volume occupied by cytoplasm. Damaged grains also tend to have dilated cisternae of endoplasmic reticulum, larger starch grains and lipid bodies, poorly preserved mitochondria and membranes, and, sometimes, numerous electron-dense globules associated with membranes. The percentage of grains exhibiting this damage syndrome correlates closely with the number of ungerminated grains in most samples, regardless of moisture content or incubation temperature. Injury due to rapid imbibition from the dry state or to imbibitional chilling appear to be similar structurally, regardless of whether the stresses are imposed singly or together. The injury is not confined to one cell component (e.g., mitochondria), but may involve a generalized disruption of membranes. These results suggest that similar stress responses are elicited by imbibition from the dry state and by imbibitional chilling.

NASA Program Space Biology↗

Cooperative Atomically Dispersed Fe–N 4 and Sn–N x Moieties for Durable and More Active Oxygen Electroreduction in Fuel Cells

One grand challenge for deploying porous carbons with embedded metal–nitrogen–carbon (M–N–C) moieties as platinum group metal (PGM)-free electrocatalysts in proton-exchange membrane fuel cells is their fast degradation and inferior activity. Here, we report the modulation of the local environment at Fe–N 4 sites via the application of atomic Sn–N x sites for simultaneously improved durability and activity. We discovered that Sn–N x sites not only promote the formation of the more stable D2 FeN 4 C 10 sites but also invoke a unique D3 SnN x –Fe II N 4 site that is characterized by having atomically dispersed bridged Sn–N x and Fe–N 4 . This new D3 site exhibits significantly improved stability against demetalation and several times higher turnover frequency for the oxygen reduction reaction (ORR) due to the shift of the reaction pathway from a single-site associative mechanism to a dual-site dissociative mechanism with the adjacent Sn site facilitating a lower overpotential cleavage of the O–O bond. This mechanism bypasses the formation of the otherwise inevitable intermediate that is responsible for demetalation, where two hydroxyl intermediates bind to one Fe site. Lastly, a mesoporous Fe/Sn-PNC catalyst exhibits a positively shifted ORR half-wave potential and more than 50% lower peroxide formation. This, in combination with the stable D3 site and enriched D2 Fe sites, significantly enhanced the catalyst’s durability as demonstrated in membrane electrode assemblies using complementary accelerated durability testing protocols.

36 MATERIALS SCIENCE↗

Light-Activated Amino Acid Transport Systems in Halobacterium halobium Envelope Vesicles: Role of Chemical and Electrical Gradients

The accumulation of 20 commonly occurring L-amino acids by cell envelope vesicles of Halobacterium halobium, in response to light-induced membrane potential and an artificially created sodium gradient, has been studied. Nineteen of these amino acids are actively accumulated under either or both of these conditions. Glutamate is unique in that its uptake is driven only by a chemical gradient for sodium. Amino acid concentrations at half-maximal uptake rates (Km) and maximal transport rates (V(sub max) have been determined for the uptake of all 19 amino acids. The transport systems have been partially characterized with respect to groups of amino acids transported by common carriers, cation effects, and relative response to the electrical and chemical components of the sodium gradient, the driving forces for uptake. The data presented clearly show that the carrier systems, which are responsible for uptake of individual amino acids, are as variable in their properties as those found in other organisms, i. e., some are highly specific for individual amino acids, some transport several amino acids competitively, some are activated by a chemical gradient of sodium only, and some function also in the complete absence of such a gradient. For all amino acids, Na(+) and K(+) are both required for maximal rate of uptake. The carriers for L-leucine and L-histidine are symmetrical in that these amino acids are transported in both directions across the vesicle membrane. It is suggested that coupling of substrate transport to metabolic energy via transient ionic gradients may be a general phenomenon in procaryotes.

