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NASA NTRS1982

Countercurrent distribution of biological cells

It is known that the addition of phosphate buffer to two polymer aqueous phase systems has a strong effect on the partition behavior of cells and other particles in such mixtures. The addition of sodium phosphate to aqueous poly(ethylene glycol) dextran phase systems causes a concentration-dependent shift in binodial on the phase diagram, progressively lowering the critical conditions for phase separation as the phosphate concentration is increased. Sodium chloride produces no significant shift in the critical point relative to the salt-free case. Accurate determinations of the phase diagram require measurements of the density of the phases; data is presented which allows this parameter to be calculated from polarimetric measurements of the dextran concentrations of both phases. Increasing polymer concentrations in the phase systems produce increasing preference of the phosphate for the dextran-rich bottom phase. Equilibrium dialysis experiments showed that poly(ethylene glycol) effectively rejected phosphate, and to a lesser extent chloride, but that dextran had little effect on the distribution of either salt. Increasing ionic strength via addition of 0.15 M NaCl to phase systems containing 0.01 M phosphate produces an increased concentration of phosphate ions in the bottom dextran-rich phase, the expected effect in this type of Donnan distribution.

Source record↗

NASA NTRS1996

Interactions of anesthetics with the membrane-water interface

Although the potency of conventional anesthetics correlates with lipophilicity, an affinity to water also is essential. It was recently found that compounds with very low affinities to water do not produce anesthesia regardless of their lipophilicity. This finding implies that clinical anesthesia might arise because of interactions at molecular sites near the interface of neuronal membranes with the aqueous environment and, therefore, might require increased concentrations of anesthetic molecules at membrane interfaces. As an initial test of this hypothesis, we calculated in molecular dynamics simulations the free energy profiles for the transfer of anesthetic 1,1,2-trifluoroethane and nonanesthetic perfluoroethane across water-membrane and water-hexane interfaces. Consistent with the hypothesis, it was found that trifluoroethane, but not perfluoroethane, exhibits a free energy minimum and, therefore, increased concentrations at both interfaces. The transfer of trifluoroethane from water to the nonpolar hexane or interior of the membrane is accompanied by a considerable, solvent-induced shift in the conformational equilibrium around the C-C bond.

NASA Center ARC↗

NASA NTRS1993

Comment on 'Summary and implications of reported amino acid concentrations in the Murchison meteorite' by E. L. Shock and M. D. Schulte

A criticism of the claim by Shock and Schulte (1990) that there is a correlation between the amino acid abundances (relative to glycine) in the Murchison meteorite and their aqueous solubilities is presented. Their suggestion that 'the same factors which control the aqueous solubility of many amino acids also control their relative abundances in the Murchison meteorite is argued to be incorrect. It is proposed that even though the water/meteorite ratio would have been less during meteorite aqueous alteration than that in the 100-C laboratory extraction procedure, amino acids are simply too soluble. The distribution of other meteorite organic components such as PAHs may have been affected by alteration because they are only slightly soluble in water and can be easily separated by geochromatographic processes. In their reply Shock and Schulte contend that the critics argue against a point not made in their paper and that their argument was supported with several unsubstantiated assertions, including an unfounded claim that the temperature dependence of amino acid solubilities are 'not greatly different', a misrepresentation of isopiestic studies on concentration solutions as equilibrium solubility measurements.

Miller, Stanley L.↗

NASA NTRS1989

Electrocatalysis for oxygen electrodes in fuel cells and water electrolyzers for space applications

Prakash, Jai↗

NASA NTRS1989

Electrocatalysts for oxygen electrodes in fuel cells and water electrolyzers for space applications

