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At least 595 records · Page 33

Flexible polyacrylamide substrata for the analysis of mechanical interactions at cell-substratum adhesions

We have described a powerful tool for the study of mechanical interactions between cells and their physical environment. Although the approach has already been used in a variety of ways to measure traction forces and to characterize active and passive responses of cultured cells to mechanical stimulation, it can be extended easily and combined with other microscopic approaches, including fluorescent analog imaging (Beningo et al., 2001), photobleaching, calcium imaging, micromanipulation, and electrophysiology. This method will be particularly useful for studying the functions of various components at focal adhesions, and the effects of mechanical forces on focal adhesion-mediated signal transduction. In addition, the method can be extended to a 3D setting, e.g., by sandwiching cultured cells between two layers of polyacrylamide to create an environment mimicking that in the tissue of a multicellular organism. Whereas chemical interactions between cells and the environment have been investigated extensively, many important questions remain as to the role of physical forces in cellular functions and the interplay between chemical and physical mechanisms of communication. The present approach, as well as other approaches capable of probing physical interactions, should fill in this important gap in the near future.

NASA Discipline Cell Biology↗

Miniature Gas Chromatograph (GC): Penning Ionization Electron Spectroscopy (PIES) Instrument for the Trace Analyses of Extraterrestrial Environments

In situ exploration of the solar system to identify its early chemistry as preserved in icy bodies and to look for compelling evidence of astrobiology will require new technology for chemical analysis. Chemical measurements in space flight environments highlight the need for a high level of positive identification of chemical compounds, since re-measurement by alternative techniques for confirmation will not be feasible. It also may not be possible to anticipate all chemical species that are observed, and important species may be present only at trace levels where they can be masked by complex chemical backgrounds. Up to now, the only techniques providing independent sample identification of GC separated components across a wide range of chemical species have been Mass Spectrometry (MS) and Ion Mobility Spectrometry (IMS). We describe here the development of a versatile and robust miniature GC detector based on Penning Ionization Electron Spectroscopy (PIES), for use with miniature GC systems being developed for planetary missions. PIES identifies the sample molecule through spectra related to its ionization potential. The combination of miniature GC technology with the primary identification capabilities of PIES provides an analytical approach ideal for planetary analyses.

Kojiro, Daniel R.↗

Tellurite Adsorption onto Bacterial Surfaces

Tellurium (Te) is an emerging contaminant and its chemical transformation in the environment is strongly influenced by microbial processes. In this study, we investigated the adsorption of tellurite [Te(IV), TeO 3 2- ] onto the common soil bacterium Bacillus subtilis. Thiol-blocking experiments were carried out to investigate the role of cell surface sulfhydryl sites in tellurite binding, and extended X-ray absorption fine structure (EXAFS) spectroscopy was performed to determine the chemical speciation of the adsorbed tellurite. The results indicate that tellurite reacts with sulfhydryl functional groups in the extracellular polymeric substances (EPS) produced by B. subtilis. Upon binding to sulfhydryl sites in the EPS, the Te changes from Te-O bonds to Te-S coordination. Further analysis of the surface-associated molecules shows that the EPS of B. subtilis contain proteins. Removal of the proteinaceous EPS dramatically decreases tellurite adsorption and the sulfhydryl surface site concentration. These findings indicate that sulfhydryl binding in EPS plays a key role in tellurite adsorption on bacterial surfaces.

54 ENVIRONMENTAL SCIENCES↗

Nuclear Thermal Propulsion Material Trade for Additively Manufactured Regenerative Chambers

Nuclear thermal propulsion (NTP) is a game changing technology with advantages over chemical propulsion systems for deep space missions but comes with many engineering challenges. This paper focuses on the challenge of material selection for a regeneratively-cooled chamber for use in a nuclear environment with minimal design margins. Chemical compatibility with reactants and products following energy extraction (be it through combustion or neutron bombardment) must be considered. Similarly, mechanical and thermophysical properties (e.g., density, thermal conductivity, yield strength, etc.) as functions of temperature are critical. While hydrogen embrittlement environment (HEE) is a risk and consideration for traditional chemical combustion chambers, application in a nuclear thermal engine adds additional material compatibility and resilience requirements to long-term nuclear radiation exposure. Chamber materials in this trade included, but were not limited to, A-286, Haynes 230, Haynes 282, CRES 347, GRCop-42, GRCop-84, Inconel 625, JBK-75, and NASA HR-1. The material trade focuses on modern additive manufacturing techniques and hypothetical geometric constraints.

