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At least 127 records · Page 7

Benthic Marine Cyanobacterial Mat Ecosystems: Biogeochemistry and Biomarkers

Cyanobacterial mats are complete ecosystems that can include processes of primary production, diagenesis and lithification. Light sustains oxygenic photosynthesis, which in turn provides energy, organic matter and oxygen to the community. Due to both absorption and scattering phenomena, incident light is transformed with depth in the mat, both in intensity and spectral composition. Mobile photo synthesizers optimize their position with respect to this light gradient. When photosynthesis ceases at night, the upper layers of the mat become reduced and sulfidic. Counteracting gradients of oxygen and sulfide combine to provide daily-contrasting environments separated on a scale of a few mm. The functional complexity of mats, coupled with the highly proximal and ordered spatial arrangement of biota, offers the potential for a staggering number of interactions. At a minimum, the products of each functional group of microorganisms affect the other groups both positively and negatively. For example, cyanobacteria generate organic matter (potential substrates) but also oxygen (a toxin for many anaerobes). Anaerobic activity recycles nutrients to the photosynthesizers but also generates potentially toxic sulfide. The combination of benefits and hazards of light, oxygen and sulfide promotes the allocation of the various essential mat processes between light and dark periods, and to various depths in the mat. Observations of mats have produced numerous surprises. For example, obligately anaerobic processes can occur in the presence of abundant oxygen, highly reduced gases are produced in the presence of abundant sulfate, meiofauna thrive at high sulfide concentrations, and the mats' constituent populations respond to environmental changes in complex ways. While photosynthetic bacteria dominate the biomass and productivity of the mat, nonphotosynthetic, anaerobic processes constitute the ultimate biological filter on the ecosystem's emergent biosignatures, including those sedimentary textures, organic compounds, and minerals that enter the fossil record. The ability of cyanobacterial mats to channel abundant solar energy into the creation and maintenance of complex structures and processes has created a multitude of consequences, both for sedimentation and for the early evolution of our biosphere.

DesMarais, David J.↗

A Preliminary Assessment of the Organic Content of Interplanetary Dust Particles

Interplanetary dust particles (IDPs) collected from the Earth's stratosphere by NASA have been shown to contain significant quantities of organic matter. Anders suggested that organic matter contributed by IDPs to the surface of the Earth may have been important for the origin of life. As part of our ongoing effort to characterize the organic carbon in IDPs, we have now compared the absorption strengths of organic features in IDPs to their strengths in meteorites and standards to estimate the concentration of each organic functional group in IDPs.

Flynn, G. J.↗

Multipole correction of atomic monopole models of molecular charge distribution. I. Peptides

The defects in atomic monopole models of molecular charge distribution have been analyzed for several model-blocked peptides and compared with accurate quantum chemical values. The results indicate that the angular characteristics of the molecular electrostatic potential around functional groups capable of forming hydrogen bonds can be considerably distorted within various models relying upon isotropic atomic charges only. It is shown that these defects can be corrected by augmenting the atomic point charge models by cumulative atomic multipole moments (CAMMs). Alternatively, sets of off-center atomic point charges could be automatically derived from respective multipoles, providing approximately equivalent corrections. For the first time, correlated atomic multipoles have been calculated for N-acetyl, N'-methylamide-blocked derivatives of glycine, alanine, cysteine, threonine, leucine, lysine, and serine using the MP2 method. The role of the correlation effects in the peptide molecular charge distribution are discussed.

NASA Discipline Exobiology↗

The Response of the North Atlantic Bloom to NAO Forcing

Results from the climatologically forced coupled ice/ocean/biogeochemical model that covers the Arctic and North Atlantic Oceans are presented and compared to the chlorophyll fields of satellite-derived ocean color measurements. Biogeochemical processes in the model are determined from the interactions among four phytoplankton functional groups (diatoms, chlorophytes, cyanobacteria and coccolithophores) and four nutrients (nitrate, ammonium, silicate and dissolved iron). The model simulates the general large-scale pattern in April, May and June, when compared to both satellite-derived and in situ observations. The subpolar North Atlantic was cool in the 1980s and warm in the latter 1990s, corresponding to the CZCS and SeaWiFS satellite observing periods, respectively. The oceanographic conditions during these periods resemble the typical subpolar upper ocean response to the NAO+ and NAO-phases, respectively. Thus, we use the atmospheric forcing composites from the two NAO phases to simulate the variability of the mid-ocean bloom during the satellite observing periods. The model results show that when the subpolar North Atlantic is cool, the NAO+ case, more nutrients are available in early spring than when the North Atlantic is warm, the NAO-case. However, the NAO+ simulation produces a later bloom than the NAO-simulation. This difference in the bloom times is also identified in SeaWiFS and CZCS satellite measurements. In the model results, we can trace the difference to the early diatom bloom due to a warmer upper ocean. The higher nutrient abundance in the NAO+ case did not provide larger total production than in the NAO- case, instead the two cases had a comparable area averaged amplitude. This leads us to conclude that in the subpolar North Atlantic, the timing of the spring phytoplankton bloom depends on surface temperature and the magnitude of the bloom is not significantly impacted by the nutrient abundance.

