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At least 55 records · Page 3

Dissolution of quartz in aqueous basic solution, 106-236 C - Surface kinetics of 'perfect' crystallographic faces

A highly accurate method, called the negative crystal method, for determining the rate of dissolution on specific crystallographic faces of crystals was developed, in which the dissolution rates of nominally perfect crystal faces are obtained by measuring the size of individual negative crystals during a sequence of dissolution steps. The method was applied to determine the apparent activation energy and rate constants for the dissolution of quartz in 0.01 M KOH solutions at temperatures from 106 to 236 C. Also investigated were the effects of hydroxyl activity and ionic strength. The apparent activation energies for the dissolution of the prism and of the rhomb were determined.

Gratz, Andrew J.↗

Dynamic light scattering analysis of solutions from which lysozyme crystals grow

The variation of the friction factor was measured by photon correlation spectroscopy during isothermal growth of chicken egg white lysozyme crystals. It was observed to initially increase to a maximum as crystals formed, and then to decrease to a constant value. The change in the friction factors was measured as a function of temperature at concentrations of lysozyme varying from one sufficiently low that molecular interactions were undetectable to concentrations near those at which crystals grow in solutions, in all cases the ionic strength was below that required for crystallization.

Bishop, J. B.↗

Aggregation-Enhanced Raman Scattering by a Water-Soluble Porphyrin

Much interest in our laboratory has focused on aggregation of organic compounds, particularly cyanine dyes and porphyrins. For this discussion we have applied absorption and Raman scattering spectroscopies to characterize aggregated TSPP (tetrakis-(p-sulfonatophynyl) porphyrin) in aqueous solution. Based on concentration, pH and ionic strength dependence of TSPP absorption, we deduce that aggregation evolves through the formation of TSPP diacid and that the diacid is the repeating unit in the aggregate. The Raman bands of TSPP in strongly acidic solution lead us further to conclude that vibrations of adjacent molecules are perturbed in a fashion that is consistent with the pyrrolic ring in the porphinato macrocycle being ruffled, and that two aggregate arrangements occur: specifically J- and H-type aggregates. Furthermore, aggregation enhancement is advanced as a viable mechanism to explain enhanced Raman Scattering for homogeneous aqueous phase TSPP, where the surface-enhancement mechanism is not applicable.

Akins, Daniel L.↗

The Effects of Acetate Buffer Concentration on Lysozyme Solubility

The micro-solubility column technique was employed to systematically investigate the effects of buffer concentration on tetragonal lysozyme solubility. While keeping the NaCl concentrations constant at 2%, 3%, 4%, 5% and 7%, and the pH at 4.0, we have studied the solubility of tetragonal lysozyme over an acetate buffer concentration range of 0.01M to 0.5M as a function of temperature. The lysozyme solubility decreased with increasing acetate concentration from 0.01M to 0.1M. This decrease may simply be due to the net increase in solvent ionic strength. Increasing the acetate concentration beyond 0.1M resulted in an increase in the lysozyme solubility, which reached a peak at - 0.3M acetate concentration. This increase was believed to be due to the increased binding of acetate to the anionic binding sites of lysozyme, preventing their occupation by chloride. In keeping with the previously observed reversal of the Hoffmeister series for effectiveness of anions in crystallizing lysozyme, acetate would be a less effective precipitant than chloride. Further increasing the acetate concentration beyond 0.3M resulted in a subsequent gradual decrease in the lysozyme solubility at all NaCl concentrations.

Forsythe, Elizabeth L.↗

Studies of a Halophilic NADH Dehydrogenase. 1: Purification and Properties of the Enzyme

An NADH dehydrogenase obtained from an extremely halophilic bacterium was purified 570-fold by a combination of gel filtration, chromatography on hydroxyapatite, and ion-exchange chromatography on QAE-Sephadex. The purified enzyme appeared to be FAD-linked and bad an apparent molecular weight of 64000. Even though enzyme activity was stimulated by NaCl, considerable activity (430 % of the maximum activity observed in the presence of 2.5 M NaCl) was observed in the absence of added NaCl. The enzyme was unstable when incubated in solutions of low ionic strength. The presence of NADH enhanced the stability of the enzyme.

