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At least 235 records · Page 13

Head-Down Suspension Alters Stress-Responsiveness and Feedback Efficacy of 9a-Fludrocortisone in Rats

9a-Fludrocortisone (9aFF) has been used to decrease orthostatic hypotension in astronauts whorl they return to earth after space flight. An earth-based model for weightlessness in space is head-down posture in man and rats. In these studies male rats were suspended head-down or not for 7 days and treated 14 and 2 hours prior to ether stress in the AM with 9aFF (20 micrograms i.u.) at -14 and -2 h or at -2 h with steroid and at -14 h with oil; controls were treated 2x with oil. Rats were decapitated 10 min after ether and ACTH and corticosterone (B) were measured. Both ACTH and B responses were greater in suspended than control rats under all three steroid conditions, and the percentage inhibition of ACTH by 9aFF was similar. Basal activity in the HPA over the 7 d suspension period was probably not elevated since adrenal and thymus weights did not differ in the ambulatory and head down groups. We conclude that headdown suspension facilitates acute stress-induced activity in the HPA axis, but that HPA axis sensitivity to corticosteroid feedback does not change.

Horsley, C. J.↗

Research to Significantly Enhance Composites Survivability at 550 F in Oxidative Environments

Methylene dianiline (MDA) and its derivatives have been used in the synthesis of polyimides to yield polymers with characteristic low-density, high tensile strength, improved solubility in organic solvents, low-melt viscosities and high thermal stability (greater than 550 F) in air. Polyimides with such properties are desirable for use in aerospace systems, e.g., jet engines, airframe, missiles, and rockets where weight is critical. Recent research at Prairie View A&M University is focused on developing monomers to generate polyimides with enhanced performance over that of NASA s PMR-15. The objective of this work is to synthesize three ring aromatic diamines which are non-toxic and when reacted with the appropriate dianhydrides will yield polyimides with lower viscosity, improve processability, good retention of mechanical properties, and oxidative stability at high environmental temperatures. Modifications of the three ring aromatic diamines include replacing the methylene linkages with aromatic ethers by nucleophilic aromatic substitution reactions and incorporating mono- and di-substituents to the center aromatic ring. An update of current reactions involved in synthesis efforts to generate three ring aromatic monomers for polyimides with methylene, carbonyl, and ether linkages separating the aromatic moieties will be displayed.

Meador, Michael A.↗

Environment Partitioning and Reactivity of Polybrominated Diphenylethers

Polybrominated diphenyl ethers (PBDEs) are an important class of flame retardants. Annual global demand for these compounds was over 67,000 metric tons in 2001. PBDEs have recently been extensively investigated as environmental contaminants because they have been detected in air, sediment, and tissue samples from urban and remote areas. Important issues include quantifying PBDE partitioning in various environmental compartments, and elucidating transformation pathways. The partitioning of PBDE congeners to aerosols was estimated for 16 sites in the United States, Canada, and Mexico. The aerosol particles were PM2.5, the total suspended particle (TSP) concentration varied between 3.0 - 55.4 micro g/cubic meter, and the organic fraction ranged from 11 - 41%; these data are published values for each site. It is estimated that the largest fraction of each PBDE associated with the aerosol particles occurs in Mexico City, and the smallest fraction in Colorado Plateau. Although the organic fraction in Mexico City is about 60% of that observed in the Colorado Plateau, the TSP is larger by a factor of about 18.5, and it is the difference in TSP that strongly influences the fraction of particle-bound PBDE in this case. PBDE partitioning to PM2.5 particles also varies seasonally because of temperature variations. For the less brominated congeners the percentage that is particle-bound is relatively low, regardless of air temperature. In contrast, the heavier congeners exhibit a significant temperature dependence: as the temperature decreases (fall, winter) the percentage of PBDE that is particle-bound increases. The partitioning calculations complement experimental data indicating that decabromodiphenyl ether (DBDE) dissolved in hexane transforms very rapidly when irradiated with solar light. DBDE is the most highly brominated PBDE congener (10 bromine atoms) and occurs in the commercial formulation which is subject to the largest global demand.