In most instances separate electrocatalysts are needed to promote the reduction of O2 in the fuel cell mode and to generate O2 in the energy storage-water electrolysis mode in aqueous electrochemical systems operating at low and moderate temperatures (T greater than or equal to 200 C). Interesting exceptions are the lead and bismuth ruthenate pyrochlores in alkaline electrolytes. These catalysts on high area carbon supports have high catalytic activity for both O2 reduction and generation (1,2). Rotating ring-disk electrode measurements provide evidence that the O2 reduction proceeds by a parallel four-electron pathway. The ruthenates can also be used as self-supported catalysts to avoid the problems associated with carbon oxidation, but the electrode performance so far achieved in the research at Case Western Reserve University (CWRU) is considerably less. At the potentials involved in the anodic mode the ruthenate pyrochlores have substantial equilibrium solubility in concentrated alkaline electrolyte. This results in the loss of catalyst into the bulk solution and a decline in catalytic activity. Furthermore, the hydrogen generation counter electrode may become contaminated with reduction products from the pyrochlores (lead, ruthenium). A possible approach to this problem is to immobilize the pyrochlore catalyst within an ionic-conducting solid polymer, which would replace the fluid electrolyte within the porous gas diffusion O2 electrode. For bulk alkaline electrolyte, an anion-exchange polymer is needed with a transference number close to unity for the Oh(-) ion. Preliminary short-term measurements with lead ruthenates using a commercially available partially-fluorinated anion-exchange membrane as an overlayer on the porous gas-fed electrode indicate lower anodic polarization and virtually unchanged cathodic polarization.

Prakash, Jai↗

NASA NTRS1998

The Effects of Impurities on Protein Crystal Growth and Nucleation: A Preliminary Study

Kubota and Mullin (1995) devised a simple model to account for the effects of impurities on crystal growth of small inorganic and organic molecules in aqueous solutions. Experimentally, the relative step velocity and crystal growth of these molecules asymptotically approach zero or non-zero values with increasing concentrations of impurities. Alternatively, the step velocity and crystal growth can linearly approach zero as the impurity concentration increases. The Kubota-Mullin model assumes that the impurity exhibits Langmuirian adsorption onto the crystal surface. Decreases in step velocities and subsequent growth rates are related to the fractional coverage (theta) of the crystal surface by adsorbed impurities; theta = Kx / (I +Kx), x = mole fraction of impurity in solution. In the presence of impurities, the relative step velocity, V/Vo, and the relative growth rate of a crystal face, G/Go, are proposed to conform to the following equations: V/Vo approx. = G/Go = 1 - (alpha)(theta). The adsorption of impurity is assumed to be rapid and in quasi-equilibrium with the crystal surface sites available. When the value of alpha, an effectiveness factor, is one the growth will asymptotically approach zero with increasing concentrations of impurity. At values less than one, growth approaches a non-zero value asymptotically. When alpha is much greater than one, there will be a linear relationship between impurity concentration and growth rates. Kubota and Mullin expect alpha to decrease with increasing supersaturation and shrinking size of a two dimensional nucleus. It is expected that impurity effects on protein crystal growth will exhibit behavior similar to that of impurities in small molecule growth. A number of proteins were added to purified chicken egg white lysozyme, the effect on crystal nucleation and growth assessed.

Schall, Constance A.↗

NASA NTRS2011

One-carbon (bio ?) Geochemistry in Subsurface Waters of the Serpentinizing Coast Range Ophiolite

Serpentinization - the aqueous alteration of ultramafic rocks - typically imparts a highly reducing and alkaline character to the reacting fluids. In turn, these can influence the speciation and potential for metabolism of one-carbon compounds in the system. We examined the aqueous geochemistry and assessed the biological potential of one-carbon compounds in the subsurface of the McLaughlin Natural Reserve (Coast Range Ophiolite, California, USA). Fluids from wells sunk at depths of 25-90 meters have pH values ranging from 9.7 to 11.5 and dissolved inorganic carbon (DIC concentrations) generally below 60 micromolar. Methane is present at concentrations up to 1.3 millimolar (approximately one-atmosphere saturation), and hydrogen concentrations are below 15 nanomolar, suggesting active consumption of H2 and production of CH4. However, methane production from CO2 is thermodynamically unfavorable under these conditions. Additionally, the speciation of DIC predominantly into carbonate at these high pH values creates a problem of carbon availability for any organisms that require CO2 (or bicarbonate) for catabolism or anabolism. A potential alternative is carbon monoxide, which is present in these waters at concentrations 2000-fold higher than equilibrium with atmospheric CO. CO is utilized in a variety of metabolisms, including methanogenesis, and bioavailability is not adversely affected by pH-dependent speciation (as for DIC). Methanogenesis from CO under in situ conditions is thermodynamically favorable and would satisfy biological energy requirements with respect to both Gibbs Energy yield and power.

