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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 919 records · Page 51
All sourcesNASA NTRSDOE OSTI
NASA NTRS1995

A Model Simulation of Pinatubo Volcanic Aerosols in the Stratosphere

A one-dimensional, time-dependent model is used to study the chemical, microphysical, and radiative properties of volcanic aerosols produced by the Mount Pinatubo eruption on June 15, 1991. Our model treats gas-phase sulfur photochemistry, gas-to-particle conversion of sulfur, and the microphysics of sulfate aerosols and ash particles under stratospheric conditions. The dilution and diffusion of the volcanic eruption clouds are also accounted for in these conditions. Heteromolecular homogeneous and heterogeneous binary H2SO4/H2O nucleation, acid and water condensational growth, coagulation, and gravitational sedimentation are treated in detail in the model. Simulations suggested that after several weeks, the volcanic cloud was composed mainly of sulfuric acid/water droplets produced in situ from the SO2 emissions. The large amounts of SO2 (around 20 Mt) injected into the stratosphere by the Pinatubo eruption initiated homogeneous nucleation which generated a high concentration of small H2SO4/H2O droplets. These newly formed particles grew rapidly by condensation and coagulation in the first few months and then reach their stabilized sizes with effective radii in a range between 0.3 and 0.5 micron approximately one-half year after the eruption. The predicted volcanic cloud parameters reasonably agree with measurements in term of the vertical distribution and lifetime of the volcanic aerosols, their basic microphysical structures (e.g., size distribution, concentration, mass ratio, and surface area) and radiative properties. The persistent volcanic aerosols can produce significant anomalies in the radiation field, which have important climatic consequences. The large enhancement in aerosol surface area can result in measurable global stratospheric ozone depletion.

Zhao , Jing-xia↗
NASA NTRS2004

Evidence for Differential Comminution/Aeolian Sorting and Chemical Weathering of Martian Soils Preserved in Mars Meteorite EET79001

Impact-melt glasses containing Martian atmospheric gases in Mars meteorite EET79001 are formed from Martian soil fines that had undergone meteoroid-comminution and aeolian sorting accompanied by chemical weathering near Mars surface. Using SiO2 and SO3 as proxy for silicates and salts respectively in Mars soils, we find that SiO2 and SO3 correlate negatively with FeO and MgO and positively with Al2O3 and CaO in these glasses, indicating that the mafic and felsic components are depleted and enriched relative to the bulk host (Lith A/B) respectively as in the case of Moon soils. Though the overall pattern of mineral fractionation is similar between the soil fines on Mars and Moon, the magnitudes of the enrichments/depletions differ between these sample-suites because of pervasive aeolian activity on Mars. In addition to this mechanical processing, the Martian soil fines, prior to impact-melting, have undergone acid-sulfate dissolution under oxidizing/reducing conditions. The S03 content in EET79001,507 (Lith B) glass is approx.18% compared to < 2% in EET79001, 506 (Lith A). SiO2 and SO3 negatively correlate with each other in ,507 glasses similar to Pathfinder soils. The positive correlation found between FeO and SO3 in ,507 glasses as well as Pathfinder rocks and soils is consistent with the deposition of ferric-hydroxysulfate on regolith grains in an oxidizing environment. As in the case of Pathfinder soils, the Al 2O3 vs SiO2 positive correlation and FeO VS S102 negative correlation observed in ,507 glasses indicate that SiO2 from the regolith is mobilized as soluble silicic acid at low pH. The large off-set in the end-member FeO abundance ( SO3=0) between Pathfinder soil-free rock and sulfur-free rock in ,507 glass precursors suggests that the soils comprising the ,507 glasses contain much larger proportion of fine-grained Martian soil fraction that registers strong mafic depletion relative to Lith B. This inference is strongly supported by the Al2O3 - SO3 negative correlation observed in both ,507 glasses and pathfinder soils. Furthermore, the flat MgO-SO3 correlation observed in the case of ,507 glasses shows that the solubilized MgSO4 is mobilized by the aqueous solutions leaving behind the rock-residue with approx.2-3% MgO. This value is similar to the approx.2% MgO found for the soil-free rock at the Pathfinder site. The EET79001 ,506 glasses, in contrast, show that Al2O3 and CaO positively correlate with SO3 indicating that Al is precipitated as amorphous hydroxysulfate at relatively high pH. The FeO - SO3 negative correlation observed in ,506 glasses yields an end-member FeO abundance of approx.21% for the sulfur-free rock, which is consistent with the 22% FeO deduced for the Viking soil-free rock. Further, the FeO and MgO negative correlation with S03 observed in ,506 glasses indicates that the divalent Fe and Mg released from ferromagnesian minerals by acid sulfate dissolution are mobilized away from the reaction sites as soluble sulfates under reducing environment. A similar negative correlation between FeO and SO3 and a positive correlation between Al2O3 and SO3 found in Viking soils suggest that they also had undergone acid-sulfate dissolution under relatively reducing conditions.