Hua, Inez↗

Homopolyrotaxanes and Homopolyrotaxane Networks of PEO

In order to identify the optimum size of macrocrown ether for threading, we first investigated the size and shape of simple crown ethers in the melt at 373 K, and their extent of threading with PEO in the melt using coarse-grained Monte Carlo simulations on the 2nnd (second nearest neighbor diamond) lattice, which is a high coordination lattice whose coarse-grained chains can be reverse mapped into fully atomistic models in continuous space.

Pugh, Coleen↗

Linking Archaeal Molecular Diversity and Lipid Biomarker Composition in a Hypersaline Microbial Mat Community

Lipid biomarkers for discrete microbial groups are a valuable tool for establishing links to ancient microbial ecosystems. Lipid biomarkers can establish organism source and function in contemporary microbial ecosystems (membrane lipids) and by analogy, potential relevance to the fossilized carbon skeletons (geolipids) extracted from ancient sedimentary rock. The Mars Exploration Rovers have provided clear evidence for an early wet Mars and the presence of hypersaline evaporitic basins. Ongoing work on an early Earth analog, the hypersaline benthic mats in Guerrero Negro, Baja California Sur, may provide clues to what may have evolved and flourished on an early wet Mars, if only for a short period. Cyanobacterial mats are a pertinent early Earth analog for consideration of evolutionary and microbial processes within the aerobic photosynthetic and adjacent anoxic layers. Fluctuations in physio-chemical parameters associated with spatial and temporal scales are expressed through vast microbial metabolic diversity. Our recent work hopes to establish the dynamic of archaeal diversity, particularly as it relates to methane production in this high sulfate environment, through the use of lipid biomarker and phylogenetic analyses. Archaeal 16s rRNA and mcrA gene assemblages, demonstrated distinct spatial separation over the 130 mm core of at least three distinct genera within the order Methanosarcinales, as well as an abundance of uncultured members of the Thermoplasmales and Crenarchaeota. Ether-bound lipid analysis identified abundant 0-alkyl and 0-isopranyl chains throughout the core, and the presence of sn-2 hydroxyarchaeol, a biomarker for methylotrophic methanogens. A unique ether isoprenoid chain, a C30:1 , possibly related to the geolipid squalane, a paleobiomarker associated with hypersaline environments, was most abundant within the oxic-anoxic transition zone.

Jahnke, Linda↗

Ethynyl terminated imidothioethers and resins therefrom

Ethynyl terminated imidothioethers (ETIs) are prepared by the reaction of a dimercaptan, such as 4,4'-dimercaptodiphenyl ether, and an ethynyl containing maleimide, such as N-(3-ethynylphenyl)maleimide. Blends of thse ETIs and ethynyl terminated polymeric materials, such as ethynyl terminated sulfones and ethynyl terminated arylene ethers, are also prepared. These resin blends exhibit excellent processability, and the cured blends show excellent fracture toughness and solvent resistance, as well as excellent adhesive and composite properties.

Hergenrother, Paul M.↗

Method and Apparatus for Forming Nanodroplets

This innovation uses partially miscible fluids to form nano- and microdroplets in a microfluidic droplet generator system. Droplet generators fabricated in PDMS (polydimethylsiloxane) are currently being used to fabricate engineered nanoparticles and microparticles. These droplet generators were first demonstrated in a T-junction configuration, followed by a cross-flow configuration. All of these generating devices have used immiscible fluids, such as oil and water. This immiscible fluid system can produce mono-dispersed distributions of droplets and articles with sizes ranging from a few hundred nanometers to a few hundred microns. For applications such as drug delivery, the ability to encapsulate aqueous solutions of drugs within particles formed from the droplets is desirable. Of particular interest are non-polar solvents that can dissolve lipids for the formation of liposomes in the droplet generators. Such fluids include ether, cyclohexane, butanol, and ethyl acetate. Ethyl acetate is of particular interest for two reasons. It is relatively nontoxic and it is formed from ether and acetic acid, and maybe broken down into its constituents at relatively low concentrations.