Hochstein, Lawrence I.↗

An Advanced Approach to Simultaneous Monitoring of Multiple Bacteria in Space

This interim report describes progress on the development of spacecraft-compatible methods of nucleic acid preparation and cleanup. Grantee found that performance of a widely-known protocol could be greatly enhanced by the addition of a sizing step to eliminate acids. Testing of alternative adsorptive methods is underway. Grantee also confirmed and extended observation of precipitation of DNA by condensing agents such a spermine at low ionic strength.

Eggers, Mitch↗

The Effect of Solution Conditions on the Nucleation Kinetics of Tetragonal Lysozyme Crystals

An understanding of protein crystal nucleation rates and the effect of solution conditions upon them, is fundamental to the preparation of protein crystals of the desired size and shape for X-ray diffraction analysis. The ability to predict the effect of supersaturation, temperature, pH and precipitant concentration on the number and size of crystals formed is of great benefit in the pursuit of protein structure analysis. In this study we experimentally examine the effect of supersaturation, temperature, pH and sodium chloride concentration on the nucleation rate of tetragonal chicken egg white lysozyme crystals. In order to do this batch crystallization plates were prepared at given solution concentrations and incubated at three different temperatures over the period of one week. The number of crystals per well with their size and dimensions were recorded and correlated against solution conditions. Duplicate experiments indicate the reproducibility of the technique. Although it is well known that crystal numbers increase with increasing supersaturation, large changes in crystal number were also correlated against solution conditions of temperature, pH and salt concentration over the same supersaturation ranges. Analysis of these results enhance our understanding of the effect of solution conditions such as the dramatic effect that small changes in charge and ionic strength can have on the number of tetragonal lysozyme crystals that form and grow in solution.

Judge, Russell A.↗

Fluorescence Studies of Protein Crystal Nucleation

Fluorescence can be used to study protein crystal nucleation through methods such as anisotropy, quenching, and resonance energy transfer (FRET), to follow pH and ionic strength changes, and follow events occurring at the growth interface. We have postulated, based upon a range of experimental evidence that the growth unit of tetragonal hen egg white lysozyme is an octamer. Several fluorescent derivatives of chicken egg white lysozyme have been prepared. The fluorescent probes lucifer yellow (LY), cascade blue, and 5-((2-aminoethyl)aminonapthalene-1-sulfonic acid (EDANS), have been covalently attached to ASP 101. All crystallize in the characteristic tetragonal form, indicating that the bound probes are likely laying within the active site cleft. Crystals of the LY and EDANS derivatives have been found to diffract to at least 1.7 A. A second group of derivatives is to the N-terminal amine group, and these do not crystallize as this site is part of the contact region between the adjacent 43 helix chains. However derivatives at these sites would not interfere with formation of the 43 helices in solution. Preliminary FRET studies have been carried out using N-terminal bound pyrene acetic acid (Ex 340 nm, Em 376 nm) lysozyme as a donor and LY (Ex -425 nm, Em 525 nm) labeled lysozyme as an acceptor. FRET data have been obtained at pH 4.6, 0.1 M NaAc buffer, at 5 and 7% NaCl, 4 C. The corresponding Csat values are 0.471 and 0.362 mg/ml (approximately 3.3 and approximately 2.5 x 10(exp -5) M respectively). The data at both salt concentrations show a consistent trend of decreasing fluorescence intensity of the donor species (PAA) with increasing total protein concentration. This decrease is more pronounced at 7% NaCl, consistent with the expected increased intermolecular interactions at higher salt concentrations reflected in the lower solubility. The calculated average distance between any two protein molecules at 5 x 10(exp -6) M is approximately 70nm, well beyond the range where any FRET can be expected. Results from these and ongoing studies will be presented.

