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At least 1,531 records · Page 85

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NASA NTRS2011

Radiation Protection Using Single-Wall Carbon Nanotube Derivatives

This invention is a means of radiation protection, or cellular oxidative stress mitigation, via a sequence of quenching radical species using nano-engineered scaffolds, specifically single-wall carbon nanotubes (SWNTs) and their derivatives. The material can be used as a means of radiation protection by reducing the number of free radicals within, or nearby, organelles, cells, tissue, organs, or living organisms, thereby reducing the risk of damage to DNA and other cellular components (i.e., RNA, mitochondria, membranes, etc.) that can lead to chronic and/or acute pathologies, including but not limited to cancer, cardiovascular disease, immuno-suppression, and disorders of the central nervous system. In addition, this innovation could be used as a prophylactic or antidote for accidental radiation exposure, during high-altitude or space travel where exposure to radiation is anticipated, or to protect from exposure from deliberate terrorist or wartime use of radiation- containing weapons.

Tour, James M.↗

NASA NTRS2011

Enhanced Synthesis of Alkyl Amino Acids in Miller's 1958 H2S Experiment

Stanley Miller's 1958 H2S-containing experiment, which included a simulated prebiotic atmosphere of methane (CH4), ammonia (NH3), carbon dioxide (CO2), and hydrogen sulfide (H2S) produced several alkyl amino acids, including the alpha-, beta-, and gamma-isomers of aminobutyric acid (ABA) in greater relative yields than had previously been reported from his spark discharge experiments. In the presence of H2S, aspariic and glutamic acids could yield alkyl amino acids via the formation of thioimide intermediates. Radical chemistry initiated by passing H2S through a spark discharge could have also enhanced alkyl amino acid synthesis by generating alkyl radicals that can help form the aldehyde and ketone precursors to these amino acids. We propose mechanisms that may have influenced the synthesis of certain amino acids in localized environments rich in H2S and lightning discharges, similar to conditions near volcanic systems on the early Earth, thus contributing to the prebiotic chemical inventory of the primordial Earth.

Parker, Eric T.↗

NASA NTRS2012

Late Effects of Heavy Ion Irradiation on Ex Vivo Osteoblastogenesis and Cancellous Bone Microarchitecture

Prolonged spaceflight causes degeneration of skeletal tissue with incomplete recovery even after return to Earth. We hypothesize that heavy ion irradiation, a component of Galactic Cosmic Radiation, damages osteoblast progenitors and may contribute to bone loss during long duration space travel beyond the protection of the Earth's magnetosphere. Male, 16 week old C57BL6/J mice were exposed to high LET (56 Fe, 600MeV) radiation using either low (5 or 10cGy) or high (50 or 200cGy) doses at the NASA Space Radiation Lab and were euthanized 3 - 4, 7, or 35 days later. Bone structure was quantified by microcomputed tomography (6.8 micron pixel size) and marrow cell redox assessed using membrane permeable, free radical sensitive fluorogenic dyes. To assess osteoblastogenesis, adherent marrow cells were cultured ex vivo, then mineralized nodule formation quantified by imaging and gene expression analyzed by RT PCR. Interestingly, 3 - 4 days post exposure, fluorogenic dyes that reflect cytoplasmic generation of reactive nitrogen/oxygen species (DAF FM Diacetate or CM H2DCFDA) revealed irradiation (50cGy) reduced free radical generation (20-45%) compared to sham irradiated controls. Alternatively, use of a dye showing relative specificity for mitochondrial superoxide generation (MitoSOX) revealed an 88% increase compared to controls. One week after exposure, reactive oxygen/nitrogen levels remained lower(24%) relative to sham irradiated controls. After one month, high dose irradiation (200 cGy) caused an 86% decrement in ex vivo nodule formation and a 16-31% decrement in bone volume to total volume and trabecular number (50, 200cGy) compared to controls. High dose irradiation (200cGy) up regulated expression of a late osteoblast marker (BGLAP) and select genes related to oxidative metabolism (Catalase) and DNA damage repair (Gadd45). In contrast, lower doses (5, 10cGy) did not affect bone structure or ex vivo nodule formation, but did down regulate iNOS by 0.54 - 0.58 fold. Thus, both low and high doses of heavy ion irradiation cause time dependent, adaptive changes in redox state within marrow cells but only high doses (50, 200cGy) inhibit osteoblastogenesis and cause cancellous bone loss. We conclude space radiation has the potential to cause persistent damage to bone marrow derived stem and progenitor cells for osteoblasts despite adaptive changes in cellular redox state.