Ackley, Donald↗

High-Temperature Shape Memory Polymers

physical conformation changes when exposed to an external stimulus, such as a change in temperature. Such materials have a permanent shape, but can be reshaped above a critical temperature and fixed into a temporary shape when cooled under stress to below the critical temperature. When reheated above the critical temperature (Tc, also sometimes called the triggering or switching temperature), the materials revert to the permanent shape. The current innovation involves a chemically treated (sulfonated, carboxylated, phosphonated, or other polar function group), high-temperature, semicrystalline thermoplastic poly(ether ether ketone) (Tg .140 C, Tm = 340 C) mix containing organometallic complexes (Zn++, Li+, or other metal, ammonium, or phosphonium salts), or high-temperature ionic liquids (e.g. hexafluorosilicate salt with 1-propyl-3- methyl imidazolium, Tm = 210 C) to form a network where dipolar or ionic interactions between the polymer and the low-molecular-weight or inorganic compound forms a complex that provides a physical crosslink. Hereafter, these compounds will be referred to as "additives". The polymer is semicrystalline, and the high-melt-point crystals provide a temporary crosslink that acts as a permanent crosslink just so long as the melting temperature is not exceeded. In this example case, the melting point is .340 C, and the shape memory critical temperature is between 150 and 250 C. PEEK is an engineering thermoplastic with a high Young fs modulus, nominally 3.6 GPa. An important aspect of the invention is the control of the PEEK functionalization (in this example, the sulfonation degree), and the thermal properties (i.e. melting point) of the additive, which determines the switching temperature. Because the compound is thermoplastic, it can be formed into the "permanent" shape by conventional plastics processing operations. In addition, the compound may be covalently cross - linked after forming the permanent shape by S-PEEK by applying ionizing radiation ( radiation, neutrons), or by chemical crosslinking to form a covalent permanent network. With respect to other shape memory polymers, this invention is novel in that it describes the use of a thermoplastic composition that can be thermally molded or solution-cast into complex "permanent" shapes, and then reheated or redissolved and recast from solution to prepare another shape. It is also unique in that the shape memory behavior is provided by a non-polymer additive.

Yoonessi, Mitra↗

Formation and Recondensation of Complex Organic Molecules During Protostellar Luminosity Outbursts

During the formation of stars, the accretion of surrounding material toward the central object is thought to undergo strong luminosity outbursts followed by long periods of relative quiescence, even at the early stages of star formation when the protostar is still embedded in a large envelope. We investigated the gas-phase formation and recondensation of the complex organic molecules (COMs) di-methyl ether and methyl formate, induced by sudden ice evaporation processes occurring during luminosity outbursts of different amplitudes in protostellar envelopes. For this purpose, we updated a gas-phase chemical network forming COMs in which ammonia plays a key role. The model calculations presented here demonstrate that ion-molecule reactions alone could account for the observed presence of di-methyl ether and methyl formate in a large fraction of protostellar cores without recourse to grain-surface chemistry, although they depend on uncertain ice abundances and gas-phase reaction branching ratios. In spite of the short outburst timescales of about 100 years, abundance ratios of the considered species higher than 10% with respect to methanol are predicted during outbursts due to their low binding energies relative to water and methanol which delay their recondensation during cooling. Although the current luminosity of most embedded protostars would be too low to produce complex organics in the hot-core regions that are observable with current sub-millimetric interferometers, previous luminosity outburst events would induce the formation of COMs in extended regions of protostellar envelopes with sizes increasing by up to one order of magnitude.

astrochemistry↗

Chemical Complexity Induced by Efficient Ice Evaporation in the Barnard 5 Molecular Cloud

Cold gas-phase water has recently been detected in a cold dark cloud, Barnard 5 located in the Perseus complex, by targeting methanol peaks as signposts for ice mantle evaporation. Observed morphology and abundances of methanol and water are consistent with a transient non-thermal evaporation process only affecting the outermost ice mantle layers, possibly triggering a more complex chemistry. Here we present the detection of the complex organic molecules (COMs) acetaldehyde (CH3CHO) and methyl formate (CH3OCHO), as well as formic acid (HCOOH) and ketene (CH2CO), and the tentative detection of di-methyl ether (CH3OCH3) towards the ''methanol hotspot'' of Barnard 5 located between two dense cores using the single dish OSO 20 m, IRAM 30 m, and NRO 45 m telescopes. The high energy cis-conformer of formic acid is detected, suggesting that formic acid is mostly formed at the surface of interstellar grains and then evaporated. The detection of multiple transitions for each species allows us to constrain their abundances through LTE and non-LTE methods. All the considered COMs show similar abundances between approx. 1 and approx. 10% relative to methanol depending on the assumed excitation temperature. The non-detection of glycolaldehyde, an isomer of methyl formate, with a [glycolaldehyde]/[methyl formate] abundance ratio lower than 6%, favours gas phase formation pathways triggered by methanol evaporation. According to their excitation temperatures derived in massive hot cores, formic acid, ketene, and acetaldehyde have been designated as ''lukewarm'' COMs whereas methyl formate and di-methyl ether were defined as ''warm'' species. Comparison with previous observations of other types of sources confirms that lukewarm and warm COMs show similar abundances in low-density cold gas whereas the warm COMs tend to be more abundant than the lukewarm species in warm protostellar cores. This abundance evolution suggests either that warm COMs are indeed mostly formed in protostellar environments and/or that lukewarm COMs are efficiently depleted by increased hydrogenation efficiency around protostars.