Rao, M. N.↗
DOE OSTI2020

Beneficiation of coal using supercritical water and carbon dioxide extraction: sulfur removal

Abstract This work explores the use of carbon dioxide, water, and their mixtures as solvent for the precombustion beneficiation of raw coal without using any toxic mineral acids in the temperature range of 200–400 °C. The fluid polarity, ionic constant, and supercritical point can be adjusted by H 2 O/CO 2 ratio and temperature. Adding carbon dioxide to hydrothermal fluid also increases the ionization by forming carbonic acid. Extractions with supercritical fluids have several benefits including enhanced mass transport, ease of separation and recycle, wide range of extractive capability and tunability, better inherent safety, and in the case of carbon dioxide and water–low cost. A semi-continuous extraction system was designed and built in which pressure, temperature and the relative flow rates of CO 2 and H 2 O can be controlled. Coal powder is kept in a packed bed and the extraction is carried out at 143 bar pressure. Using sulfur as a model heteroatom, extractive efficiency is examined as a function of the temperature, fluid composition, fluid flow, and extraction time. The results indicate that carbon dioxide, water, and supercritical water-carbon dioxide (ScWC) all can effectively extract about 50% of total sulfur from bituminous coal in 1 h. Extraction above 350 °C decreased effectiveness, and extraction above the supercritical point of pure water caused hydrothermal carbonization. ScWC extraction may provide necessary control to prevent organic dissolution while removing sulfur.

DeCuir, Matthew J.↗
DOE OSTI2021

Development of an Enzyme-Inhibitor Reaction Using Cellular Retinoic Acid Binding Protein II for One-Pot Megamolecule Assembly

This paper presents an enzyme building block for the assembly of megamolecules. The system is based on the inhibition of the human-derived cellular retinoic acid binding protein II (CRABP2) domain. We synthesized a synthetic retinoid bearing an arylfluorosulfate group, which uses sulfur fluoride exchange click chemistry to covalently inhibit CRABP2. We conjugated both the inhibitor and a fluorescein tag to an oligo(ethylene glycol) backbone and measured a second-order rate constant for the protein inhibition reaction of approximately 3,600 M -1 s -1 . We used this new enzyme-inhibitor pair to assemble multi-protein structures in one-pot reactions using three orthogonal assembly chemistries to demonstrate exact control over the placement of protein domains within a single, homogeneous molecule. This work enables a new dimension of control over specificity, orientation, and stoichiometry of protein domains within atomically precise nanostructures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1974

Pathogenetic validation of the use of biological protective agents and early treatment in cases of radiation injury simulating radiation effects under space flight conditions

In considering a radiation safety system for space flights, the various measures to protect man against radiation include drug prophylaxis. At the present time a great deal of experimental material has been accumulated on the prevention and treatment of radiation injuries. Antiradiation effectiveness has been established for sulfur- and nitrogen-containing substances, auxins, cyanides, polynucleotides, mucopolysaccharides, lipopolysaccharides, aminosaccharides, synthetic polymers, vitamins, hormones, amino acids and other compounds which can be divided into two basic groups - biological and chemical protective agents.