Pusey, Marc L.↗

Radioprotection of Human Cell Nuclear DNA by Polyamines: Radiosensitivity of Chromatin is Influenced by Tightly Bound Spermine

The polyamines putrescine (PUT) and spermine (SPM) were examined for their ability to protect human cell Deoxyribonucleic Acid (DNA) against the formation of radiation-induced double-strand breaks (DSBs). As observed previously, under conditions where polyamines were shown to be almost completely absent, association with nuclear matrix protein into a nucleoid, and organization into chromatin structure, protected DNA from induction of DSBs by factors of 4.5 and 95, respectively. At concentrations below 1 mM, PUT or SPM provided equivalent levels of protection to deproteinized nuclear DNA, consistent with their capacity to scavenge radiation-induced radicals. At constant ionic strength, 5 mM SPM protected deproteinized DNA and nucleoid DNA and DNA in nuclear chromatin by factors of 100 and 26, respectively. At 5 mM, SPM provided 15 times greater protection of deproteinized DNA than did PUT. Under physiologically relevant conditions, 5 mM SPM protected DNA in the intact nucleus from the induction of DSBs by a factor of 2 relative to DNA in the absence of SPM. Studies of SPM binding during cellular fractionation revealed that a significant fraction of the cellular SPM is tightly bound in the nucleus but can be removed by extended washing. Thus the association of SPM with nuclear chromatin appears to be a significant contributor to the resistance of the cell's DNA to the induction of DSBs.

Warters, Raymond L.↗

An Energetic Concept of Habitability for the Deep Subsurface

Universally, life must be characterized by a characteristic level of order and complexity. In the most general sense, habitability could then be defined as the set of factors required to allow the creation and maintenance of molecular complexity. These factors are: chemical raw materials; energy with which to assemble those materials into complex molecules and sustain the resultant state of complexity; a solvent that allows the interaction of complex molecules, promotes tertiary structure, and permits compartmentalization; and environmental conditions that permit the assembly and maintenance of complex molecules. On Earth, these general requirements correspond to the major biogenic elements C, H, O, N, P, S; chemical or light energy; the solvent water; and specific ranges of temperature, pH, radiation, ionic strength, and so forth, which have thus far been determined on and exclusively empirical basis. Importantly, while the complete absence of any of these factors ensures uninhabitable conditions, the mere presence of all four does not guarantee habitability. In each case - even that of water - it is a question of degree. This question can be couched in quantitative terms by considering the impact of each of these factors on cellular energy balance. More "extreme" conditions (e.g., high temperature, high or low pH, etc.), lower water activity, and low concentrations of nutrients incur or have potential to be addressed by increased investment of energy on the part of the cell. This must be balanced by energy conservation in the cell, noting that biochemical, mass transport, and abiotic chemical limitations intervene between environmental energy availability and biological energy capture. Similarly, lower boundary conditions are emplaced on useful environmental energy yields by the "quantized" nature of biological energy conservation, and upper boundary conditions are emplaced by energy levels or fluxes that are destructive with respect to complexity. This energetic framework, with boundary conditions supplied by the specifics of the biochemistry in question, offers a generalized, yet quantitative means of assessing the habitability of any system with respect to complex life.

Hoehler, Tori M.↗

Confirmation of Soluble Sulfate at the Phoenix Landing Site: Implications for Martian Geochemistry and Habitability

Over the past several decades, elemental sulfur in martian soils and rocks has been detected by a number of missions using X-ray spectroscopy [1-3]. Optical spectroscopy has also provided evidence for widespread sulfates on Mars [4,5]. The ubiquitous presence of sulfur in soils has been interpreted as a widely distributed sulfate mineralogy [6]. However, direct confirmation as to the identity and solubility of the sulfur species in martian soil has never been obtained. One goal of the Wet Chemistry Laboratory (WCL) [7] on board the 2007 Phoenix Mars Lander [8] was to determine soluble sulfate in the martian soil. The WCL received three primary samples. Each sample was added to 25 mL of leaching solution and analysed for solvated ionic species, pH, and conductivity [9,10]. The analysis also showed a discrepancy between charge balance, ionic strength, and conductivity, suggesting unidentified anionic species.