Tran, Luan Hoang↗

NASA NTRS2014

The Antarctic Ozone Hole: An Update

The stratospheric ozone hole, an annual occurrence during austral spring, is caused by heterogeneous conversion of hydrogen chloride and chlorine nitrate to chlorine radicals. These reactions take place of polar stratospheric cloud particles in the cold, isolate Antarctic winter vortex. The chlorine radicals participate in chemical reactions that rapidly deplete ozone when sunlight returns at the end of polar night. International agreements eliminated production of the culprit anthropogenic chlorofluorocarbons in the late 1990s, but due to their long stratospheric lifetime (50-100 years), the ozone hole will continue its annual appearance for years to come.

chlorofluorcarbons↗

NASA NTRS2015

The Formation of Organic Compounds of Astrobiological Interest by the Irradiation Processing of Astrophysical Ices

Many environments in space contain very low temperature mixed molecular ices that are exposed to ionizing radiation in the form of cosmic rays and high-energy photons. While traditional chemistry would not be expected to occur at the temperatures typical of these ices (T < 50 K), ionizing radiation can break bonds in the original molecules in the ices to form highly reactive ions and radicals. These ions and radicals are subsequently free to react despite the low temperatures of the original ices. Laboratory experiments, many of them carried out at the Astrochemistry Laboratory at NASA-Ames, show that the irradiation of ices made of even simple molecules like H2O, CO, CO2, CH4, NH3, etc. can result in the robust formation of large numbers of far more complex organic compounds. Many of these new products are of direct interest to astrobiology. For example, the irradiation of mixed molecular ices has been shown to produce amino acids, amphiphiles, quinones, sugars, heterocyclic compounds, and nucleobases, all molecular building blocks used by terrestrial life. Insofar as the presence of these materials plays a role in the origin of life on planets, this has profound implications for the potential abundance of life in the universe since these experiments simulate universal conditions that are expected to be found wherever new stars and planets form.

Astrobiology↗

NASA NTRS2016

Development of Hydroxyl Tagging Velocimetry for Low Velocity Flows

Hydroxyl tagging velocimetry (HTV) is a molecular tagging technique that relies on the photo-dissociation of water vapor into OH radicals and their subsequent tracking using laser induced fluorescence. Velocities are then obtained from time-of-flight calculations. At ambient temperature in air, the OH species lifetime is relatively short (<50 μs), making it suited for high speed flows. Lifetime and radicals formation increases with temperature, which allows HTV to also probe low-velocity, high-temperature flows or reacting flows such as flames. The present work aims at extending the domain of applicability of HTV, particularly towards low-speed (<10 m/s) and moderate (<500 K) temperature flows. Results are compared to particle image velocimetry (PIV) measurements recorded in identical conditions. Single shot and averaged velocity profiles are obtained in an air jet at room temperature. By modestly raising the temperature (100-200 degC) the OH production increases, resulting in an improvement of the signal-to-noise ratio (SNR). Use of nitrogen - a non-reactive gas with minimal collisional quenching - extends the OH species lifetime (to over 500 μs), which allows probing of slower flows or, alternately, increases the measurement precision at the expense of spatial resolution. Instantaneous velocity profiles are resolved in a 100degC nitrogen jet (maximum jet-center velocity of 6.5 m/s) with an uncertainty down to 0.10 m/s (1.5%) at 68% confidence level. MTV measurements are compared with particle image velocimetry and show agreement within 2%.