McLaughlin Natural Reserve↗

NASA NTRS2001

Surfactant Facilitated Spreading of Aqueous Drops on Hydrophobic Surfaces

Microgravity technologies often require aqueous phases to spread over nonwetting hydrophobic solid surfaces. Surfactants facilitate the wetting of water on hydrophobic surfaces by adsorbing on the water/air and hydrophobic solid/water interfaces and lowering the surface tensions of these interfaces. The tension reductions decrease the contact angle, which increases the equilibrium wetted area. Hydrocarbon surfactants; (i.e., amphiphiles with a hydrophobic moiety consisting of an extended chain of (aliphatic) methylene -CH2- groups attached to a large polar group to give aqueous solubility) are capable of reducing the contact angles on surfaces which are not very hydrophobic, but do not reduce significantly the contact angles of the very hydrophobic surfaces such as parafilm, polyethylene or self assembled monolayers. Trisiloxane surfactants (amphiphiles with a hydrophobe consisting of methyl groups linked to a trisiloxane backbone in the form of a disk ((CH3)3-Si-O-Si-O-Si(CH3)3) and an extended ethoxylate (-(OCH2CH2)a-) polar group in the form of a chain with four or eight units) can significantly reduce the contact angle of water on a very hydrophobic surface and cause rapid and complete (or nearly complete) spreading (termed superspreading). The overall goal of the research described in this proposal is to establish and verify a theory for how trisiloxanes cause superspreading, and then use this knowledge as a guide to developing more general hydrocarbon based surfactant systems which superspread. We propose that the trisiloxane surfactants superspread because their structure allows them to strongly lower the high hydrophobic solid/aqueous tension when they adsorb to the solid surface. When the siloxane adsorbs, the hydrophobic disk parts of the molecule adsorb onto the surface removing the surface water. Since the cross-sectional area of the disk is larger than that of the extended ethoxylate chain, the disks can form a space-filling mat on the surface which removes a significant amount of the surface water. In this presentation, we report the results of measurements of the molecular packing and rates of kinetic exchange of the trisiloxane surfactants at the air/water interface in order to confirm our picture of trisiloxane packing, and provide additional insight into the superspreading process. We used the pendant bubble technique as a Langmuir trough to measure the trisiloxane equation of state which relates the tension to the surface concentration. From these measurements we obtain accurate values for the maximum packing density. We find that trisiloxanes with 4 and 8 ethoxylate groups have the same maximum packing concentration, indicating that the maximum packing is controlled by the cross section of the head group. For trisiloxanes with larger than eight ethoxylates, the maximum packing increases with ethoxylate number, indicating that the disposition of the ethoxylate chain (i.e., its effective size) is controlling. This supports our picture of superspreading: The superspreading ability of trisiloxanes decreases considerably for trisiloxanes with larger than eight ethoxylates; the packing measurements indicate that for the higher ethoxylate number trisiloxanes, the compact nonpolar head groups are pushed apart by the ethoxylate chain. They leave spaces of surface water on adsorption and do not lower the solid tension as much as their lower chain analogues. Finally the report measurements of the dynamic tension reduction accompanying the adsorption of trisiloxanes onto an initially clean interface using the pendant bubble technique, and we obtain from these relaxations, the equation of state and a mass transfer model, the rate constants for kinetic exchange. We find that the rate constants for desorption of trisiloxanes are generally much slower than for analogous aliphatic polyethoxylate surfactants with identical ethoxylate chain lengths. When an aqueous drop of a superspreader solution is placed on a hydrophobic surface and begins to spread, the lower desorption rates allows the tension at the drop center to remain reduced relative to the tension of the expanding periphery, thus strengthening Marangoni forces which can assist the spreading. Marangoni forces can be especially significant in the case of superspreaders because their maximum equilibrium reduction in tension is several dynes/cm lower than for aliphatic surfactants.

Kumar, Nitin↗

NASA NTRS2000

Depositional facies and aqueous-solid geochemistry of travertine-depositing hot springs (Angel Terrace, Mammoth Hot Springs, Yellowstone National Park, U.S.A.)