Kounaves, S. P.↗

Ion Exchange Technology Development in Support of the Urine Processor Assembly

The urine processor assembly (UPA) on the International Space Station (ISS) recovers water from urine via a vacuum distillation process. The distillation occurs in a rotating distillation assembly (DA) where the urine is heated and subjected to sub-ambient pressure. As water is removed, the original organics, salts, and minerals in the urine become more concentrated and result in urine brine. Eventually, water removal will concentrate the urine brine to super saturation of individual constituents, and precipitation occurs. Under typical UPA DA operating conditions, calcium sulfate or gypsum is the first chemical to precipitate in substantial quantity. During preflight testing with ground urine, the UPA achieved 85% water recovery without precipitation. However, on ISS, it is possible that crewmember urine can be significantly more concentrated relative to urine from ground donors. As a result, gypsum precipitated in the DA when operating at water recovery rates at or near 85%, causing the failure and subsequent re14 NASA Tech Briefs, September 2013 placement of the DA. Later investigations have demonstrated that an excess of calcium and sulfate will cause precipitation at water recovery rates greater than 70%. The source of the excess calcium is likely physiological in nature, via crewmembers' bone loss, while the excess sulfate is primarily due to the sulfuric acid component of the urine pretreatment. To prevent gypsum precipitation in the UPA, the Precipitation Prevention Project (PPP) team has focused on removing the calcium ion from pretreated urine, using ion exchange resins as calcium removal agents. The selectivity and effectiveness of ion exchange resins are determined by such factors as the mobility of the liquid phase through the polymer matrix, the density of functional groups, type of functional groups bound to the matrix, and the chemical characteristics of the liquid phase (pH, oxidation potential, and ionic strength). Previous experience with ion exchange resins has demonstrated that the most effective implementation for an ion exchange resin is a cartridge, or column, in which the resin is contained. Based on the results of equilibrium and sub-scale dynamic column testing, a possible solution for mitigating the calcium precipitation issue on the ISS has been identified. From an original pool of 13 ion exchange resins, two candidates have been identified that demonstrate substantial calcium removal on the sub-scale. The dramatic reduction in resin performance from published calcium uptake demonstrates the need for thorough evaluation of resins at the low pH and strong oxidizing environment present in the UPA. Chemical variations in the influent (calcium concentrations and pretreatment dosing) appear to have a noticeable impact on the calcium capacity of the resin. Low calcium concentrations and high pretreatment dosing will likely result in a decrease in calcium capacity. Conversely, low pre trea t - ment dosing will likely result in an increase in calcium capacity. In contrast, investigations at a variety of flow rates, length-to-diameter ratios, resin volumes, and flow regimes (continuous versus pulsed) show that changes in physical parameters do not have substantial impacts on resin performance in the very low specific velocity ranges of interest. This result is particularly useful because most commercial applications at higher specific velocities do show a relatively strong relationship between flow and capacity. The lack of a strong relationship will allow more flexibility in the implementation of an ion exchange bed for flight. Verification of subscale tests with flight-scale resin beds is recommended prior to implementation in the on-orbit UPA.

Mitchell, Julie↗

Estimating the Rate of Occurrence of Renal Stones in Astronauts

Changes in urine chemistry, during and post flight, potentially increases the risk of renal stones in astronauts. Although much is known about the effects of space flight on urine chemistry, no inflight incidence of renal stones in US astronauts exists and the question "How much does this risk change with space flight?" remains difficult to accurately quantify. In this discussion, we tackle this question utilizing a combination of deterministic and probabilistic modeling that implements the physics behind free stone growth and agglomeration, speciation of urine chemistry and published observations of population renal stone incidences to estimate changes in the rate of renal stone presentation. The modeling process utilizes a Population Balance Equation based model developed in the companion IWS abstract by Kassemi et al. (2016) to evaluate the maximum growth and agglomeration potential from a specified set of urine chemistry values. Changes in renal stone occurrence rates are obtained from this model in a probabilistic simulation that interrogates the range of possible urine chemistries using Monte Carlo techniques. Subsequently, each randomly sampled urine chemistry undergoes speciation analysis using the well-established Joint Expert Speciation System (JESS) code to calculate critical values, such as ionic strength and relative supersaturation. The Kassemi model utilizes this information to predict the mean and maximum stone size. We close the assessment loop by using a transfer function that estimates the rate of stone formation from combining the relative supersaturation and both the mean and maximum free stone growth sizes. The transfer function is established by a simulation analysis which combines population stone formation rates and Poisson regression. Training this transfer function requires using the output of the aforementioned assessment steps with inputs from known non-stone-former and known stone-former urine chemistries. Established in a Monte Carlo system, the entire renal stone analysis model produces a probability distribution of the stone formation rate and an expected uncertainty in the estimate. The utility of this analysis will be demonstrated by showing the change in renal stone occurrence predicted by this method using urine chemistry distributions published in Whitson et al. 2009. A comparison to the model predictions to previous assessments of renal stone risk will be used to illustrate initial validation of the model.