MacDonald, Russell E.↗

Probing Electrode Transformation under Dynamic Operation for Alkaline Water Electrolysis

Alkaline water electrolyzers (AWEs) play a pivotal role in the realm of large-scale hydrogen production. However, AWEs face significant challenges in electrode degradation particularly under dynamic operating conditions, induced by reverse current phenomenon during frequent startup/shutdown. Herein, this study aims to rationalize the degradation mechanisms of AWEs under these conditions. A three-electrode membrane electrode assembly (MEA) setup is first utilized to decouple polarization behaviors of anode and cathode in AWEs. Following a proposed accelerated stress testing protocol, the setup allows for tracking individual electrode performance transformations during frequent reverse current operation. Integrating operando cell studies with in situ and post-mortem characterizations, it is showed that continuous formation of highly active species, nickel (oxy)hydroxides, improves the anode performance for oxygen evolution reaction. On the contrary, irreversible oxidation of nickel to β-nickel hydroxide results in a severe degradation of cathode, leading to material dissolution, poor electrical conductivity and loss of catalytic activity for hydrogen evolution reaction. These results provide insights in nickel-based electrode transformation mechanisms for alkaline water electrolysis and indicate that cathode with higher redox reversibility can potentially improve durability of AWEs under dynamic conditions.

08 HYDROGEN↗

Development of single crystal membranes

The design and construction of a high pressure crystal growth chamber was accomplished which would allow the growth of crystals under inert gas pressures of 2 MN/sq m (300 psi). A novel crystal growth technique called EFG was used to grow tubes and rods of the hollandite compounds, BaMgTi7O16, K2MgTi7O16, and tubes of sodium beta-alumina, sodium magnesium-alumina, and potassium beta-alumina. Rods and tubes grown are characterized using metallographic and X-ray diffraction techniques. The hollandite compounds are found to be two or three-phase, composed of coarse grained orientated crystallites. Single crystal c-axis tubes of sodium beta-alumina were grown from melts containing excess sodium oxide. Additional experiments demonstrated that crystals of magnesia doped beta-alumina and potassium beta-alumina also can be achieved by this EFG technique.

Stormont, R. W.↗

Enhancing Acidic Oxygen Evolution Activity by Supporting Iridium Electrocatalysts on Tantalum Carbide

For a high-performance proton exchange membrane water electrolyzer (PEMWE), acidic oxygen evolution reaction (OER) electrocatalysts require highly dispersed iridium oxide (IrO x ) nanoparticles. Although carbon-based materials have been explored as promising supports for IrO x nanoparticles, their limited stability under harsh oxidative and acidic PEMWE conditions remains a significant challenge. Here, in this study, we report the synthesis and in situ characterization of active and durable IrOx electrocatalysts supported on electrochemically stable and electrically conducting tantalum carbide (TaC). When applied in a PEMWE, the IrO x /TaC electrocatalyst achieves a cell voltage of 1.71 V at 1.0 A cm –2 , outperforming the commercial IrO 2 catalyst (1.82 V at 1.0 A cm –2 ). Furthermore, the IrO x /TaC catalyst maintains a stable operation for 200 h at 0.5 A cm –2 with a low degradation rate of 36 μV h –1 . Density functional theory calculations further confirm that Ir–O–Ta bond formation at the IrO x /TaC interface reduces the overpotential of the OER compared to IrO 2 . This study underscores the pivotal role of supporting IrO x over stable and conducting metal carbides, providing guidance for the design of advanced acidic OER catalysts.

58 GEOSCIENCES↗

Structural architecture of TolQ-TolR inner membrane protein complex from opportunistic pathogen Acinetobacter baumannii

Gram-negative bacteria harness the proton motive force (PMF) within their inner membrane (IM) to uphold cell envelope integrity, an indispensable aspect for both division and survival. The IM TolQ-TolR complex is the essential part of the Tol-Pal system, serving as a conduit for PMF energy transfer to the outer membrane. Here we present cryo–electron microscopy reconstructions ofAcinetobacter baumanniiTolQ in apo and TolR-bound forms at atomic resolution. The apo TolQ configuration manifests as a symmetric pentameric pore, featuring a transmembrane funnel leading toward a cytoplasmic chamber. In contrast, the TolQ-TolR complex assumes a proton nonpermeable stance, characterized by the TolQ pentamer’s flexure to accommodate the TolR dimer, where two protomers undergo a translation-based relationship. Our structure-guided analysis and simulations support the rotor-stator mechanism of action, wherein the rotation of the TolQ pentamer harmonizes with the TolR protomers’ interplay. These findings broaden our mechanistic comprehension of molecular stator units empowering critical functions within the Gram-negative bacterial cell envelope.

