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At least 19 records

Large steric effect in the substitution reaction of amines with phosphoimidazolide-activated nucleosides

Aliphatic amines react with phosphoimidazolide-activated derivatives of guanosine and cytidine (ImpN) by replacing the imidazole group. The kinetics of reaction of guanosine 5'-phospho-2-methylimidazolide (2-MeImpG) with glycine ethyl ester, glycinamide, 2-methoxyethylamine, n-butylamine, morpholine, dimethylamine (Me2NH), ethylmethylamine (EtNHMe), diethylamine (Et2NH), pyrrolidine, and piperidine were determined in water at 37 degrees C. With primary amines, a plot of the logarithm of the rate constant for attack by the amine on the protonated substrate, log kSH(A), versus the pKa of the amine exhibits a good linear correlation with a Bronsted slope, beta nuc = 0.48. Most of the secondary amines tested react with slightly higher reactivity than primary amines of similar pKa. Interestingly, some secondary amines show substantially lower reactivity than might be expected: EtNHMe reacts about eight times, and Et2NH at least 100 times, more slowly than Me2NH although all three amines are of similar basicity. For comparison, the kinetics of reaction of guanosine 5'-phosphoimidazolide (ImpG) and cytidine 5'-phosphoimidazolide (ImpC) were determined with Me2NH, EtNHMe, and Et2NH, and similar results were obtained. These results establish that the increased steric hindrance observed with the successive addition of ethyl groups are not due to any special steric requirements imposed by the guanosine or the methyl on the 2-methylimidazole leaving group of 2-MeImpG. It is concluded that addition of ethyl and, perhaps, groups larger than ethyl dramatically increases the kinetic barrier for addition of aliphatic secondary amines to the P-N bond of ImpN. This study supports the observation that the primary amino groups on the natural polyamines are at least 2 orders of magnitude more reactive than the secondary amino groups in the reaction with ImpN.

Non-NASA Center↗

The sugar model: catalysis by amines and amino acid products

Ammonia and amines (including amino acids) were shown to catalyze the formation of sugars from formaldehyde and glycolaldehyde, and the subsequent conversion of sugars to carbonylcontaining products under the conditions studied (pH 5.5 and 50 degrees C). Sterically unhindered primary amines were better catalysts than ammonia, secondary amines, and sterically hindered primary amines (i.e. alpha-aminoisobutyric acid). Reactions catalyzed by primary amines initially consumed formaldehyde and glycolaldehyde about 15-20 times faster than an uncatalyzed control reaction. The amine-catalyzed reactions yielded aldotriose (glyceraldehyde), ketotriose (dihydroxyacetone), aldotetroses (erythrose and threose), ketotetrose (erythrulose), pyruvaldehyde, acetaldehyde, glyoxal, pyruvate, glyoxylate, and several unindentified carbonyl products. The concentrations of the carbonyl products, except pyruvate and ketotetrose, initially increased and then declined during the reaction, indicating their ultimate conversion to other products (like larger sugars or pyruvate). The uncatalyzed control reaction yielded no pyruvate or glyoxylate, and only trace amounts of pyruvaldehyde, acetaldehyde and glyoxal. In the presence of 15 mM catalytic primary amine, such as alanine, the rates of triose and pyruvaldehyde of synthesis were about 15-times and 1200-times faster, respectively, than the uncatalyzed reaction. Since previous studies established that alanine is synthesized from glycolaldehyde and formaldehyde via pyruvaldehyde as its direct precursor, the demonstration that the alanine catalyzes the conversion of glycolaldehyde and formaldehyde to pyruvaldehyde indicates that this synthetic pathway is capable of autocatalysis. The relevance of this synthetic process, named the Sugar Model, to the origin of life is discussed.

Acetaldehyde/analogs & derivatives/chemistry↗

Aliphatic amines in the Murchison meteorite

The paper reports on the determination of aliphatic amines in water extracts of the Murchison meteorite. The amines were analyzed by gas chromatography both as the free amines and as 2,4-dinitrophenyl (DNP) derivatives. The results give evidence for the presence of all of the possible primary aliphatic monoamines (eight) with fewer than five carbon atoms. Two of the seven possible secondary or tertiary aliphatic monoamines were identified. The identified primary amines total 80 nmol per g meteorite, and seem to be chemically or physically trapped in the meteorite. Similarities between the water-extractable amines and amino acids suggest that (1) a simple carbon compound, methane, for example, is the precursor of meteorite amines and amino acids, and (2) both amines and amino acids are extracted from the meteorite both as such and in the form of acid-hydrolyzable derivative or precursor species.