Rogozkin, V. D.↗
NASA NTRS2019

Acid-Sulfate Weathering Environment at Shergottite Provenance on Mars

In some impact melt (IM) glasses in the shergottites such as EET79001, Shergotty and Tissint, recently showed that secondary mineral assemblages having large sulfur excesses cannot be produced in-situ by impact shock melting of the host rock constituents. Instead, these putative secondary minerals inferred to be present in IM glasses were produced somewhere else in the shergottite source region and were subsequently mobilized into the host rock voids (by lava erosion or aolian activity) prior to impact ejection. In this abstract, we examine the aqueous conditions (pH and water/rock ratios) under which the acid sulfate solutions could have interacted with the primary minerals in the basaltic rocks and precipitated the secondary minerals such as Fe-sulfates in some cases and Ca- and Al-sulfates in other cases under favorable conditions at the shergottite provenance on Mars.

Rao, M. N.↗
NASA NTRS1995

Isolation, characterization, and primary structure of rubredoxin from the photosynthetic bacterium, Heliobacillus mobilis

Rubredoxin is a small nonheme iron protein that serves as an electron carrier in bacterial systems. Rubredoxin has now been isolated and characterized from the strictly anaerobic phototroph, Heliobacillus mobilis. THe molecular mass (5671.3 Da from the amino acid sequence) was confirmed and partial formylation of the N-terminal methionyl residue was established by matrix-assisted laser desorption mass spectroscopy. The complete 52-amino-acid sequence was determined by a combination of N-terminal sequencing by Edman degradation and C-terminal sequencing by a novel method using carboxypeptidase treatment in conjunction with amino acid analysis and laser desorption time of flight mass spectrometry. The molar absorption coefficient of Hc. mobilis rubredoxin at 490 nm is 6.9 mM-1 cm-1 and the midpoint redox potential at pH 8.0 is -46 mV. The EPR spectrum of the oxidized form shows resonances at g = 9.66 and 4.30 due to a high-spin ferric iron. The amino acid sequence is homologous to those of rubredoxins from other species, in particular, the gram-positive bacteria, and the phototrophic green sulfur bacteria, and the evolutionary implications of this are discussed.

NASA Discipline Number 52-30↗
DOE OSTI2022

Impact of Acid–Base Stimulation Sequence on Mineral Stability for Tight/Impermeable Unconventional Carbonate-Rich Rocks: A Delaware Basin Case Study

We report mineral precipitation due to reactions with injected fluids during unconventional fracture stimulation is a well-recognized problem. The goal of this study is to evaluate secondary mineral precipitation and permeability attenuation under chemical injection scenarios specific to the Delaware basin. Whole cylindrical cores (2.54 cm diameter and 2.54 cm height) and ground shale (150–250 μm) from the carbonate-rich Bone Spring Formation, Delaware Basin TX (Leonardian), were reacted at 80 °C and 85 bar using a hydraulic fracturing fluid (HFF) recipe and an injection sequence typical of the Delaware Basin. The reacted shales and solutions were analyzed using a variety of laboratory- and synchrotron-based techniques to characterize both the chemical and spatial distributions of secondary mineral precipitation and identify changes in permeability and mineralogy. This carbonate-rich shale (>84% calcite) rapidly neutralized the acidic HFF. Synchrotron-based X-ray fluorescence mapping coupled with X-ray absorption spectroscopy (both bulk and micro) showed that most of the iron was in an oxidized form prior to exposure to HFF and that almost all iron(II) became fully oxidized after the reaction. Scanning electron microscopy images of the ground shale samples primarily identified iron(oxyhydr)oxide microcrystals on grain surfaces. A few small isolated iron-rich areas also contained sulfur, suggesting that some pyrite was preserved when isolated within a calcite crystal but that most was oxidized. The rapid neutralization of the acid spearhead in these carbonate-rich samples demonstrates that the acid spearhead is useful for initiating fractures in extremely calcite-rich rocks but does little to enhance rock permeability. This suggests that the impact of the acid spearhead is significantly smaller for carbonate-rich shales compared to clay-rich shales, which has broad implications for acidizing in carbonate-rich shale formations and iron transformations within these shales.