Mizoguchi, Ken-Ichi↗

In-situ polymerized PLOT columns III: divinylbenzene copolymers and dimethacrylate homopolymers

Studies of divinylbenzene copolymers and dimethacrylate homopolymers indicate that the polymer pore size controls the separation of water and ammonia on porous-layer-open-tubular (PLOT) columns. To a lesser degree, the polarity of the polymers also affects the separation of a water-ammonia gas mixture. Our results demonstrate that the pore size can be regulated by controlling the cross-linking density or the chain length between the cross-linking functional groups. An optimum pore size will provide the best separation of water and ammonia.

NASA Discipline Exobiology↗

Neural network recognition of chemical class information in mobility spectra obtained at high temperatures

A minimal neural network was applied to a large library of high-temperature mobility spectra drawn from 16 chemical classes including 154 substances with 2000 spectra at various concentrations. A genetic algorithm was used to create a representative subset of points from the mobility spectrum as input to a cascade-type back-propagation network. This network demonstrated that significant information specific to chemical class was located in the spectral region near the reactant ions. This network failed to generalize the solution to unfamiliar compounds necessitating the use of complete spectra in network processing. An extended back-propagation network classified unfamiliar chemicals by functional group with a mean for average values of 0.83 without sulfides and 0.79 with sulfides. Further experiments confirmed that chemical class information was resident in the spectral region near the reactant ions. Deconvolution of spectra demonstrated the presence of ions, merged with the reactant ion peaks that originated from introduced samples. The ability of the neural network to generalize the solution to unfamiliar compounds suggests that these ions are distinct and class specific.

NASA Discipline Environmental Health↗

Prebiotic synthesis of 5-substituted uracils: a bridge between the RNA world and the DNA-protein world

Under prebiotic conditions, formaldehyde adds to uracil at the C-5 position to produce 5-hydroxymethyluracil with favorable rates and equilibria. Hydroxymethyluracil adds a variety of nucleophiles, such as ammonia, glycine, guanidine, hydrogen sulfide, hydrogen cyanide, imidazole, indole, and phenol, to give 5-substituted uracils with the side chains of most of the 20 amino acids in proteins. These reactions are sufficiently robust that, if uracil had been present on the primitive Earth, then these substituted uracils would also have been present. The ribozymes of the RNA world would have included many of the functional groups found in proteins today, and their catalytic activities may have been considerably greater than presently assumed.

NASA Program NSCORT↗

Simulated Space Environment Effects on Tether Materials with Protective Coatings

Atomic oxygen (AO) erodes most organic materials. and ultraviolet radiation embrittles polymers. A previous study indicated untreated polymers such as ultra-high molecular weight polyethylene (UHMWPE) are severely degraded when exposed to AO. This test series was performed to determine the effect of AO and UV on the mechanical integrity of tether materials that were treated with AO-protective coatings. Three coating systems were evaluated for their ability to protect the underlying material from AO erosion. The first coating system is the Photosil surface modification process which incorporates silicon-containing functional groups into the top micron of an organic material. The Photosil process has had favorable results with polyurethane- and epoxy-based thermal control coatings . The second coating system is metallization, in this case nickel. The third coating system is silsesquioxane. The Marshall Space Flight Center Atomic Oxygen Beam Facility (AOBF) was used to simulate low Earth orbit AO of 5 eV energy. In addition, some tether samples were exposed to ultraviolet radiation then evaluated for any changes in mechanical strength. Tether missions, such as a momentum-exchange/electrodynamic reboost (MXER) tether, may benefit from this research.

Finckenor, Miria M.↗

Strained Hydrocarbons as Potential Hypergolic Fuels

A storable combination of high-energy hypergolic fuel and oxidizer is advantageous to the future of reusable launch vehicles (RLVs). The combination will allow an increase in energy per unit volume of fuel and eliminate the need for an external ignition system. Strained systems have been studied as potential high-density fuels. Adding hypergolic functional groups, such as amino groups, to these hydrocarbons will potentially allow auto ignition of strained systems with hydrogen peroxide. Several straight chain amines and their strained counterparts containing an equivalent number of carbon atoms have been purchased and synthesized. These amines provide initial studies to determine the effects of fuel vapor pressure, strain energy, fuel miscibility, and amine substitution upon fuel ignition time and hypergolicity with hydrogen peroxide as an oxidizer.