Andre, Matthieu A.↗

NASA NTRS2017

Radiation Chemistry of Solid Acetone in the Interstellar Medium - A New Dimension to an Old Problem

A laboratory investigation of acetone, an interstellar and cometary molecule, has produced new results concerning its decomposition in a radiation environment. Mid-infrared spectroscopy has been used to follow amorphous acetone's destruction by ionizing radiation (1 MeV protons) at 20 K. Radiation products identified are the CH4, CO, and CO2 usually made in such experiments, along with ketene, allene, and the acetonyl radical, all identified here for the first time in irradiated solid acetone. Evidence for the reduction product 2-propanol was suggestive, but a firm identification could not be made either for it or for the C2 hydrocarbons (i.e., C2H6, C2H4, C2H2). The acetyl radical was not observed as a radiation product. Isotopically labeled reagents were used to demonstrate ketene formation and to emphasize that multiple approaches are needed for robust assignments of infrared spectral features of irradiated icy solids. Results from a supporting radiation experiment with isotopically labeled acetic acid are described. Comparisons are made to a previous study of acetone's stability in extraterrestrial radiation environments, and caution is urged in measuring and interpreting CO abundances in irradiated icy solids.

cometary molecule↗

NASA NTRS2018

Late Effects of Heavy-Ion Irradiation on Ex Vivo Osteoblastogenesis and Cancellous Bone Microarchitecture

Prolonged spaceflight causes degeneration of skeletal tissue with incomplete recovery even after return to Earth. We hypothesize that heavy-ion irradiation, a component of Galactic Cosmic Radiation, damages osteoblast progenitors and may contribute to bone loss during long duration space travel beyond the protection of the Earth's magnetosphere. Male, 16 week-old C57BL6/J mice were exposed to high-LET (56-Fe, 600MeV) radiation using either low (5 or 10cGy) or high (50 or 200cGy) doses at the NASA Space Radiation Lab and were euthanized 3-4, 7, or 35 days later. Bone structure was quantified by microcomputed tomography (6.8 μm pixel size) and marrow cell redox assessed using membrane permeable, free radical-sensitive fluorogenic dyes. To assess osteoblastogenesis, adherent marrow cells were cultured ex vivo, then mineralized nodule formation quantified by imaging and gene expression analyzed by RT-PCR. Interestingly, 3-4 days post-exposure, fluorogenic dyes that reflect cytoplasmic generation of reactive nitrogen/oxygen species (DAF-FM Diacetate or CM-H2DCFDA) revealed irradiation (50cGy) reduced free radical generation (20-45%) compared to sham-irradiated controls. Alternatively, use of a dye showing relative specificity for mitochondrial superoxide generation (MitoSOX) revealed an 88% increase compared to controls. One week after exposure, reactive oxygen/nitrogen levels remained lower (24%) relative to sham-irradiated controls. After one month, high dose irradiation (200 cGy) caused an 86% decrement in ex vivo nodule formation and a 16-31% decrement in bone volume to total volume and trabecular number (50, 200cGy) compared to controls. High dose irradiation (200cGy) up-regulated expression of a late osteoblast marker (BGLAP) and select genes related to oxidative metabolism (Catalase) and DNA damage repair (Gadd45). In contrast, lower doses (5, 10cGy) did not affect bone structure or ex vivo nodule formation, but did down-regulate iNOS by 0.54-0.58 fold. Thus, both low- and high-doses of heavy-ion irradiation cause time-dependent, adaptive changes in redox state within marrow cells but only high doses (50, 200cGy) inhibit osteoblastogenesis and cause cancellous bone loss. We conclude space radiation has the potential to cause persistent damage to bone marrow-derived stem and progenitor cells for osteoblasts despite adaptive changes in cellular redox state.

LATE EFFECTS OF HEAVY-ION IRRADIATION↗

NASA NTRS2018

Forming Perchlorates on Mars Through Plasma Chemistry During Dust Events

We report experimental evidences to support a new formation mechanism, multiphase redox plasma chemistry, for perchlorate on Mars observed during the Phoenix mission, whose high concentrations and high ClO4/Cl ratio cannot be fully interpreted by photochemistry. This chemical reaction occurs between Cl-bearing minerals on the Mars surface and free radicals generated by electrostatic discharge (ESD) during Mars dust events (dust storms, dust devils, and grain saltation). We conducted simulated ESD experiments in a Mars chamber with pure CO2, CO2+H2O(g), and Mars Simulate Gas Mixture at Martian atmospheric pressure. We directly observed (1) the instantaneous generation of atmospheric free radicals CO2+, CO+, OI, HIII, HII, OH, ArI, N2, and N2+in normal glow discharge (NGD), detected by in situ plasma emission spectroscopy, and O3by UV and Mid-IR spectroscopy; (2) the fast transformation of NaCl to NaClO3and NaClO4detected by laser Raman spectroscopy, with oxychlorine enrichment at the sample surfaces confirmed by ion chromatography. Through two sets of experimental comparison, we found that the oxidation power of ESD-electron is three orders of magnitude higher than that of UVC-photon. We scaled our experimental results to the modeled ESD in Mars dust events and Mars surface UV radiation level, and concluded that plasma chemistry occurred during Mars dust events can be an additional important formation mechanism for the large amounts of perchlorates observed during various missions to Mars.