gravitational physiology↗

The Effect of Solution Chemistries and Freezing Temperatures on the Morphology of Cryogenic Opal-A (COA): Implications for Past Climates on Mars

Cryogenic opal-A (COA) is a type of hydrated amorphous silica that forms when silica-rich geothermal fluids erupt sub-aerially and are exposed to air temperatures below 0 °C. As the fluid cools and water-ice forms, the solution increases in ionic strength and reaches saturation of opal-A. This results in the precipitation of opal-A between water ice crystals. Natural COA is found embedded within frozen fluids near hydrothermal sources, and has been shown to preserve signs of biological activity. In this study, two solution chemistries (hydrochloric acid (HCl) and sulfuric acid (H2SO4)) and three freezing temperatures (-20, -80, -196 ºC) were used to synthesize COA in the lab. SEM analyses showed that COA frozen at -20 ºC in HCl solutions produced smooth silica branches similar to what was observed in previous studies. COA precipitated at lower freezing temperatures demonstrated progressively smaller particle sizes and unique morphologies such as halite dendrites within silica, desiccation cracks, and pores. COA made in H2SO4 solutions was more angular and fragmented than COA made in HCl solutions. Particle size also decreased with decreasing freezing temperature. COA textures have implications for terrestrial samples as well as future samples returned from Mars because they can provide information about past climate and fluid chemistry.

J V Hogancamp↗

Predicting the Seawater Chemistry of an Ocean World Using Machine Learning on Isotopic Measurements of Volatile CO2

Introduction: Given the long time intervals required for data transmission to and from ocean worlds targets, low bandwidth for data transmission, time required for data processing and analysis, and potentially extreme radiation environments (e.g., Europa), it is clear that ocean worlds missions will need more autonomous flight instruments and software in order to achieve established science goals. Protracted time intervals for data analysis (e.g., Europa Lander) strongly motivates the development of rapid, consistent and streamlined methods for interpreting data from flight mass spectrometers to e.g., determine how mass spectra from a plume or surface liquid/ice relates to the surface/subsurface. Since mass spectrometry also has the potential to correctly identify biosignatures[1], it is imperative that such methods for interpreting data are consistent and accurate. We used 848 isotope ratio mass spectra from laboratory analyses of CO2 that interacted with ocean worlds-relevant seawaters as a ‘training’ dataset for ‘unsupervised’ machine learning. In unsupervised learning, characteristics of the data are not labeled or linked, and any similarities found only result from the neural network. CO2 isotopologues analyzed for this dataset mimic the remote measurements of CO2 by a flight mass spectrometer, and are detailed in Theiling [2]. From this dataset, we used measured features of the spectra, such as retention time, intensity, and (isotopologue) mass ratios as inputs for our autoencoder neural network. Our neural network was trained to find similarities in these and other spectral features for seawaters of a particular composition and amount of initial CO2. Successful training then created an output of these similarities for various seawaters, which included MgSO4, Na2SO4, NaCl, MgCl2, KCl, and NaHCO3, and combinations of these salts. We then applied dimensionality reduction techniques such as Principal Component Analysis (PCA), T-Distributed Stochastic Neighbor Embedding (TSNE), and Uniform Manifold Approximation and Projection (UMAP) to demonstrate latent data features as a two-dimensional projection in a unitless, high-dimensional space. In this projection, a data point represents the combined effect of spectral features such as intensity, retention time, and isotope ratio. Our initial UMAP demonstrates data clustering (organization of the data by the neural network) based on the amount of CO2 that had initially interacted with each seawater. Further training using more ‘supervised’ learning techniques demonstrate strong clustering of preliminary data based on initial CO2 concentration, seawater chemical composition, and ionic strength (salinity). Our preliminary work therefore suggests that machine learning has the potential to identify compositional variants of an ocean world seawater based on mass spectra from volatile CO2 measurements. Acknowledgments: This work was funded through a Strategic Task Group at NASA Goddard Space Flight Center. The training dataset was collected through funding from the Oklahoma Space Grant Consortium. References: [1] Pappalardo, R. et al. (2013) Astrobiology, 13, 740–773. [2] Theiling (2020) Icarus, 114216.