Jungclaus, G.↗

Spacesuit Portable Life Support System Breadboard (PLSS 1.0) Development and Test Results

A multi-year effort has been carried out at NASA-JSC to develop an advanced Extravehicular Activity (EVA) PLSS design intended to further the current state of the art by increasing operational flexibility, reducing consumables, and increasing robustness. Previous efforts have focused on modeling and analyzing the advanced PLSS architecture, as well as developing key enabling technologies. Like the current International Space Station (ISS) Extravehicular Mobility Unit (EMU) PLSS, the advanced PLSS comprises of three subsystems required to sustain the crew during EVA including the Thermal, Ventilation, and Oxygen Subsystems. This multi-year effort has culminated in the construction and operation of PLSS 1.0, a test rig that simulates full functionality of the advanced PLSS design. PLSS 1.0 integrates commercial off the shelf hardware with prototype technology development components, including the primary and secondary oxygen regulators, ventilation loop fan, Rapid Cycle Amine (RCA) swingbed, and Spacesuit Water Membrane Evaporator (SWME). Testing accumulated 239 hours over 45 days, while executing 172 test points. Specific PLSS 1.0 test objectives assessed during this testing include: confirming key individual components perform in a system level test as they have performed during component level testing; identifying unexpected system-level interactions; operating PLSS 1.0 in nominal steady-state EVA modes to baseline subsystem performance with respect to metabolic rate, ventilation loop pressure and flow rate, and environmental conditions; simulating nominal transient EVA operational scenarios; simulating contingency EVA operational scenarios; and further evaluating individual technology development components. Successful testing of the PLSS 1.0 provided a large database of test results that characterize system level and component performance. With the exception of several minor anomalies, the PLSS 1.0 test rig performed as expected; furthermore, many system responses trended in accordance with pre-test predictions.

Vogel, Matt R.↗

Spacesuit Portable Life Support System Breadboard (PLSS 1.0) Development and Test Results

A multi-year effort has been carried out at the Johnson Space Center to develop an advanced EVA PLSS design intended to further the current state of the art by increasing operational flexibility, reducing consumables, and increasing robustness. This multi-year effort has culminated in the construction and operation of PLSS 1.0, a test rig that simulates full functionality of the advanced PLSS design. PLSS 1.0 integrates commercial off-the-shelf hardware with prototype technology development components, including the primary and secondary oxygen regulators, ventilation loop fan, Rapid Cycle Amine (RCA) swingbed, and Spacesuit Water Membrane Evaporator (SWME). PLSS 1.0 was tested from June 17th through September 30th, 2011. Testing accumulated 233 hours over 45 days, while executing 119 test points. An additional 164 hours of operational time were accrued during the test series, bringing the total operational time for PLSS 1.0 testing to 397 hours. Specific PLSS 1.0 test objectives assessed during this testing include: (1) Confirming prototype components perform in a system level test as they have performed during component level testing, (2) Identifying unexpected system-level interactions (3) Operating PLSS 1.0 in nominal steady-state EVA modes to baseline subsystem performance with respect to metabolic rate, ventilation loop pressure and flow rate, and environmental conditions (4) Simulating nominal transient EVA operational scenarios (5) Simulating contingency EVA operational scenarios (6) Further evaluating prototype technology development components Successful testing of the PLSS 1.0 provided a large database of test results that characterize system level and component performance. With the exception of several minor anomalies, the PLSS 1.0 test rig performed as expected. Documented anomalies and observations include: (1) Ventilation loop fan controller issues at high fan speeds (near 70,000 rpm, whereas the fan speed during nominal operations would be closer to 35,000 rpm) (2) RCA performance at boundary conditions, including carbon dioxide and water vapor saturation events, as well as reduced vacuum quality (3) SWME valve anomalies (4 documented cases where the SWME failed to respond to a control signal or physically jammed, preventing SWME control) (4) Reduction of SWME hollow fiber hydrophobicity and significant reduction of the SWME degassing capability after significant accumulated test time.