Wu, Zhongchen↗

NASA NTRS2016

Electronically Excited States of Anistropically Extended Singly-Deprotonated PAH Anions

Polycyclic Aromatic Hydrocarbons (PAHs) play a significant role in the chemistry of the interstellar medium (ISM) as well as in hydrocarbon combustion. These molecules can have high levels of diversity with the inclusion of heteroatoms and the addition or removal of hydrogens to form charged or radical species. There is an abundance of data on the cationic forms of these molecules, but there have been many fewer studies on the anionic species. The present study focuses on the anionic forms of deprotonated PAHs. It has been shown in previous work that PAHs containing nitrogen heteroatoms (PANHs) have the ability to form valence excited states giving anions electronic absorption features. This work analyzes how the isoelectronic pure PAHs behave under similar structural constructions. Singly-deprotonated forms of benzene, naphthalene, anthracene, and teteracene classes are examined. None of the neutral-radicals possess dipole moments large enough to support dipole-bound excited states in their corresponding closed-shell anions. Even though the PANH anion derivatives support valence excited states for three-ringed structures, it is not until four-ringed structures of the pure PAH anion derivatives that valence excited states are exhibited. However, anisotropically-extended PAHs larger than tetracene will likely exhibit valence excited states. The relative energies for the anion isomers are very small for all of the systems in this study.

Theis, Mallory L.↗

NASA NTRS2019

Anthropogenic Control over Wintertime Oxidation of Atmospheric Pollutants

Anthropogenic air pollutants such as nitrogen oxides (NO(x) = NO + NO(2)), sulfur dioxide (SO(2)), and volatile organic compounds (VOC), among others, are emitted to the atmosphere throughout the year from energy production and use, transportation, and agriculture. These primary pollutants lead to the formation of secondary pollutants such as fine particulate matter (PM(2.5)) and ozone (O(3)) and perturbations to the abundance and lifetimes of short-lived greenhouse gases. Free radical oxidation reactions driven by solar radiation govern the atmospheric lifetimes and transformations of most primary pollutants and thus their spatial distributions. During winter in the mid and high latitudes, where a large fraction of atmospheric pollutants are emitted globally, such photochemical oxidation is significantly slower. Using observations from a highly instrumented aircraft, we show that multi-phase reactions between gas-phase NO(x) reservoirs and aerosol particles, as well as VOC emissions from anthropogenic activities, lead to a suite of atypical radical precursors dominating the oxidizing capacity in polluted winter air, and thus, the distribution and fate of primary pollutants on a regional to global scale.

Haskins, J. D.↗

NASA NTRS2017

Radiation Chemistry of Solid Acetone in the Interstellar Medium - A New Dimension to an Old Problem

A laboratory investigation of acetone, an interstellar and cometary molecule, has produced new results concerning its decomposition in a radiation environment. Mid-infrared spectroscopy has been used to follow amorphous acetone’s destruction by ionizing radiation (1 MeV protons) at 20 K. Radiation products identified are the CH4, CO, and CO2 usually made in such experiments, along with ketene, allene, and the acetonyl radical, all identified here for the first time in irradiated solid acetone. Evidence for the reduction product 2-propanol was suggestive, but a firm identification could not be made either for it or for the C2 hydrocarbons (i.e., C2H6, C2H4, C2H2). The acetyl radical was not observed as a radiation product. Isotopically labeled reagents were used to demonstrate ketene formation and to emphasize that multiple approaches are needed for robust assignments of infrared spectral features of irradiated icy solids. Results from a supporting radiation experiment with isotopically labeled acetic acid are described. Comparisons are made to a previous study of acetone’s stability in extraterrestrial radiation environments, and caution is urged in measuring and interpreting CO abundances in irradiated icy solids.