Europa↗

Interpretable Machine Learning Models for Autonomous Characterization of Analogue Ocean World Seawater Chemistry and Biosignature Potential Using Isotope Ratio Data

Background: Future missions to ocean worlds, such as Enceladus and Europa, will attempt to characterize the subsurface seawater chemistry and assess the potential for life. Such missions will be equipped with capabilities to precisely measure volatile isotopes in plumes, atmospheres, and exospheres. Motivation: While large isotopic fractionations can indicate a biological source, there are signatures resulting from abiotic geochemical processes that mimic isotopic biosignatures. While machine learning (ML) has the potential to disentangle competing effects and biotic mimicry, high-dimensional isotope ratio mass spectrometry (IRMS) data is likely to contain noise/irrelevant features and involve complex statistical interactions that make human inference and interpretation difficult. Further, ML predictions with as far-reaching implications as an extraterrestrial biosignature on an ocean world requires the use of interpretable models (i.e., not “black box” models) with physically and mathematically meaningful feature spaces along with false positive diagnostics. Methods: We use volatile CO2 IRMS data of analogue ocean world seawaters to validate an ML approach to provide biogeochemical context for biosignature detection. We employ a feature selection method called nearest-neighbor projected distance regression (NPDR) that detects statistical interactions and helps elucidate the mechanisms of the Random Forest classification models. Results: We train and validate predictive ML models on volatile CO2 IRMS data of analogue ocean world seawaters to predict major salt components (e.g., MgSO4, NaHCO3), pH, ionic strength, and the presence of biosignatures. Features derived from IRMS measurements are augmented with extracted time-series features. Our results show high test accuracy and interpretability, which is increased by interaction network visualization, sample-wise variable importance scores, and single-sample class probability estimates. We demonstrate an ML mission software solution that triggers autonomous data transmission and biogeochemical sample prediction.

geochemistry↗

Molecular Dynamics Simulations of Liquid and Polymer Electrolytes for Energy Storage Devices

Advancing beyond current lithium-ion technology is necessary in order to enable energy storage devices for electric airplanes. Electrolyte stability is a key limiting factor, yet the design of improved electrolytes remains a formidable challenge. Molecular dynamics (MD) simulations are a powerful tool for studying electrolytes, since they can be used to evaluate structural, thermodynamic, and transport properties, and can provide molecular-level detail often inaccessible to experimental techniques. Our computational materials groups at the NASA Ames Research Center has developed models and methods to accurately simulate both liquid and polymer electrolytes.We report the results from atomistic MD simulations of several electrolyte materials, with lithium salts dissolved in ionic liquids, dimethoxyethane (DME), and polyethylene oxide (PEO). For improved accuracy, we employ polarizable models, where each atom is given an environment-dependent atomic dipole. The simulations accurately predict bulk transport properties, including viscosity, diffusion, and ionic conductivity, in quantitative agreement with available experimental data. Moreover, the simulations provide important insights into the solvation structure of the lithium ions.We also report the results from coarse-grained MD simulations of polyanion electrolytes. In order to more efficiently capture the longer length- and time-scales of these systems, we employ a generic bead-spring model. These simulations provide important insight into how the polymer chain architecture and ionic interaction strengths affect the ionic aggregation behavior and cation dynamics. Despite the simplicity of the model, the simulations yield qualitative agreement with experimental data for similar systems.

Abbott, Lauren J.↗

Friction and wear behavior of glasses and ceramics

Adhesion, friction, and wear behavior of glasses and ionic solids are reviewed. These materials are shown to behave in a manner similar to other solids with respect to adhesion. Their friction characteristics are shown to be sensitive to environmental constituents and surface films. This sensitivity can be related to a reduction in adhesive bonding and the changes in surficial mechanical behavior associated with Rehbinder and Joffe effects. Both friction and wear properties of ionic crystalline solids are highly anisotropic. With metals in contact with ionic solids the fracture strength of the ionic solid and the shear strength in the metal and those properties that determine these will dictate which of the materials undergoes adhesive wear. The chemical activity of the metal plays an important role in the nature and strength of the adhesive interfacial bond that develops between the metal and a glass or ionic solid.

Buckley, D. H.↗