Science & Technology - Other Topics↗

Innovative duo-recombination layer design for effective hydrogen crossover mitigation in advanced MEAs for PEM water electrolyzers

Hydrogen crossover in proton exchange membrane water electrolyzers (PEMWEs) poses a safety hazard, reduces the overall efficiency, and limits the operational differential pressure range. Here, in this study, a membrane electrode assembly (MEA) with innovative Pt duo-recombination layer (DRL) design is developed by the unique reactive spray deposition technology (RSDT). The novel design comprises two thin RLs integrated within the volume of the membrane and has a total Pt loading of only 0.04 mg Pt cm −2 . Long-term durability test for over 3000 h is performed with as-fabricated MEA at steady-state conditions typical for an industrial hydrogen production system. The results from the durability test show that the newly developed DRL design effectively suppresses the H2 crossover to below 0.5 vol%. Furthermore, comprehensive post-test characterization of the MEA is performed and potential failure mechanisms in the Pt RLs observed during the durability test are identified and discussed in detail for the first time.

08 HYDROGEN↗

Use of T7 RNA polymerase to direct expression of outer Surface Protein A (OspA) from the Lyme disease Spirochete, Borrelia burgdorferi

The OspA gene from a North American strain of the Lyme disease Spirochete, Borrelia burgdorferi, was cloned under the control of transciption and translation signals from bacteriophage T7. Full-length OspA protein, a 273 amino acid (31kD) lipoprotein, is expressed poorly in Escherichia coli and is associated with the insoluble membrane fraction. In contrast, a truncated form of OspA lacking the amino-terminal signal sequence which normally would direct localization of the protein to the outer membrane is expressed at very high levels (less than or equal to 100 mg/liter) and is soluble. The truncated protein was purified to homogeneity and is being tested to see if it will be useful as an immunogen in a vaccine against Lyme disease. Circular dichroism and fluorescence spectroscopy was used to characterize the secondary structure and study conformational changes in the protein. Studies underway with other surface proteins from B burgdorferi and a related spirochete, B. hermsii, which causes relapsing fever, leads us to conclude that a strategy similar to that used to express the truncated OspA can provide a facile method for producing variations of Borrelia lipoproteins which are highly expressed in E. coli and soluble without exposure to detergents.

Dunn, John J.↗

Preparation and Analysis of RNA Crystals

The crystallization of RiboNucleic Acids (RNA) was studied from the standpoint of mechanisms of crystal growth in three tasks: (1) preparation of high-quality crystals of oligonuclotides for X-ray diffraction, (2) finding pathways to the growth of high-quality crystals for X-ray diffraction and (3) investigation of mechanisms of action of inertial acceleration on crystal growth. In these tasks: (1) RNA crystals were prepared and studied by X-ray diffraction; (2) a pathway to high-quality crystals was discovered and characterized; a combination of kinetic and equilibrium factors could be optimized as described below; and (3) an interplay between purity and gravity was found in a combination of space and ground experiments with nucleic acids and proteins. Most significantly, the rate of concentration of precipitant and RNA can be controlled by membrane-based methods of water removal or by diffusion of multivalent cations across an interface stabilized by a membrane. Oligonucleotide solutions are electrokinetically stabilized colloids, and crystals can form by the controlled addition of multivalent cations.