ISM: molecules↗

Complex Organic Molecules in the Star-Forming Regions of the Magellanic Clouds

The Large and Small Magellanic Clouds (LMC and SMC), gas-rich dwarf companions of the Milky Way, are the nearest laboratories for detailed studies on the formation and survival of complex organic molecules (COMs) under metal-poor conditions. To date, only methanol, methyl formate, and dimethyl ether have been detected in these galaxiesall three toward two hot cores in the N113 star-forming region in the LMC, the only extragalactic sources exhibiting complex hot-core chemistry. We describe a small and diverse sample of the LMC and SMC sources associated with COMs or hot-core chemistry, and compare the observations to theoretical model predictions. Theoretical models accounting for the physical conditions and metallicity of hot molecular cores in the Magellanic Clouds have been able to broadly account for the existing observations, but they fail to reproduce the dimethyl ether abundance by more than an order of magnitude. We discuss future prospects for research in the eld of complex chemistry in the low- metallicity environment. The detection of COMs in the Magellanic Clouds has important implications for astrobiology. The metallicity of the Magellanic Clouds is similar to that of galaxies in the earlier epochs of the universe; thus, the presence of COMs in the LMC and SMC indicates that a similar prebiotic chemistry leading to the emergence of life, as it happened on Earth, is possible in low-metallicity systems in the earlier universe.

Sewilo, Marta M.↗

Chemical Complexity Induced by Efficient Ice Evaporation in the Barnard 5 Molecular Cloud

Cold gas-phase water has recently been detected in a cold dark cloud, Barnard 5 located in the Perseus complex, by targeting methanol peaks as signposts for ice mantle evaporation. Observed morphology and abundances of methanol and water are consistent with a transient non-thermal evaporation process only affecting the outermost ice mantle layers, possibly triggering a more complex chemistry. Here we present the detection of the complex organic molecules (COMs) acetaldehyde (CH3CHO) and methyl formate (CH3OCHO), as well as formic acid (HCOOH) and ketene (CH2CO), and the tentative detection of di-methyl ether (CH3OCH3) towards the ‘methanol hotspot’ of Barnard 5 located between two dense cores using the single dish OSO 20m, IRAM 30m, and NRO 45m telescopes. The high energy cis- conformer of formic acid is detected, suggesting that formic acid is mostly formed at the surface of interstellar grains and then evaporated. The detection of multiple transitions for each species allows us to constrain their abundances through LTE and non-LTE methods. All the considered COMs show similar abundances between ∼ 1 and ∼ 10 % relative to methanol depending on the assumed excitation temperature. The non-detection of glycolaldehyde, an isomer of methyl formate, with a [glycolaldehyde]/[methyl formate] abundance ratio lower than 6 %, favours gas phase formation pathways triggered by methanol evaporation. According to their excitation temperatures derived in massive hot cores, formic acid, ketene, and acetaldehyde have been designated as ‘lukewarm’ COMs whereas methyl formate and di-methyl ether were defined as ‘warm’ species. Comparison with previous observations of other types of sources confirms that lukewarm and warm COMs show similar abundances in low-density cold gas whereas the warm COMs tend to be more abundant than the lukewarm species in warm protostellar cores. This abundance evolution suggests either that warm COMs are indeed mostly formed in protostellar environments and/or that lukewarm COMs are efficiently depleted by increased hydrogenation efficiency around protostars.