58 GEOSCIENCES↗
NASA NTRS2003

Astrobiological Significance of Chemolithoautotrophic Acidophiles

For more than a century (since Winogradsky discovered lithoautotrophic bacteria) a dilemma in microbiology has concerned life that first inhabited the Earth. Which types of life forms first appeared in the primordial oceans during the earliest geological period on Earth as the primary ancestors of modem biological diversity? How did a metabolism of ancestors evolve: from lithoautotrophic to lithohetherotrophic and organoheterotrophic or from organoheterotrophic to organoautotrophic and lithomixotrophic types? At the present time, it is known that chemolithoheterotrophic and chemolithoautotrophic metabolizing bacteria are wide spread in different ecosystems. On Earth the acidic ecosystems are associated with geysers, volcanic fumaroles, hot springs, deep sea hydrothermal vents, caves, acid mine drainage and other technogenic ecosystems. Bioleaching played a significant role on a global geological scale during the Earth's formation. This important feature of bacteria has been successfully applied in industry. The lithoautotrophs include Bacteria and Archaea belonging to diverse genera containing thermophilic and mesophilic species. In this paper we discuss the lithotrophic microbial acidophiles and present some data with a description of new acidophilic iron- and sulfur- oxidizing bacterium isolated from the Chena Hot Springs in Alaska. We also consider the possible relevance of microbial acidophiles to Venus, Io, and acidic inclusions in glaciers and icy moons.

Pikuta, Elena V.↗
DOE OSTI2023

Effect of bimetallic modification on blast furnace slag and its application in low‐temperature selective catalytic reduction

Abstract Objective In order to control NO x in low‐temperature flue gases emitted from non‐power industries and to reduce the preparation cost of denitration catalysts, this study uses inexpensive blast furnace slag as raw material to prepare denitration catalysts. Methods After cooling, drying and grinding, the blast furnace slag becomes a powder with considerable fineness and meets the requirements of activity index, which is called GGBS (ground granulated blast furnace slag). Using GGBS as denitration catalyst carrier, the active components M (M = Fe, Co, Ni, Cu and Ce) are loaded on Mn‐based GGBS catalyst using an impregnation method. Conclusions The effect of different active components on the denitration performance and sulfur resistance of Mn‐based GGBS catalysts is investigated. The results show that the Mn‐Ce/GGBS catalyst has better denitration performance and sulfur resistance. The Mn‐Ce/GGBS catalyst has a significant denitration performance when load ratio is 2:1. The active component Ce improves the denitration performance of the catalyst, reduces sulfur poisoning and extends the life of the catalyst. The SO 2 in the flue gas increases the acid sites on the catalyst surface and improves catalyst activity. The larger the ratios of Mn 4+ /Mn 3+ , Ce 4+ /Ce 3+ and O α /O β , the stronger the catalyst activity and the better the denitration performance. © 2022 Society of Chemical Industry (SCI).

Zhang, Lei↗
DOE OSTI2021

Novel metabolic interactions and environmental conditions mediate the boreal peatmoss-cyanobacteria mutualism

Abstract Interactions between Sphagnum (peat moss) and cyanobacteria play critical roles in terrestrial carbon and nitrogen cycling processes. Knowledge of the metabolites exchanged, the physiological processes involved, and the environmental conditions allowing the formation of symbiosis is important for a better understanding of the mechanisms underlying these interactions. In this study, we used a cross-feeding approach with spatially resolved metabolite profiling and metatranscriptomics to characterize the symbiosis between Sphagnum and Nostoc cyanobacteria. A pH gradient study revealed that the Sphagnum–Nostoc symbiosis was driven by pH, with mutualism occurring only at low pH. Metabolic cross-feeding studies along with spatially resolved matrix-assisted laser desorption/ionization mass spectrometry imaging (MALDI-MSI) identified trehalose as the main carbohydrate source released by Sphagnum, which were depleted by Nostoc along with sulfur-containing choline-O-sulfate, taurine and sulfoacetate. In exchange, Nostoc increased exudation of purines and amino acids. Metatranscriptome analysis indicated that Sphagnum host defense was downregulated when in direct contact with the Nostoc symbiont, but not as a result of chemical contact alone. The observations in this study elucidated environmental, metabolic, and physiological underpinnings of the widespread plant–cyanobacterial symbioses with important implications for predicting carbon and nitrogen cycling in peatland ecosystems as well as the basis of general host-microbe interactions.