Nuclear Thermal Propulsion↗

Nuclear Thermal Propulsion Material Trade for Additively Manufactured Regenerative Chambers

Nuclear thermal propulsion (NTP) is a game changing technology with advantages over chemical propulsion systems for deep space missions but comes with many engineering challenges. This paper focuses on the challenge of material selection for a regeneratively-cooled chamber for use in a nuclear environment with minimal design margins. Chemical compatibility with reactants and products following energy extraction (be it through combustion or neutron bombardment) must be considered. Similarly, mechanical and thermophysical properties (e.g., density, thermal conductivity, yield strength, etc.) as functions of temperature are critical. While hydrogen embrittlement environment (HEE) is a risk and consideration for traditional chemical combustion chambers, application in a nuclear thermal engine adds additional material compatibility and resilience requirements to long-term nuclear radiation exposure. Chamber materials in this trade included, but were not limited to, A-286, Haynes 230, Haynes 282, CRES 347, GRCop-42, GRCop-84, Inconel 625, JBK-75, and NASA HR-1. The material trade focuses on modern additive manufacturing techniques and hypothetical geometric constraints.

Nuclear Thermal Propulsion↗

Use of Laboratory Data to Model Interstellar Chemistry

Our laboratory research program is about the formation of molecules on dust grains analogues in conditions mimicking interstellar medium environments. Using surface science techniques, in the last ten years we have investigated the formation of molecular hydrogen and other molecules on different types of dust grain analogues. We analyzed the results to extract quantitative information on the processes of molecule formation on and ejection from dust grain analogues. The usefulness of these data lies in the fact that these results have been employed by theoreticians in models of the chemical evolution of ISM environments.

Vidali, Gianfranco↗

Shifts in belowground processes along a temperate forest edge

Abstract Context Forests are increasingly fragmented, and as a result most forests in the United States are within one km of an edge. Edges change environmental conditions of the forest—especially radiation, roughness, temperature, and moisture—that can have consequences for plant productivity and ecosystem functions. However, edge effects on aboveground characteristics of plants and the environment are better understood relative to plant roots and soil in the belowground environment. Objectives Our main objectives were to determine if soil C pools and fluxes are higher at the edge relative to other landscape positions, and to understand how specific belowground processes contribute to bulk differences in pools and fluxes. Methods We measured environmental conditions, live and dead fine root traits, soil chemistry, and soil respiration along a 75 m transect from interior forest to meadow in Gaithersburg, MD. Results We observed differences in the soil chemical, biological and hydrological environment between the forest interior, edge and adjacent meadow. In some cases, the forest edge represented a mid-point in environmental or belowground characteristics between the forest interior and meadow ( e.g. , pH, C-to-N ratio [C:N], live fine root biomass, heterotrophic respiration), likely reflecting the change in litter type and quality associated with the transition from grass to woody species. In other cases, neighboring landscape positions were different from the forest edge, which was drier and had higher dead fine root biomass. Although soil C contents were not significantly different across landscape positions, there was a tendency towards higher average soil C content at the edge relative to other landscape positions, suggesting that increased C loss related to root decay and greater soil respiration at the edge relative to the forest interior may have been offset by increased C gain from high plant productivity and subsequent inputs to soil. Conclusions This research provides insight into how forest edge environments may differ from the interior and how concurrent processes above- and belowground may contribute to those differences.