Todd, Paul↗

Influence of crossover on capacity fade of symmetric redox flow cells

Volumetrically unbalanced compositionally symmetric cell cycling with potentiostatic (CV) or galvanostatic-with-potential-hold (CCCV) protocols is a rigorous technique for evaluating the calendar lifetime of reactants for redox flow batteries. Here, we evaluate the influence of reactant crossover through the membrane on symmetric cell cycling behavior. We tested symmetric cells of anthraquinone disulfonic acid (AQDS) with Nafion membranes of varied thickness and manufacture (NR211, NR212, N115, and N117, ranging 25–183 μm). Membranes were tested both as-received and pretreated with a common procedure of soaking in water at elevated temperature and then in dilute hydrogen peroxide. We found no significant difference in capacity fade rates of symmetric cells with any of the membranes as-received, indicating a negligible influence of crossover. However, we observed increased capacity fade with increased permeability through pretreated membranes. Supported by zero-dimensional modeling and operando UV-vis spectrophotometry, we propose a mechanism for net crossover in AQDS symmetric cells based on a higher time-averaged concentration of quinhydrone dimers in the non-capacity limiting side (NCLS) compared to the capacity limiting side (CLS), driving net crossover of AQDS reactants out of the CLS. Further, we illustrate other hypothetical scenarios of net crossover using the zero-dimensional model. Overall, many membrane–electrolyte systems used in symmetric cell studies have sufficiently low crossover flux as to avoid the influence of crossover on capacity fade, but under conditions of higher crossover flux, complex interactions of crossover and chemical reactions may result in diverse capacity fade trajectories, the mechanisms of which may be untangled with operando characterization and modeling.

25 ENERGY STORAGE↗

Modeling with uncertainty quantification reveals the essentials of a non-canonical algal carbon-concentrating mechanism

The thermoacidophilic red alga Cyanidioschyzon merolae survives its challenging environment likely in part by operating a carbon-concentrating mechanism (CCM). Here, we demonstrated that C. merolae 's cellular affinity for CO 2 is stronger than the affinity of its rubisco for CO 2 . This finding provided additional evidence that C. merolae operates a CCM while lacking the structures and functions characteristic of CCMs in other organisms. To test how such a CCM could function, we created a mathematical compartmental model of a simple CCM, distinct from those we have seen previously described in detail. The results of our modeling supported the feasibility of this proposed minimal and non-canonical CCM in C. merolae . To facilitate the robust modeling of this process, we measured and incorporated physiological and enzymatic parameters into the model. Additionally, we trained a surrogate machine-learning model to emulate the mechanistic model and characterized the effects of model parameters on key outputs. This parameter exploration enabled us to identify model features that influenced whether the model met the experimentally derived criteria for functional carbon concentration and efficient energy usage. Such parameters included cytosolic pH, bicarbonate pumping cost and kinetics, cell radius, carboxylation velocity, number of thylakoid membranes, and CO 2 membrane permeability. Our exploration thus suggested that a non-canonical CCM could exist in C. merolae and illuminated the essential features generally necessary for CCMs to function.

Steensma, Anne K. [Michigan State Univ., East Lans↗

Rational sub-nanometer manipulation of polymer morphology for efficient chemical separations

The ability to control polymer morphology on the sub-nanometer length scale has broad implications for chemical separations. To achieve such control on easily processable systems, this proposal focuses on the synthesis and characterization of polymers containing appended labile moieties that are easily detached by thermolysis or UV irradiation deep within the glassy state. Once liberated, these moieties can diffuse from the polymer matrix as gaseous products, leaving behind templated pathways for selective diffusion and sorption of small molecules. With a specific target of creating polymeric membrane materials with unprecedented diffusion and (ad)sorption characteristics for chemical separations, synthesis of new materials will be complemented with advanced metrologies, simulations, and evaluation of thermodynamic and transport theory.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA PEMFC Development Background and History