Watts, Carly A.↗

Space Suit Portable Life Support System Test Bed (PLSS 1.0) Development and Testing

A multi-year effort has been carried out at NASA-JSC to develop an advanced extra-vehicular activity Portable Life Support System (PLSS) design intended to further the current state of the art by increasing operational flexibility, reducing consumables, and increasing robustness. Previous efforts have focused on modeling and analyzing the advanced PLSS architecture, as well as developing key enabling technologies. Like the current International Space Station Extra-vehicular Mobility Unit PLSS, the advanced PLSS comprises three subsystems required to sustain the crew during extra-vehicular activity including the Thermal, Ventilation, and Oxygen Subsystems. This multi-year effort has culminated in the construction and operation of PLSS 1.0, a test bed that simulates full functionality of the advanced PLSS design. PLSS 1.0 integrates commercial off the shelf hardware with prototype technology development components, including the primary and secondary oxygen regulators, Ventilation Subsystem fan, Rapid Cycle Amine swingbed carbon dioxide and water vapor removal device, and Spacesuit Water Membrane Evaporator heat rejection device. The overall PLSS 1.0 test objective was to demonstrate the capability of the Advanced PLSS to provide key life support functions including suit pressure regulation, carbon dioxide and water vapor removal, thermal control and contingency purge operations. Supplying oxygen was not one of the specific life support functions because the PLSS 1.0 test was not oxygen rated. Nitrogen was used for the working gas. Additional test objectives were to confirm PLSS technology development components performance within an integrated test bed, identify unexpected system level interactions, and map the PLSS 1.0 performance with respect to key variables such as crewmember metabolic rate and suit pressure. Successful PLSS 1.0 testing completed 168 test points over 44 days of testing and produced a large database of test results that characterize system level and component performance. With the exception of several minor anomalies, the PLSS 1.0 test rig performed as expected; furthermore, many system responses trended in accordance with pre-test predictions.

Watts, Carly↗

V-SUIT Model Validation Using PLSS 1.0 Test Results

The dynamic portable life support system (PLSS) simulation software Virtual Space Suit (V-SUIT) has been under development at the Technische Universitat Munchen since 2011 as a spin-off from the Virtual Habitat (V-HAB) project. The MATLAB(trademark)-based V-SUIT simulates space suit portable life support systems and their interaction with a detailed and also dynamic human model, as well as the dynamic external environment of a space suit moving on a planetary surface. To demonstrate the feasibility of a large, system level simulation like V-SUIT, a model of NASA's PLSS 1.0 prototype was created. This prototype was run through an extensive series of tests in 2011. Since the test setup was heavily instrumented, it produced a wealth of data making it ideal for model validation. The implemented model includes all components of the PLSS in both the ventilation and thermal loops. The major components are modeled in greater detail, while smaller and ancillary components are low fidelity black box models. The major components include the Rapid Cycle Amine (RCA) CO2 removal system, the Primary and Secondary Oxygen Assembly (POS/SOA), the Pressure Garment System Volume Simulator (PGSVS), the Human Metabolic Simulator (HMS), the heat exchanger between the ventilation and thermal loops, the Space Suit Water Membrane Evaporator (SWME) and finally the Liquid Cooling Garment Simulator (LCGS). Using the created model, dynamic simulations were performed using same test points also used during PLSS 1.0 testing. The results of the simulation were then compared to the test data with special focus on absolute values during the steady state phases and dynamic behavior during the transition between test points. Quantified simulation results are presented that demonstrate which areas of the V-SUIT model are in need of further refinement and those that are sufficiently close to the test results. Finally, lessons learned from the modelling and validation process are given in combination with implications for the future development of other PLSS models in V-SUIT.

Olthoff, Claas↗

Rett syndrome - Stimulation of endogenous biogenic amines

Transient hypercapnic hyperoxemia was induced in two Rett syndrome children by the administration of a gaseous mixture of 80 percent O2 and 20 percent CO2. Time course studies of neurotransmitters and their metabolites showed an immediate and marked increase in central biogenic amine turnover following inhalation of the gas mixture. The increased turnover of biogenic amines was associated with improved clinical changes. This suggests a coupled relationship and provides further support for an etiological role of neurotransmitter dysfunction in Rett syndrome. In a complementary study, elevation of pulmonary CO2 by application of a simple rebreathing device resulted in improvement of abnormal blood gases and elimination of the Cheyne-Stokes-like respiratory pattern of the Rett syndrome. Near normalization of the EEG occurred when a normal respiratory pattern was imposed by means of a respirator. Taken together, these results lead to the preliminary conclusion that cerebral hypoxemia secondary to abnormal respiratory function may contribute to diminished production of biogenic amines in Rett syndrome.