54 ENVIRONMENTAL SCIENCES↗

Photoelectron spectroscopy in molecular physical chemistry

Photoelectron spectroscopy has long been a powerful method in the toolbox of experimental physical chemistry and molecular physics. Recent improvements in coincidence methods, charged-particle imaging, and electron energy resolution have greatly expanded the variety of environments in which photoelectron spectroscopy can be applied, as well as the range of questions that can now be addressed. In this Perspectives Article, we focus on selected recent studies that highlight these advances and research areas. Furthermore, the topics include reactive intermediates and new thermochemical data, high-resolution comparisons of experiment and theory using methods based on pulsed-field ionisation (PFI), and the application of photoelectron spectroscopy as an analytical tool to monitor chemical reactions in complex environments, like model flames, catalytic or high-temperature reactors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Integration of experiments for the detection of biological activity in extraterrestrial exploration

Although many experiments have been suggested and described for the detection of biological activity in planetary exploration, each experiment has required its own sample for the detection of a specific phenomenon. An experimental design which could detect growth, catabolic and anabolic activity on a single sample is described. Growth is monitored in a liquid medium which is in contact with, and chemically influenced by, a relatively large sample. Catabolic activity is indicated by changes in the gas composition of the atmosphere above the sample. Anabolic activity is indicated by the appearance of reduced carbon compounds, from oxidized precursors, in the liquid medium.

Space Flight/instrumentation↗

Measuring the Chemical Potential of the Martian Regolith to Generate and Sustain Life

A critical component for identifying chemical biosignatures is the ability to assess in-situ the potential of an aqueous geochemical environment to generate and sustain life. On Mars or other solar bodies, in-situ chemical characterization could provide evidence as to whether the chemical composition of the regolith or evaporites in suspected ancient water bodies have been biologically influenced or possess the chemical parameters within which life may have existed, or may still exist. A variety of analytical techniques have been proposed for use in detecting and identify signatures of past or present life. These techniques fall into two groups; visual observation with instruments such as cameras or optical/atomic-force microscopes; or elemental chemical analysis with such instruments as X-ray fluorescence (XRF) and diffraction (XRD), a-proton backscatter (APX), y-ray, Mossbauer, Raman, IR, UV/VIS spectroscopies, gas chromatography (GC), or mass spectrometry (MS). Direct observation of an identifiable lifeform by the first set of instruments in a single sample is highly unlikely, especially for extinct organisms or on the surface. The later instruments can provide vital data as to the elemental mineralogy and geological history of the planet, but are highly inadequate for understanding the chemistry of the planet in terms of indigenous life or interactions with human explorers. Techniques such as XRD, XRF, and APX, provide elemental composition at high limits of detection. Some of this data can be extrapolated or interpolated to provide chemical parameters such as oxidation state or composition. Gas chromatography (GC) without standards and non-specific detectors, has little chance of identifying a mixture of unknown components. Combined with GC or by itself, mass spectrometry (MS) can provide identification of compounds, but in both cases the sample must be appropriately prepared for accurate and reliable analysis. Life as we know it, and probably identify it as such, requires an aqueous environment. Deciphering die chemical speciation of this aqueous environment is the key to recognizing therein the biosignatures of any extinct or present life forms. Identifying the soluble (ionic and nonionic) components by reacting a currently dormant environment can provide a "picture" of the thermodynamics and chemical components of a possibly bioactive environment. The only devices which can provide such information are electrochemical sensors based on the potentiometric ion selective electrodes (ISEs) and on dynamic techniques such as cyclic voltammetry (CV) and stripping voltammetry (SV). Such an array of devices can provide not only the chemical composition of a water-soluble Martian soil sample, but also several other vital chemical parameters such as pH, conductivity, redox potential, and dissolved gases. To address these issues we have been investigating the possible use of an electrochemically-based ion sensor array as a new integrated approach to quantitative analytical and chemometric electrochemical measurements. The sensor array will consist of specific and semispecific ion selective and amperometric transducers, which can simultaneously and continuously identify and semiquantitatively determine over 50 organic and inorganic analytes in water-based environments. Several individual sensors, based on the same principle, have been flight-tested and have been installed as part of the MECA instrumentation on the Mars 2001 Lander for in-situ analyses. However, the microfabrication, integration and multiplexing of such a large number of these sensors on a single substrate have not been previously attempted.