astrochemistry – ISM: abundances – ISM: clouds – I↗

Complex Organic Molecules in Star-Forming Regions of the Magellanic Clouds

The Large and Small Magellanic Clouds (LMC and SMC), gas-rich dwarf companions of the Milky Way, are the nearest laboratories for detailed studies on the formation and survival of complex organic molecules (COMs) under metal poor conditions. To date, only methanol, methyl formate, and dimethyl ether have been detected in these galaxies – all three toward two hot cores in the N113 star-forming region in the LMC, the only extragalactic sources exhibiting complex hot core chemistry. We describe a small and diverse sample of the LMC and SMC sources associated with COMs or hot core chemistry, and compare the observations to theoretical model predictions. Theoretical models accounting for the physical conditions and metallicity of hot molecular cores in the Magellanic Clouds have been able to broadly account for the existing observations, but fail to reproduce the dimethyl ether abundance by more than an order of magnitude. We discuss future prospects for research in the field of complex chemistry in the low-metallicity environment. The detection of COMs in the Magellanic Clouds has important implications for astrobiology. The metallicity of the Magellanic Clouds is similar to galaxies in the earlier epochs of the Universe, thus the presence of COMs in the LMC and SMC indicates that a similar prebiotic chemistry leading to the emergence of life, as it happened on Earth, is possible in low-metallicity systems in the earlier Universe.

Magellanic Clouds, star formation, astrochemistry,↗

Manufacturing and Mechanical Testing of TC1225/LM-PAEK and TC1200/PEEK Thermoplastic Composite Panels

Development of thermoplastic composites (TPCs) for aerospace structures is experiencing renewed enthusiasm attributed to the availability of rapid manufacturing technology, ease of joining through fusion welding processes, and the successful utilization of the material in flight critical structures. Semicrystalline thermoplastics such as polyether ether ketone (PEEK), polyether ketone ketone (PEKK), and polyphenylene sulfide (PPS) have been successfully demonstrated as thermoplastic skins, keel beams, and angle brackets for commercial aircraft. Composite specimens were fabricated from the Toray TC1225 and TC1200 unidirectional prepreg systems and tested to gain confidence with NASA in-house TPC processing as part of the Thermoplastics Development for Exploration Application (TDEA) project. TC1225 is a relatively new material system that uses T700GC fibers and low-melt polyaryl ether ketone (LM-PAEK) resin. TC1200 is the latest version of a material system that has been available for several decades with AS4 fibers and PEEK resin. Results for ultrasonic inspection, optical microscopy, acid digestion, and differential scanning calorimetry establish the quality of the panels. Mechanical test data for unnotched and notched laminate tension and compression as well as compression after impact provide data for equivalency assessment and support material selection in TDEA. Satisfactory equivalence of the TC1225 results and the National Center for Advanced Materials Performance (NCAMP) database was found. The results indicate high-quality manufacturing was achieved, and the resulting mechanical test data are in agreement with that in the literature.

Thermoplastic Composites↗

Joining, Disassembly, and Reconfiguration of Thermoplastic Composites for Space Applications

Thermoplastic composites are increasingly being investigated for aerospace applications because of their relatively short processing time, good chemical and radiation resistance, and potential for reforming and reuse via melting. The manufacturing, reforming, and reuse of thermoplastic composites can be leveraged to advance joining, disassembly, and reassembly of structures for space exploration activities. Potential applications include, but are not limited to, habitats and on-orbit assembly and reassembly of large-scale truss structures. This work focuses on demonstrating the feasibility of joining, disassembly, and reassembly of a thermoplastic bond using heat and pressure. Polyether ether ketone (PEEK) composite adherends were joined using low-melt polyaryl ether ketone (LM-PAEK) thermoplastic films at the bonding interface. The single lap shear specimens with LM-PAEK film were tested and had a maximum shear strength between 5 and 8 MPa and consistently failed adhesively at the bondline. Reassembly of disassembled specimens was successfully demonstrated using additional thermoplastic interlayers. Thus, the reassembly of thermoplastic composite joints was found to be feasible. However, additional work is required to reduce film flowout and optimize consolidation parameters for an in space environment.

thermoplastic composites↗