Pelligra, R.↗

Isotopic analyses of nitrogenous compounds from the Murchison meteorite: ammonia, amines, amino acids, and polar hydrocarbons

The combined volatile bases (ammonia, aliphatic amines, and possibly other bases), ammonia, amino acids, and polar hydrocarbons were prepared from the Murchison meteorite for isotopic analyses. The volatile bases were obtained by cryogenic transfer after acid-hydrolysis of a hot-water extract and analyzed by combined gas chromatography-mass spectrometry of pentafluoropropionyl derivatives. The aliphatic amines present in this preparation comprise a mixture that includes both primary and secondary isomers through C5 at a total concentration of > or = 100 nmoles g-1. As commonly observed for meteoritic organic compounds, almost all isomers through C5 are present, and the concentrations within homologous series decrease with increasing chain length. Ammonia was chromatographically separated from the other volatile bases and found at a concentration of 1.1-1.3 micromoles g-1 meteorite. The ammonia analyzed includes contributions from ammonium salts and the hydrolysis of extractable organic compounds, e.g., carboxamides. Stable isotope analyses showed the volatile bases to be substantially enriched in the heavier isotopes, relative to comparable terrestrial compounds delta D < or = +1221%; delta 13C = +22%; delta 15N = +93%). Ammonia, per se, was found to have a somewhat lower delta 15N value (+69%) than the total volatile bases; consequently, a higher delta 15N (>93%) can be inferred for the other bases, which include the amines. Solvent-extractable polar hydrocarbons obtained separately were found to be enriched in 15N (delta 15N = +104%). Total amino acids, prepared from a hydrolyzed hot-water extract by cation exchange chromatography, gave a delta 15N of +94%, a value in good agreement with that obtained previously. Nitrogen isotopic data are also given for amino acid fractions separated chromatographically. The delta 15N values of the Murchison soluble organic compounds analyzed to date fall within a rather narrow range (delta 15N = +94 +/- 8%), an observation consistent with their formation, or formation of their precursors, by interstellar chemistry.

Non-NASA Center↗

Packing the PLSS

NASA Engineers design spacesuits for ultimate protection and functionality in the extreme environment of space. The spacesuit is often referred to as a "personal spacecraft" because it provides the astronaut with everything he or she needs to survive and work in space outside of the vehicle or habitat. The systems within the spacesuit include the pressure garment system (PGS), the Portable Life Support System (PLSS), and the power, avionics, and software (PAS) system. These elements are necessary to protect crewmembers and allow them to work effectively in the pressure and temperature extremes of space environments. Development of the spacesuit system is necessary to support future human extravehicular exploration activities to Lunar, Martian, microgravity, and possibly other space destinations. Although all the systems that makeup the space suit are important, the PLSS is one of the most complex. The PLSS provides the life support needed by the astronaut and consists of the oxygen (O2) subsystem, ventilation subsystem, and thermal control subsystem. Within each subsystem, there are many different components, a few of which are explained as follows. The oxygen tanks hold the oxygen that the crewmember uses to breath and pressurizes the suit. The primary oxygen tank is responsible during normal operations and the secondary oxygen tank kicks on in the case of an emergency. The Rapid Cycle Amine (RCA) canister is used to remove the carbon dioxide (CO2) and extra humidity in the crewmember's ventilation/breathing gas. The fan moves the oxygen around the suit. Suit Water Membrane Evaporator (SWME) is used within the thermal control loop to cool the water that is used to maintain a comfortable temperature for both the crew member and the other equipment inside the suit. Another component is the battery, which supplies the power needed to operate all these and the many other pieces. The battery is one of the biggest and heavies components within the PLSS. These are just a few of the components that encompass the PLSS. Each component has a weight and a certain volume that the NASA Engineers must take into account when building the PLSS, because the weight and volumes affect the crewmembers center of gravity (CG). [See the Notes Section for the link to an Apollo video that demonstrates the issues some of the crewmembers had picking up tools and dealing with center of gravity/tools on the surface of the Moon.] In this activity, students will simulate engineering design techniques that NASA Engineers and Designers are currently implementing to configuring the components within the PLSS. Through testing, students will consider the comfort, mobility, and center of gravity for their test subjects and how that changes after adjusting the placement of their simulated PLSS components.