59 BASIC BIOLOGICAL SCIENCES↗
NASA NTRS1989

Observations of some oxygen-containing and sulfur-containing organic molecules in cold dark clouds

Observations of nine oxygen- and sulfur-containing organic molecules have been made toward the cold dark clouds TMC-1 and L134N. The presence of paraketene (H2C2O) in TMC-1 is confirmed for orthoketene, and has been observed for the first time and a total ketene column density of about 10 to the 13th/sq cm is found. Thioformaldehyde (H2CS) is easily detectable in both TMC-1 and L134N, with a column density about five times larger in the former source. The fractional abundance of ketene is comparable to the predictions of ion-molecule chemistry, while that of thioformaldehyde in TMC-1 is one to two orders of magnitude greater than that expected from such models at steady state. Interstellar sulfur chemistry thus continues to be poorly understood. Upper limits are set for the column densities of formic acid (HCOOH), vinyl alcohol (CH2CHOH), methyl formate (HCO2CH3), formamide (NH2CHO), methyl mercaptan (CH3SH), isothiocyanic acid (HNCS), and thioketene (H2C2S) in both sources.

Irvine, W. M.↗
DOE OSTI2025

Evolutionary and functional relationships between plant and microbial C 1 metabolism in terrestrial ecosystems

One-carbon (C 1 ) metabolism, centered on the universal methyl donor S-adenosyl methionine (SAM), plays critical roles in biosynthesis, redox regulation, and stress responses across plants and microbes. A recently proposed photosynthetic C 1 pathway links SAM methyl groups directly to RuBisCO-mediated CO 2 assimilation and integrates with nitrogen and sulfur metabolism. Light-dependent SAM synthesis may regulate the methylation of biopolymers and specialized metabolites and help mitigate photorespiratory stress under elevated temperature and drought. Phylogenetic analysis of two core enzymes suggests evolutionary continuity from methylotrophic microbes to land plants, supporting microbial origins via endosymbiotic gene transfer. Beyond intracellular roles, C 1 metabolism drives biosphere–atmosphere exchange via gases such as methane, methanol, formic acid, and formaldehyde, and numerous specialized volatiles synthesized through SAM methylation. S-methylmethionine, a mobile C 1 metabolite, may mediate phloem transport of reduced sulfur, nitrogen, and methyl groups, linking above- and belowground C 1 cycling in plants. Advances in real-time gas sensing now allow the high-frequency quantification of C 1 fluxes from leaves, stems, and soils, highlighting C 1 metabolism as a critical and underrecognized component of terrestrial carbon and nutrient cycling. Given its microbial ancestry and the production of diverse volatile biosignatures, C 1 metabolism may also offer unique insights into life's origins and biosignature detection on exoplanets.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Chamber studies of OH + dimethyl sulfoxide and dimethyl disulfide: insights into the dimethyl sulfide oxidation mechanism