R. L. Hudson↗

NASA NTRS2021

Limits on Runoff Episode Duration for Early Mars: Integrating Lake Hydrology and Climate Models

Fluvio-lacustrine features on the martian surface attest to a climate that was radically different in the past. Since climate models have difficulty sustaining a liquid hydrosphere at the surface, multiple cycles of runoff episodes may have characterized the ancient Mars climate. A fundamental question thus remains: what was the duration of these runoff-producing episodes? Here we use morphometric measurements from newly identified coupled lake systems, containing both an open- and a closed-basin lake (n=7). We combined hydrological balances with precipitation outputs from climate models, and found that breaching runoff episodes likely lasted 102−105yr; other episodes may have been shorter but could not be longer. Runoff episode durations are model-dependent and spatiallyvariable, and no27climate model scenario can satisfy a unique duration for all coupled systems. In the near future, these quantitative constraints on early Mars lake persistence may be tested through in situ observations from Perseverance rover. Plain Language Summary Ancient river and lake beds on the martian surface point to a climate that was radically different in the past, unlike the dry, cold desert that Mars is today. It experienced significant liquid water flowing across the surface (i.e., ‘runoff’) and hosted long-lived bodies of water (lakes and seas). However, scientists that generate models to simulate the ancient Mars climate have difficulty sustaining this proposed liquid water cycle at the surface. One possible hypothesis is that multiple cycles of individual liquid water episodes may have characterized the ancient martian climate (i.e. runoff episodes). A fundamental question thus remains: what was the duration of these individual runoff-producing episodes? Here we use an approach that takes advantage of unique martian lake system, ‘coupled’ lake systems, and their shapes. We combined these measurements with precipitation results from previous climate models, and found that runoff episodes likely lasted 100-10,000 years, requiring a global climate mechanism that generated repeated cycles of this duration. Ultimately, our results can be tested through observations made by NASA’s Perseverance rover, shedding light on the uninterrupted duration of surface water on Mars and its potential to host life in the past.

Gaia Stucky de Quay↗

NASA NTRSDate not supplied

Characterization of Reactant Refill and Detonation Wave Dynamics in a GOx/Natural-gas RDRE Using Simultaneous High Repetition-Rate OH-PLIF and Chemiluminescence

The potential application of rotating detonation engines (RDEs) in rocket combustors hinges on a fundamental understanding of detonation wave structure and injector characteristics with fuel and oxidizer compositions relevant in rocket systems. Simultaneous 300 kHz-rate broadband OH* chemiluminescence and OH-PLIF imaging is employed in a fully optically accessible Natural Gas-GOx rotating detonation rocket engine (RDRE) to visualize reactant refill dynamics and detonation wave structure. A custom-built KTP-type optical parametric oscillator (OPO) is coupled with a nanosecond high-repetition-rate burst-mode laser to output284 nm light and target excitation of the Q1(9) transition in the OH radical. Significant deflagrative burning is observed throughout the chamber as a consequence of the oxygen-rich environment. Trailing Azimuthal Reflected Shock Combustion (ARSC) system, similar to those in a H2-air RDE are observed, burning unburned reactants in the region immediately following the primary detonation wave. Contact burning, as indicated in this study, does not seem to be a primary loss mechanism. The simultaneous measurement of OH and OH* show that axial locations exist in the refill process where OH radicals are present, and produced due to shear layer induced deflagration, however, these zones do not produce excited state OH*. While a deeper understanding of the underlying physics in RDRE systems requires further investigation, this work highlights a first-of-its-kind visualization of the turbulent combustion product field and reactant refill characteristics in this highly unsteady environment.