Petrographic and geochemical analyses of travertine-depositing hot springs at Angel Terrace, Mammoth Hot Springs, Yellowstone National Park, have been used to define five depositional facies along the spring drainage system. Spring waters are expelled in the vent facies at 71 to 73 degrees C and precipitate mounded travertine composed of aragonite needle botryoids. The apron and channel facies (43-72 degrees C) is floored by hollow tubes composed of aragonite needle botryoids that encrust sulfide-oxidizing Aquificales bacteria. The travertine of the pond facies (30-62 degrees C) varies in composition from aragonite needle shrubs formed at higher temperatures to ridged networks of calcite and aragonite at lower temperatures. Calcite "ice sheets", calcified bubbles, and aggregates of aragonite needles ("fuzzy dumbbells") precipitate at the air-water interface and settle to pond floors. The proximal-slope facies (28-54 degrees C), which forms the margins of terracette pools, is composed of arcuate aragonite needle shrubs that create small microterracettes on the steep slope face. Finally, the distal-slope facies (28-30 degrees C) is composed of calcite spherules and calcite "feather" crystals. Despite the presence of abundant microbial mat communities and their observed role in providing substrates for mineralization, the compositions of spring-water and travertine predominantly reflect abiotic physical and chemical processes. Vigorous CO2 degassing causes a +2 unit increase in spring water pH, as well as Rayleigh-type covariations between the concentration of dissolved inorganic carbon and corresponding delta 13C. Travertine delta 13C and delta 18O are nearly equivalent to aragonite and calcite equilibrium values calculated from spring water in the higher-temperature (approximately 50-73 degrees C) depositional facies. Conversely, travertine precipitating in the lower-temperature (< approximately 50 degrees C) depositional facies exhibits delta 13C and delta 18O values that are as much as 4% less than predicted equilibrium values. This isotopic shift may record microbial respiration as well as downstream transport of travertine crystals. Despite the production of H2S and the abundance of sulfide oxidizing microbes, preliminary delta 34S data do not uniquely define the microbial metabolic pathways present in the spring system. This suggests that the high extent of CO2 degassing and large open-system solute reservoir in these thermal systems overwhelm biological controls on travertine crystal chemistry.