Abstract. The oxidation of dimethyl sulfide (DMS) in the marine atmosphere represents an important natural source of non-sea-salt sulfate aerosol, but the chemical mechanisms underlying this process remain uncertain. While recent studies have focused on the role of the peroxy radical isomerization channel in DMS oxidation, this work revisits the impact of the other channels (OH addition and OH abstraction followed by bimolecular RO2 reaction) on aerosol formation from DMS. Due to the presence of common intermediate species, the oxidation of dimethyl sulfoxide (DMSO) and dimethyl disulfide (DMDS) can shed light on these two DMS reaction channels; they are also both atmospherically relevant species in their own right. This work examines the OH oxidation of DMSO and DMDS, using chamber experiments monitored by chemical ionization mass spectrometry and aerosol mass spectrometry to study the full range of sulfur-containing products across a range of NO concentrations. The oxidation of both compounds is found to lead to rapid aerosol formation (which does not involve the intermediate formation of SO2), with a substantial fraction (14 %–47 % S yield for DMSO and 5 %–21 % for DMDS) of reacted sulfur ending up in the particle phase and the highest yields observed under elevated NO conditions. Aerosol is observed to consist mainly of sulfate, methanesulfonic acid, and methanesulfinic acid. In the gas phase, the NOx dependence of several products, including SO2 and S2-containing organosulfur species, suggest reaction pathways not included in current mechanisms. Based on the commonalities with the DMS oxidation mechanism, DMSO and DMDS results are used to reconstruct DMS aerosol yields; these reconstructions roughly match DMS aerosol yield measurements from the literature but differ in composition, underscoring remaining uncertainties in sulfur chemistry. This work indicates that both the abstraction and addition channels contribute to rapid aerosol formation from DMS and highlights the need for more study into the fate of small sulfur radical intermediates (e.g., CH3S, CH3SO2, and CH3SO3) that are thought to play central roles in the DMS oxidation mechanism.

Goss, Matthew B. (ORCID:0000000226885463)↗
DOE OSTI2022

Sustainable Biofuels for Low-Carbon Maritime Transportation

The marine shipping sector heavily depends on fossil fuels and is one of the largest petroleum fuel consumers [1,2]. The annual global marine fuel consumption was estimated to be around 400 million metric tons in 2019 (2.5 billion barrels). Moreover, ocean shipping is one of the most significant contributors to sulfur oxides, nitrogen oxides, and particulate matter emissions. Global shipping contributes 13% of human-caused sulfur emissions and 2.6% of anthropogenic carbon dioxide emissions. As a major source of pollutant emissions, the marine industry faces several challenges related to emission regulations. The International Maritime Organization (IMO) has established a framework for reducing the carbon intensity of shipping: 40% reduction relative to 2008 levels by 2030 and 70% reduction by 2050. As the aviation sector, the maritime shipping sector is difficult to decarbonize through electrification. Biofuels offer the best opportunities for decarbonizing marine shipping in the near and medium-term. Advanced biofuels such as pyrolysis bio-oil offer the low-cost potential for meeting carbon reduction goals. For instance, the pyrolysis bio-oil exhibited promising marginal CO2 abatement costs at less than $100/tonne CO2-equivalent at a heavy fuel oil price greater than $1.10/gal [1]. As a potential biofuel option for low-carbon maritime shipping, this presentation focuses on a comparative techno-economic analysis (TEA) of bio-oils produced via a fast pyrolysis-based conversion pathway. The pathway converts a 50/50 blend of forest residues and clean pine to bio-oil via three process options: fast pyrolysis without vapor upgrading, and fast pyrolysis with vapor phase upgrading over ZSM-5 zeolite catalyst and Pt/TiO2 catalyst. The process configuration and operation variation led to different capital and operating costs, as well as the resulting raw bio-oil’s yield and quality, e.g., the water content, total acid number, and carboxylic acid number. The study also determined the minimum upgrading of bio-oils required to enable blending with very low sulfur fuel oil (VLSFO), with the associated costs reflected in TEA. This study shows that bio-oil could be a cost-effective fuel option for decarbonizing maritime shipping. Further research is required with respect to biofuel blending properties, such as compatibility with existing fuel system infrastructure and suitable engine performance.