NASA has been developing proton-exchange-membrane (PEM) fuel cell power systems for the past decade, as an upgraded technology to the alkaline fuel cells which presently provide power for the Shuttle Orbiter. All fuel cell power systems consist of one or more fuel cell stacks in combination with appropriate balance-of-plant hardware. Traditional PEM fuel cells are characterized as flow-through, in which recirculating reactant streams remove product water from the fuel cell stack. NASA recently embarked on the development of non-flow-through fuel cell systems, in which reactants are dead-ended into the fuel cell stack and product water is removed by internal wicks. This simplifies the fuel cell power system by eliminating the need for pumps to provide reactant circulation, and mechanical water separators to remove the product water from the recirculating reactant streams. By eliminating these mechanical components, the resulting fuel cell power system has lower mass, volume, and parasitic power requirements, along with higher reliability and longer life. Four vendors have designed and fabricated non-flow-through fuel cell stacks under NASA funding. One of these vendors is considered the "baseline" vendor, and the remaining three vendors are competing for the "alternate" role. Each has undergone testing of their stack hardware integrated with a NASA balance-of-plant. Future Exploration applications for this hardware include primary fuel cells for a Lunar Lander and regenerative fuel cells for Surface Systems.

Hoberecht, Mark↗

The Advantages of Non-Flow-Through Fuel Cell Power Systems for Aerospace Applications

NASA has been developing proton-exchange-membrane (PEM) fuel cell power systems for the past decade, as an upgraded technology to the alkaline fuel cells which presently provide power for the Shuttle Orbiter. All fuel cell power systems consist of one or more fuel cell stacks in combination with appropriate balance-of-plant hardware. Traditional PEM fuel cells are characterized as flow-through, in which recirculating reactant streams remove product water from the fuel cell stack. NASA recently embarked on the development of non-flow-through fuel cell systems, in which reactants are dead-ended into the fuel cell stack and product water is removed by internal wicks. This simplifies the fuel cell power system by eliminating the need for pumps to provide reactant circulation, and mechanical water separators to remove the product water from the recirculating reactant streams. By eliminating these mechanical components, the resulting fuel cell power system has lower mass, volume, and parasitic power requirements, along with higher reliability and longer life. These improved non-flow-through fuel cell power systems therefore offer significant advantages for many aerospace applications.

Hoberecht, Mark↗

Development of Field-Controlled Smart Optic Materials (ScN, AlN) with Rare Earth Dopants

The purpose of this investigation is to develop the fundamental materials and fabrication technology for field-controlled spectrally active optics that are essential for industry, NASA, and DOD applications such as: membrane optics, filters for LIDARs, windows for sensors, telescopes, spectroscopes, cameras, flat-panel displays, etc. ScN and AlN thin films were fabricated on c-axis Sapphire (0001) or quartz substrate with the RF and DC magnetron sputtering. The crystal structure of AlN in fcc (rocksalt) and hcp (wurtzite) were controlled. Advanced electrical characterizations were performed, including I-V and Hall Effect Measurement. ScN film has a free carrier density of 5.8 x 10(exp 20)/per cubic centimeter and a conductivity of 1.1 x 10(exp 3) per centimeter. The background ntype conductivity of as-grown ScN has enough free electrons that can readily interact with the photons. The high density of free electrons and relatively low mobility indicate that these films contain a high level of shallow donors as well as deep levels. Also, the UV-Vis spectrum of ScN and AlN thin films with rare earth elements (Er or Ho) were measured at room temperature. Their optical band gaps were estimated to be about 2.33eV and 2.24eV, respectively, which are obviously smaller than that of undoped thin film ScN (2.4eV). The red-shifted absorption onset gives direct evidence for the decrease of band gap (Eg) and the energy broadening of valence band states are attributable to the doping. As the doped elements enter the ScN crystal lattices, the localized band edge states form at the doped sites with a reduction of Eg. Using a variable angle spectroscopic ellipsometer, the decrease in refractive index with applied field is observed with a smaller shift in absorption coefficient.