Non-NASA Center↗

NASA NTRSDate not supplied

Geochemical Insights Into Volcanic and Lithospheric Evolution of Mars

Introduction: The Martian lithosphere plays a pivotal role in volcanic processes, altering surface features, climate shifts, and the planet's early habitability. Crucially, the rigid lithosphere significantly influences Mars' long-term thermal conditions. Studying various geological eons’ volcanic compositions unveils how the lithosphere has evolved, even though understanding the early Noachian volcanic chemistry remains challenging due to weathering and resurfacing. In this study, newly discovered Noachian volcanic terranes[1-2] along with Hesperian and Amazonian volcanic terranes[3] are considered(Figure 1), to infer the evolution of the Martian lithosphere. Figure 1:Mars topographic map derived from MOLA-HRSC data [4] highlights the study regions including the Noachian volcanic terranes, Arabia Terra (AT), Thaumasia Minor (TM), and the Southwest Margin of Icaria Planum (SWIP)[5].Additionally, the Hesperian volcanic terranes such as Syrtis Major (SM), Hesperia Planum (HP), and, the Amazonian volcanic terranes encompass Elysium Mons (EM), Alba Patera (AP), and Olympus Mons (OM) are marked. Methods and Datasets: We use the most recent elemental mass fraction maps derived from gamma spectroscopy data from the Mars Odyssey 2001mission [6]to ascertain the bulk composition of the Martian landscape. Utilizing the updated geochemical provinces dataset of Mars[7], we consider bulk chemistry variations within our study regions. The maps, at a resolution of 50×50, encompass elements like Al, Ca, Fe, Si, K, Th, H2O, Cl, and S, detected through Gamma-Ray Spectroscopy (GRS) with decimeter scale depth sensitivity[6].Additional major and minor elements like Mg, Na, Ti, P, and Mn, using mass balance methods [8]serve as inputs for melting and crystallization simulations. We employ the pMELTS model with FMQ-3to FMQ oxygen fugacity to estimate the Pressure(P)and melting degree(F)in various eons of volcanic terranes. We have also used conventional thermobarometric calculations to determine their formation P-T conditions, using silica activity and olivine-melt Mg-exchange thermometry[9-10]. Results: Chemical Composition of Studied Volcanic Terranes: To assess formation conditions, we have investigated if GRS-measured compositions signify primary igneous processes by evaluating weathering through the Chemical Index of Alteration (CIA), K/Th ratios, and ternary plots for aqueous alteration. Consistent K/Th ratios and low CIA (<50) across volcanic regions suggest minimal large-scale weathering, affirming well-preserved igneous material extending at decimeter depths. In addition, the calculated bulk compositions align with Martian mantle equilibrium, confirming studied volcanic terranes-Arabia Terra, Thaumasia Minor, and SWIP -as primary or less altered compositions, reinforcing their representativeness at a regional GRS scale on Mars. We have also estimated the bulk compositions of Hesperian and Amazonian volcanic terranes shown in Figure 1. All volcanic terranes represent the primary or minimally altered composition. Temporal Evolution of Martian Volcanic Terranes: Our results show P-T conditions ranging from 1.3-1.6 GPa and 1350-1390°C for Noachian terranes, while Hesperian volcanic terranes vary from 1.6-1.7 GPa and 1370-1395°C, and Amazonian volcanic terranes range between 1.9-2.8 GPa and 1380-1415°C. Our analyses correspond to lithospheric thicknesses/ depth of melting for Noachian which ranges from110-135 km, 120-235 km for Hesperian terranes, and 160-235 km for Amazonian terranes. Partial melting percentages (F) range from 8-12% for Noachian, 10-11% for Hesperian, and 10-12% for Amazonian. We have also calculated mantle potential temperatures (Tp) to show variations across epochs(Figure 2). Heat flux estimation shows variations from 51-65 mW/m2 for Noachian, 38-45 mW/m2for Hesperian, and 27-39 mW/m2for Amazonian terranes, implying temporal changes in lithospheric thickness and heat flow. Comparison of Noachian volcanic terranes with Hesperian and Amazonian reveals variations in lithospheric thickness and heat flux, indicating potential implications for Martian surface conditions, including volcanic activity, climate evolution, and early habitability. Figure 2: P-T diagram displays formation conditions of studied Martian volcanic regions using GRS data, alongside Noachian-age surface basalt samples from Gusev, Gale, and Jezero. Dashed lines represent Martian mantle potential temperatures, calculated by adding the latent heat of fusion to the equilibrium temperature at which melt and solid mantle coexist and subtracting the Martian adiabatic gradient corresponding to the depth of melt. The solid line shows the Martian mantle solidus [11].Discussion& Implication: The study explores Martian volcanic activity across eons. Uniform lithospheric thickness from the Noachian to Hesperian eons suggests persistent weak plumes until Hesperian, influencing heat flow variations. Noachian's high heat flux, likely due to concentrated radioactive elements, shows spatial heterogeneity, indicating early Mars' differentiated mantle. Volcanic outgassing plays avital role in the formation of the Martian climate, likely sustained water on the surface, influencing warm-wet or cold-dry conditions. Hesperian's favorable lithospheric heat flow (45 mW/m2) supports extended water existence, resembling Earth's conditions. Whereas, Amazonian's diminished heat flux (25 mW/m2) corresponds to water loss and arid climate. Hesperian's similar lithospheric thickness to mid-Noachian implies prolonged water retention, influencing climate and potential for astrobiological research, expanding perspectives for future Martian missions. Future work: As volcanism was active throughout its history. The emergence of Mars' extensive volcanic regions, known as large igneous provinces, which are linked to intermittent volcanic activity driven by mantle plumes, poses challenges to understanding the scale and persistence of these phenomena in Martian convection models. Therefore, understanding the regional-scale changes in eruptive processes within Martian volcanic provinces over time remains unclear and crucial for deciphering the evolution of the Martian interior without Earth-like plate tectonics. We will continue this work with petrological and thermoelastic analyses to study the compositional and spatiotemporal evolution of the Elysium Volcanic Province.

A Rani↗