BIOMASS FUELS↗
DOE OSTI2020

Long-Term Trends for Marine Sulfur Aerosol in the Alaskan Arctic and Relationships With Temperature

Marine aerosol plays a vital role in cloud-aerosol interactions during summer in the Arctic. The recent rise in temperature and decrease in sea ice extent have the potential to impact marine biogenic sources. Compounds like methanesulfonic acid (MSA) and non-sea-salt sulfate (nss-SO 4 2- ), oxidation products of dimethyl sulfide (DMS) emitted by marine primary producers, are likely to increase in concentration. Long-term studies are vital to understand these changes in marine sulfur aerosol and potential interactions with Arctic climate. Samples were collected over three summers at two coastal sites on the North Slope of Alaska (Utqiagvik and Oliktok Point). MSA concentrations followed previously reported seasonal trends, with evidence of high marine primary productivity influencing both sites. When added to an additional data set collected at Utqiagvik, an increase in MSA concentration of + 2.5% per year and an increase in nss-SO 4 2- of + 2.1% per year are observed for the summer season over the 20-year record (1998–2017). This study identifies ambient air temperature as a strong factor for MSA, likely related to a combination of interrelated factors including warmer sea surface temperature, reduced sea ice, and temperature-dependent chemical reactions. Analysis of individual particles at Oliktok Point, within the North Slope of Alaska oil fields, showed evidence of condensation of MSA onto anthropogenic particles, highlighting the connection between marine and oil field emissions and secondary organic aerosol. Finally, this study shows the continued importance of understanding MSA in the Arctic while highlighting the need for further research into its seasonal relationship with organic carbon.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1980

A study on the electrolysis of sulfur dioxide and water for the sulfur cycle hydrogen production process

Experimental electrolysis cells using various platinum catalyzed carbon electrodes were tested. When operated at 200 mA/sq cm current density using 50 w/o acid at 50 C and 1 atm, a reference cell required 1.22 volts and degraded rapidly. After several improvements were incorporated into electrodes and the test cell configuration, a later cell required only 0.77 volts under identical operating conditions. At a lower current density, 100 mA/sq cm, the cell required only 0.63 volts. Kinetic studies on metal electrodes, measurements of temperature effects on electrode kinetics, investigations of electrocatalytic activities of metal electrodes over a wide range of acid concentrations, cyclic voltametric studies and evaluation of alternate catalysts were also conducted. From diffusivity experiments, a cation exchange membrane material, P-4010, exhibited an excellent diffusion coefficient, more than two orders of magnitude lower than that of rubber. Ionic resistivity measurements of eight materials showed that microporous rubber had the lowest resistivity.

Source record↗
DOE OSTI2023

Structural insights into plasmalemma vesicle-associated protein (PLVAP): Implications for vascular endothelial diaphragms and fenestrae

In many organs, small openings across capillary endothelial cells (ECs) allow the diffusion of low–molecular weight compounds and small proteins between the blood and tissue spaces. These openings contain a diaphragm composed of radially arranged fibers, and current evidence suggests that a single-span type II transmembrane protein, plasmalemma vesicle-associated protein-1 (PLVAP), constitutes these fibers. Here, we present the three-dimensional crystal structure of an 89-amino acid segment of the PLVAP extracellular domain (ECD) and show that it adopts a parallel dimeric alpha-helical coiled-coil configuration with five interchain disulfide bonds. The structure was solved using single-wavelength anomalous diffraction from sulfur-containing residues (sulfur SAD) to generate phase information. Biochemical and circular dichroism (CD) experiments show that a second PLVAP ECD segment also has a parallel dimeric alpha-helical configuration—presumably a coiled coil—held together with interchain disulfide bonds. Overall, ~2/3 of the ~390 amino acids within the PLVAP ECD adopt a helical configuration, as determined by CD. We also determined the sequence and epitope of MECA-32, an anti-PLVAP antibody. Taken together, these data lend strong support to the model of capillary diaphragms formulated by Tse and Stan in which approximately ten PLVAP dimers are arranged within each 60- to 80-nm-diameter opening like the spokes of a bicycle wheel. Passage of molecules through the wedge-shaped pores is presumably determined both by the length of PLVAP—i.e., the long dimension of the pore—and by the chemical properties of amino acid side chains and N-linked glycans on the solvent-accessible faces of PLVAP.

59 BASIC BIOLOGICAL SCIENCES↗