Kounaves, S. P.↗

Fundamental considerations for future solid lubricants

Properties important to the performance of solid lubricants are discussed. Those properties include shear characteristics, coherence between particles, resistance to cold flow, adherence to the substrate, applicable chemical thermodynamics and kinetics of materials and environments, polymorphism, and rheology. The following generalizations are made: (1) chemical thermodynamics and kinetics are powerful tools for use in determining the useful environments and methods of application for solid film lubricants; (2) the primary requirement for a solid lubricant is low shear strength; (3) the rheology of solid film constituents and formulations is likely to be of vital importance to performance and life; and (4) adherence and mobility of surface films is another primary requirement for long lived solid lubricants.

Johnson, R. L.↗

Atomic Oxygen Environment, Effects and Simulation

Atomic oxygen is the most predominant constituent in the low Earth orbital environment between the altitudes of 180 and 650 km. It is also a major constituent of the Mars orbital environment. It is very chemically reactive and can oxidize materials on the outside of spacecraft. In many cases the reaction products are volatile which can lead to mechanical failure. Stable oxides can also form that change the optical or thermal properties of the material. The importance of understanding atomic oxygen reactions with materials has led to both flight experiments in low Earth orbit and ground-based testing in vacuum chambers containing atomic oxygen to study its’ effect on materials. This presentation will focus on defining atomic oxygen environments, discussing atomic oxygen effects on spacecraft materials, reviewing some methods of atomic oxygen simulation, and discussing differences in ground-based testing and space testing as well as synergistic effects.

atomic oxygen, space environment, ground-based tes↗

Oleoresin, Chemistry and Spectral Reflectance in "Stressed" Lodgepole and White Bark Pine, Mammoth Mountain, California

Development of methods to identify the physical and chemical character of materials on the earth's surface is one of the foci of hyperspectral remote sensing activities. Enhancing the ability to elucidate changes in foliar chemistry that relate to the health of a plant is a benefit to plant physiologists, foresters, and plant ecologists, as well as geologist and environmental scientists. Vegetation covers the landscape throughout the temperate and tropical regions of the earth. The existence of vegetation in these areas presents special problems to remote sensing systems since geologic bedrock and alteration zones are masked. At times, however, alterations in the soil/sediment geochemical environment result in foliar chemical changes that are detectable via remote sensing. Examples include monitoring of chlorophyll reflectance/fluorescence and equivalent water thickness indices as indicators of drought-induced plant stress. Another processing and interpretation approach used with hyperspectral data has been principal components analysis (PCA). Rowan et al. used PCA to identify absorption feature patterns obtained from vegetated areas with discrete bedrock geology or mineralization as the substrate. Many researchers highlight the need to advance our ability for hyperspectral imaging in vegetated areas as a near-term priority.

Hickey, James C.↗

Hazardous Chemical Inventory Guidelines, Purpose, and Process

The Environment, Safety, and Health Planning department at Sandia National Laboratories is interested in the purchase and storage of chemicals and their potential impact following an uncontrolled release. The large number of projects conducted at SNL make tracking every chemical purchase impractical; therefore, attention is focused on hazardous substances purchased in large quantities. Chemicals and quantities of concern are determined through regulatory guidelines; e.g., the OSHA Process Safety Management list, the EPA Risk Management Plan list, and the Department of Energy Subcommittee on Consequence Assessment and Protective Actions Emergency Response Planning Guidelines. Based on these regulations, a list of chemicals with quantities of concern was created using the Aerial Locations of Hazardous Atmospheres (ALOHA) and SCREEN View chemical dispersion modelling software. The nature of this report does not draw conclusions, rather it documents the logic for a chemicals of concern list to ensure compliance with various regulations and form the basis for monitoring chemicals that may affect hazard classification. Hazardous Chemical Inventory Guidelines, Purpose, and Process 4 This page left blank.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Biologically Derived Herders for petroleum-oceanic spillage: An Eco-friendly Herder

The petroleum industry is a vital international energy market, expected to generate $\$$5.3 trillion in US revenue is expected to generate in 2024. However, the market poses an environmental danger due to petroleum spillage in either extraction or aquatic transportation. In previous years there has been efforts to develop chemical herders compounds that aid in in situ burning (ISB) as a remedy to extract spilled petroleum in aquatic environments. Although, when implementing these chemical herders they tend to release toxic and non-biodegradable products upon ISB that may negatively impact aquatic. We suggest novel herder compounds that are biologically derived and biodegradable, which will not negatively impact aquatic environments. The proposed biological compounds will be synthesized from a Phytol chain and will be further functionalized with polyalcohols to construct amphipathic surfactants to safely implement ISB or extract petroleum to be recycled.