Kim, Hyun-Jung↗

NASA Tech Briefs, October 2012

Topics discussed include: Detection of Chemical Precursors of Explosives; Detecting Methane From Leaking Pipelines and as Greenhouse Gas in the Atmosphere; Onboard Sensor Data Qualification in Human-Rated Launch Vehicles; Rugged, Portable, Real-Time Optical Gaseous Analyzer for Hydrogen Fluoride; A Probabilistic Mass Estimation Algorithm for a Novel 7-Channel Capacitive Sample Verification Sensor; Low-Power Architecture for an Optical Life Gas Analyzer; Online Cable Tester and Rerouter; A Three-Frequency Feed for Millimeter-Wave Radiometry; Capacitance Probe Resonator for Multichannel Electrometer; Inverted Three-Junction Tandem Thermophotovoltaic Modules; Fabrication of Single Crystal MgO Capsules; Inflatable Hangar for Assembly of Large Structures in Space; Mars Aqueous Processing System; Hybrid Filter Membrane; Design for the Structure and the Mechanics of Moballs; Pressure Dome for High-Pressure Electrolyzer; Cascading Tesla Oscillating Flow Diode for Stirling Engine Gas Bearings; Compact, Low-Force, Low-Noise Linear Actuator; Ultra-Compact Motor Controller; Extreme Ionizing-Radiation-Resistant Bacterium; Wideband Single-Crystal Transducer for Bone Characterization; Fluorescence-Activated Cell Sorting of Live Versus Dead Bacterial Cells and Spores; Nonhazardous Urine Pretreatment Method; Laser-Ranging Transponders for Science Investigations of the Moon and Mars; Ka-Band Waveguide Three-Way Serial Combiner for MMIC Amplifiers; Structural Health Monitoring with Fiber Bragg Grating and Piezo Arrays; Low-Gain Circularly Polarized Antenna with Torus-Shaped Pattern; Stereo and IMU- Assisted Visual Odometry for Small Robots; Global Swath and Gridded Data Tiling; GOES-R: Satellite Insight; Aquarius iPhone Application; Monitoring of International Space Station Telemetry Using Shewhart Control Charts; Theory of a Traveling Wave Feed for a Planar Slot Array Antenna; Time Manager Software for a Flight Processor; Simulation of Oxygen Disintegration and Mixing With Hydrogen or Helium at Supercritical Pressure; A Superfluid Pulse Tube Refrigerator Without Moving Parts for Sub-Kelvin Cooling; Sapphire Viewports for a Venus Probe; The Mobile Chamber; Electric Propulsion Induced Secondary Mass Spectroscopy; and Radiation-Tolerant DC-DC Converters.

Source record↗

Influence of Pt-Metal Alloy Catalysts with Various Ionomers on Oxygen Reduction Reaction in Fuel Cell Application

Pt-M/C (M = Co, Ni, Mn, etc.) alloy catalysts exhibit superior oxygen reduction reaction (ORR) activity compared to pure Pt/C, leading to a high energy efficiency in hydrogen fuel cells. However, many Pt-M/C alloy catalysts were synthesized and evaluated at the lab scale in model test-bed systems like rotating disc electrodes, which don't always correlate to performance within a fuel cell system; there is a clear need to evaluate catalysts in electrodes that can be prepared at industrially relevant scales to evaluate how factors like ink formulation can greatly affect device-level of fuel cell performance. Herein, three commercial Pt-M/C alloy catalysts (two Pt-Co/C and one Pt-Ni/C) were comprehensively characterized by various techniques. The results show that the average particle sizes of the three catalysts are close to 5 nm; the atomic ratio of Pt/M is around 4; and the M was successfully embedded into Pt lattice, resulting in the positive shift of Pt 4f in XPS spectra and XRD patterns. These catalytic materials were incorporated into 9 different cathode catalyst layers (CCLs) with three kinds of ionomers (Nafion D2020, high oxygen permeability ionomer (HOPI), and Aquivion D79-25BS), and their performance in proton exchange membrane fuel cells (PEMFCs) were investigated. The results demonstrate that the Pt-Co/C catalysts possess a higher mass activity (MA) than Pt-Ni/C; the cathodes with Nafion ionomer provide the highest MA while electrodes with Aquivion ionomer showed the lowest activity, attributed to poor H+ conductivity resulting from suboptimal ionomer incorporation. Finally, these alloys were shown to exceed DOE targets for MA and H2/Air performance reported in the recent publications at beginning of life and after 90k cycle catalyst AST protocol. This study provides valuable performance benchmarks for these materials guiding future Pt-M/C catalyst design and material integration for heavy duty PEMFC applications.

08 HYDROGEN↗