Jennings, Mallory↗

Carbon Nanofiber Incorporated Silica Based Aerogels with Di-Isocyanate Cross-Linking

Lightweight materials with excellent thermal insulating properties are highly sought after for a variety of aerospace and aeronautic applications. (1) Silica based aerogels with their high surface area and low relative densities are ideal for applications in extreme environments such as insulators for the Mars Rover battery. (2) However, the fragile nature of aerogel monoliths prevents their widespread use in more down to earth applications. We have shown that the fragile aerogel network can be cross-linked with a di-isocyanate via amine decorated surfaces to form a conformal coating. (3) This coating reinforces the neck regions between secondary silica particles and significantly strengthens the aerogels with only a small effect on density or porosity. Scheme 1 depicts the cross-linking reaction with the di-isocyanate and exhibits the stages that result in polymer cross-linked aerogel monoliths.

Vivod, Stephanie L.↗

Surface characterization in composite and titanium bonding: Carbon fiber surface treatments for improved adhesion to thermoplastic polymers

The effect of anodization in NaOH, H2SO4, and amine salts on the surface chemistry of carbon fibers was examined by X-ray photoelectron spectroscopy (XPS). The surfaces of carbon fibers after anodization in NaOH and H2SO4 were examined by scanning transmission electron microscopy (STEM), angular dependent XPS, UV absorption spectroscopy of the anodization bath, secondary ion mass spectrometry, and polar/dispersive surface energy analysis. Hercules AS-4, Dexter Hysol XAS, and Union Carbide T-300 fibers were examined by STEM, angular dependent XPS, and breaking strength measurement before and after commercial surface treatment. Oxygen and nitrogen were added to the fiber surfaces by anodization in amine salts. Analysis of the plasmon peak in the carbon 1s signal indicated that H2SO4 anodization affected the morphological structure of the carbon fiber surface. The work of adhesion of carbon fibers to thermoplastic resins was calculated using the geometric mean relationship. A correlation was observed between the dispersive component of the work of adhesion and the interfacial adhesion.

Devilbiss, T. A.↗

TPSAS-NF1676L-31522-DND

Currently, there are limitations in launch capability regarding requisite payload volume and mass for long duration extra-terrestrial missions. In-space additive manufacturing may provide a solution to this challenge and is applicable for articles ranging from large system and subsystem architectures to small consumables and replacement articles. For small articles, additive manufacturing is becoming more feasible through advances in instrumentation and novel manufacturing strategies capable of generating complex shapes. Many approaches, however, utilize feedstock materials that, once consumed, must be replenished before additional architectures can be generated. Thus, although promising, a major challenge with additive manufacturing is the required starting materials to support on-demand article generation. This presentation describes research toward reversibly assembling materials that can revert to the starting material state for subsequent fabrication. Polyimides were synthesized with thermally reversible Diels-Alder reaction functionalities, furan or maleimide moieties. These materials were characterized utilizing typical spectroscopic, thermal, and mechanical techniques. Amine hardener-enriched epoxy microparticles were synthesized for use as a mechanically robust substrate. Integration of these technologies into a single system and application toward generation of secondary structures on a launch vehicle as a means of in-situ resource utilization will be described.