02 PETROLEUM↗

Covariant C and O Isotope Trends in Arctic Carbonate Crusts and ALH 84001: Potential Biomarker or Indicator of Cryogenic Formation Environment?

This work seeks to use the chemical, isotopic, and mineralogical characteristics of secondary carbonate minerals produced during brief aqueous events to identify the conditions of the aqueous environment in which they formed. Liquid water near the surface of Mars is subject to either rapid freezing and/or evaporation. These processes are also active on Earth, and produce secondary minerals that have complex chemical, mineralogical, and isotopic textures and compositions that can include covariant relationships between Delta C-13 (sub VPDB) and delta O-18 (sub VSMOW). The extremely well studied four billion year old carbonates preserved in martian meteorite ALH 84001 also show covariant delta C-13 and delta O-18 compositions, but these variations are manifested on a micro-scale in a single thin section while the variation observed so far in terrestrial carbonates is seen between different hand samples.

Socki, Richard A.↗

Atomic Oxygen Environment and Effects Overview

Atomic oxygen is the most predominant constituent in the low Earth orbital environment between the altitudes of 180 and 650 km. It is also a major constituent of the Mars orbital environment. It is very chemically reactive and can oxidize many spacecraft surfaces to form volatile reaction products. The importance of understanding atomic oxygen reactions with materials has led to both flight experiments in low Earth orbit and ground-based testing in vacuum chambers containing atomic oxygen to study its’ effect on materials. Testing has been performed in order to determine the extent of the atomic oxygen reaction and assess material and component durability. In addition, the effectiveness of mitigation techniques such as application of a protective coating, adding fillers, or using shielding and getter materials has also been studied both in flight and ground-based experiments. This presentation will focus on defining atomic oxygen environments, discussing its effect on spacecraft materials, and describing some of the testing and mitigation techniques that have been investigated.

Atomic Oxygen, Low Earth Orbit, Low Mars Orbit, ox↗

Gas chromatographic concepts for the analysis of planetary atmospheres

Over the last few years, new gas chromatographic (GC) concepts were developed for use on board spacecraft or any other restricted environments for determining the chemical composition of the atmosphere and surface material of various planetary bodies. Future NASA Missions include an entry probe that will be sent to Titan and various spacecraft that will land on Mars. In order to be able to properly respond to the mission science requirements and physical restrictions imposed on the instruments by these missions, GC analytical techniques are being developed. Some of these techniques include hardware and mathematical techniques that will improve GC sensitivity and increase the sampling rate of a GC descending through a planetary atmosphere. The technique of Multiplex Gas Chromatography (MGC) is an example of a technique that was studied in a simulated Titan atmosphere. In such an environment, the atmospheric pressure at instrument deployment is estimated to be a few torr. Thus, at such pressures, the small amount of sample that is acquired might not be enough to satisfy the detection requirements of the gas chromatograph. In MGC, many samples are pseudo-randomly introduced to the chromatograph without regard to elution of preceding components. The resulting data is then reduced using mathematical techniques such as cross-correlation of Fourier Transforms. Advantages realized from this technique include: improvement in detection limits of several orders of magnitude and increase in the number of analyses that can be conducted in a given period of time. Results proving the application of MGC at very low pressures emulating the same atmospheric pressures that a Titan Probe will encounter when the instruments are deployed are presented. The sample used contained hydrocarbons that are expected to be found in Titan's atmosphere. In addition, a new selective modulator was developed to monitor water under Martian atmospheric conditions. Since this modulator is selective only to water, the need for a GC column is eliminated. This results in further simplification of the instrument.

Valentin, J. R.↗