Propulsion↗

NASA NTRSDate not supplied

Commercially-viable Hydrogen Aircraft for Reduction of Greenhouse Emissions

NASA assembled a cross-organizational multidisciplinary “radical” project team combining a diverse set of skills including aircraft architecture modelling and optimization, advanced material science, and engineering of high performance cryogenic, thermal management and fuel cell systems components and subsystems to tackle the challenging problem of development of commercially viable mid-size aircraft that would radically transform air transportation. Our team is developing an integrated conceptual and experimental methodology to realize a medium-range hydrogen aircraft design based on fuel cells, hydrogen burning engines, advanced power management and distribution, cryogenic hydrogen storage systems, and novel thermal management systems combined with an integrated aircraft concept of operations both during the flight and at the airports. The resulting analyses suggested the aircraft architecture options, sizes and layouts for the propulsion subsystem and cryogenic liquid hydrogen (LH2) tankage to verify the weight-scaling relationships for a medium-range aircraft carrying 100-200 passengers flying 1000 - 5000 km. Hydrogen - based distributed electric propulsion and cryogenic systems were further analysed, and more detailed study identified systems goals for a viable overall system weight for missions of various lengths. The developed aircraft architecture is being optimized by total specific energy density, specific power, size and mission profiles.

aircraft architecture↗

NASA NTRSDate not supplied

Commercially-viable Hydrogen Aircraft for Reduction of Greenhouse Emissions

aircraft architecture↗

NASA NTRSDate not supplied

Stress-Activated Positive Holes (O− in a Matrix of O2–) Cause DNA Damage in Surface-Dwelling Organisms: Unveiling Mutation-Induced Secrets of Nature

Peroxy defects consist of pairs of tightly bonded oxygen anions in the –1 valence state such as in O3X/OO\YO3 with X, Y = Si4+, Al3+ etc. They commonly occur in igneous, metamorphic and many sedimentary rocks. When such rocks are stressed by tectonic forces, peroxy defects break up, releasing highly mobile electronic charge carriers: defect electrons in the O2– sublattice, i.e. unbound O–, known as “positive holes”, h•. The h• can flow out of stressed rock volumes, spreading far and wide, causing electric currents and electrochemical reactions. This study explores how the h• impact the electron flow in the electron transport chain (ETC) of organisms on the surface of rocks such as gabbro and granite. We found that, by forming hydroxyl radicals and superoxide anions, the h• disrupt the in vivo coordination of reduction-oxidation reactions that are essential for the timing of the redox cycle. Our observations show that stress activation of h• delays the sprouting of certain plant seeds and impedes the growth of yeast cultures, Saccharomyces cerevisiae. The h• induce mutations and affect plant development as evidenced by reduced stem length and leaf size. At the same time, the h• serve as a source of abiotic oxidation, capable of forming various organic compounds in situ. Through the generation of radical species that create new carbon-carbon bonds the h• facilitate the abiotic synthesis of hydrocarbons and other organic molecules essential to life, including porphyrins. Our findings highlight the intricate interplay between positive holes, redox timing, and biological processes, revealing their significant role in influencing the growth and development of organisms in tectonically stressed crustal environments. Understanding these effects enhances our broader comprehension of redox biology and the influence of environmental factors on cellular development in natural settings.

astrobiology↗

DOE OSTI2021

Effects of non-thermal termolecular chemistry on detonation development in hydrogen (H2) / methane (CH4) - air mixtures

In combustion simulations, it is usually assumed that highly-energized collision complexes (either radical or stable species) formed in exothermic reactions are always under thermal equilibrium as they evolve through competing networks of reactions. However, in practical flames, non-trivial amounts of reactive radicals such as H, O and OH are present apart from O2. As a result, collisions of these reactive species with the energized collision complexes have been shown in recent studies to induce non-thermal reactivity. These studies have also demonstrated that such non-thermal reactions can be suitably represented in macroscopic kinetics models as chemically termolecular reactions. The present work was focused on identifying and quantifying the effects of including such reactions on the evolution of an initial deflagration front to a developing detonation in H2/CH4-air mixtures under boosted internal combustion (IC) engine conditions. Specifically, fully resolved simulations, with and without non-thermal reactivity, were performed for a constant volume reactor containing stoichiometric H2/CH4-air mixture. It was found that inclusion of termolecular chemistry resulted in a delayed onset of end-gas auto-ignition. Concurrently, the developing detonation intensity was observed to be significantly higher. Chemical explosive mode analysis (CEMA) was performed to identify the dominant species/reactions responsible for the observed variation in the results.

Detonation↗