Christopher J. Wohl↗

Use of phosphoimidazolide-activated guanosine to investigate the nucleophilicity of spermine and spermidine

Guanosine 5'-phosphate 2-methylimidazolide (2-MeImpG), a labile phosphoimidazolide analog of guanosine triphosphate, was used to test the reactivity of the natural polyamines (PAs), spermine (spm) and spermidine (spd). The products are the guanosine 5'-phosphate-polyamine derivatives (PA-pG: spd-pG and spm-pG) which are quite stable in the range 4 < pH < 11. Our study is the first of which we are aware that reports on the nucleophilicity of these amines. The main findings are as follows. (i) HPLC analysis of the products indicates the formation of only two of the three possible spd products and only one of the two possible spm products. These results can be explained if only the primary amino groups of the two polyamines are reactive, while the secondary amino groups are rendered unreactive by a steric effect. The reactions of 2-MeImpG and other phosphoimidazolide derivatives of nucleosides (ImpNs) with primary and secondary monoamines support this interpretation (Kanavarioti et al. J. Org. Chem. 1995, 60, 632). (ii) The product ratio of the two spd-pG adducts derived from the primary amino groups varies between 2.40 and 0.71 in the range 6.1 < or equal to pH < or equal to 11.9. Such small variation in the product ratio can only be rationalized by the similar, but not identical, basicity of the two primary amino groups and provides strong support for a previously reported model for polyamine ionization (Onasch et. al. Biophys. Chem. 1984, 19, 245). (iii) On the basis of our kinetic determinations conditions at which the nucleophilicity of these amines is at a minimum and at which other interactions with ImpNs could be tested can be chosen.

NASA Discipline Exobiology↗

Short Exploration Extravehicular Mobility Unit Testing Setup: Evaluation Under Realistic Pressure and Thermal Conditions

The purpose of Short Exploration Extravehicular Mobility Unit (SxEMU) thermal vacuum testing was to verify the functionality of the Design Verification Testing (DVT) prototype xEMU (SxEMU for this test) at vacuum pressures and extreme space and lunar surface temperature conditions. The SxEMU Thermal Vacuum Test was the culmination of the DVT xEMU project. This paper’s focus is on the pre-Extravehicular Activity (EVA) test setup, and general performance of the SxEMU Portable Life Support Subsystem (xPLSS), with focus on the performance of the Primary Oxygen Assembly (POA) and Secondary Oxygen Assembly (SOA), including Secondary Oxygen Regulator (SOR) takeover and the POA and SOA low-setpoint change inhibit. The initial pre-EVA test preparation included recharging the batteries and replenishing consumables, including test-system water, oxygen assemblies (with gaseous nitrogen), and the integrated thermal loops, including the Feedwater Supply Assemblies. xPLSS functionality testing included carbon dioxide (CO2) removal via the Rapid Cycle Amine swingbed system, thermal loop temperature control, and monitoring of suit ventilation loop pressure, temperature, and CO2 percentages. Testing evaluated automatic takeover of suit pressure control by the SOR after the primary oxygen supply is depleted. The Primary Oxygen Regulator and SOR low-setpoint change inhibit function prevents the crewmember from inadvertently setting the primary regulator to a low pressure setpoint during an EVA.

xPLSS↗

Design concepts for pressurized lunar shelters utilizing indigenous materials

The objective is to design a pressurized shelter build of indigenous lunar material. The topics are presented in viewgraph form and include the following: lunar conditions which impact design; secondary factors; review of previously proposed concepts; cross section of assembly facility; rationale for indigenous materials; indigenous material choices; cast basalt properties; design variables; design 1, cylindrical segments; construction sequence; design 2, arch-slabs with post-tensioned ring girders; and future research.

Happel, John Amin↗

Latent Hardeners for the Assembly of Epoxy Composites

Large-scale composite structures are commonly joined by secondary bonding of molded-and-cured thermoset components. This approach may result in unpredictable joint strengths. In contrast, assemblies made by co-curing, although limited in size by the mold, result in stable structures, and are certifiable for commercial aviation because of structural continuity through the joints. Multifunctional epoxy resins were prepared that should produce fully-cured subcomponents with uncured joining surfaces, enabling them to be assembled by co-curing in a subsequent out-of-autoclave process. Aromatic diamines were protected by condensation with a ketone or aldehyde to form imines. Properties of the amine-cured epoxy were compared with those of commercially available thermosetting epoxy resins and rheology and thermal analysis were used to demonstrate the efficacy of imine protection. Optimum conditions to reverse the protecting chemistry in the solid state using moisture and acid catalysis were determined. Alternative chemistries were also investigated. For example, chain reaction depolymerization and photoinitiated catalysts would be expected to minimize liberation of volatile organic content upon deprotection and avoid residual reactive species that could damage the resin. Results from the analysis of protected and deprotected resins will be presented.

Palmieri, Frank↗