Source record↗

Structure and Bonding of Carbon in Clays from CI Carbonaceous Chondrites

Carbonaceous chondrites (CC) contain a diverse suite of C-rich materials. Acid dissolution of these meteorites leaves a C-rich residue with chemical and structural affinities to kerogen. This material has primarily been analyzed in bulk, and much information has been provided regarding functional groups and elemental and isotopic compositions. However, comparatively little work has been done on C in unprocessed meteorites. Studies of CCs suggest a spatial relationship of some C-rich materials with products of aqueous alteration. Recent studies revealed discrete submicronsized, C-rich particles in Tagish Lake and a range of CM2 meteorites. A challenge is to correlate the findings from the bulk acid-residue studies with those of high-spatial resolution-mineralogical and spectroscopic observations of unprocessed meteorites. Hence, the relationship between the C-rich materials in the acid residues and its form and locations in the unprocessed meteorite remains unclear. Here we provide information on the structure and bonding of C associated with clays in CI carbonaceous chondrites. Additional information is included in the original extended abstract.

Garview, Laurence a. J.↗

Single Pulse Remote Raman Detection of Minerals and Organics Under Illuminated Condition from 10 Meters Distance

A directly coupled portable remote Raman instrument developed by the University of Hawaii has been shown here to identify several minerals, chemicals and organics from a distance of 10 m using a single laser pulse in a well illuminated background. Raman spectra, obtained during a very short period of time, of common minerals e.g., dolomite, calcite, marble, barite, gypsum, quarts, rutile, fluorapatite etc. clearly show Raman features which could be used as fingerprints for mineral identification. Raman features of organics such as benzene, cyclohexane, 2-propanol, naphthalene, etc. and other chemicals containing various functional groups like oxides, silicates, sulphates, nitrates, phosphates and carbonates were also easily detected. Ability to measure Raman spectra with a single laser pulse would be promising for future space missions where power consumption is critical and a rapid survey of the minerals with moderate to high Raman cross section might be desirable for selecting rocks that would provide high scientific return or for acquiring rocks for sample return to the Earth.

Misra, A. K.↗

The Insoluble Carbonaceous Material of CM Chondrites as Possible Source of Discrete Organics During the Asteroidal Aqueous Phase

The larger portion of the organic carbon in carbonaceous chondrites (CC) is present as a complex and heterogeneous macromolecular material that is insoluble in acids and most solvents (IOM). So far, it has been analyzed only as a whole by microscopy (TEM) and spectroscopy (IR, NMR, EPR), which have offered and overview of its chemical nature, bonding, and functional group composition. Chemical or pyrolytic decomposition has also been used in combination with GC-MS to identify individual compounds released by these processes. Their value in the recognition of the original IOM structure resides in the ability to properly interpret the decomposition pathways for any given process. We report here a preliminary study of IOM from the Murray meteorite that combines both the analytical approaches described above, under conditions that would realistically model the IOM hydrothermal exposure in the meteorite parent body. The aim is to document the possible release of water and solvent soluble organics, determine possible changes in NMR spectral features, and ascertain, by extension, the effect of this loss on the frame of the IOM residue. Additional information is included in the original extended abstract.

Yabuta, H.↗

Modeling of Radiation Risks for Human Space Missions

Prior to any human space flight, calculations of radiation risks are used to determine the acceptable scope of astronaut activity. Using the supercomputing facilities at NASA Ames Research Center, Ames researchers have determined the damage probabilities of DNA functional groups by space radiation. The data supercede those used in the current Monte Carlo model for risk assessment. One example is the reaction of DNA with hydroxyl radical produced by the interaction of highly energetic particles from space radiation with water molecules in the human body. This reaction is considered an important cause of DNA mutations, although its mechanism is not well understood.

Fletcher, Graham↗

The Synthesis and Testing of Highly Strained Cyclic and Polycyclic Molecules as Hypergolic Fuels

Increasing fuel efficiency has been a goal for chemists for several decades. Particularly, a more efficient fuel can increase the range of liquid-hydrocarbon-fueled ram-jets and cruise missiles. A storable high-energy fuel that spontaneously ignites upon addition of an oxidizer is defined as a hypergolic fuel. Hypergolic storable fuels provide an increase in energy per unit volume of fuel and eliminate the need for an external ignition system. Several classes of functionalized hydrocarbons such as amines, boranes, and phosphines are known to be hypergolic with nitric acid oxidizers, but only hydrazine and its simple derivatives5 have been found to exhibit true hypergolic behavior with H2O2. Hydrogen peroxide is a good candidate for an oxidizer due to its reduced toxicity and improved storage capability. Hydrazine-based fuels are expensive, highly corrosive, and toxic, thus providing the need for investigation of other fuels that may be hypergolic with H2O2. Strained hydrocarbons have been studied as high-density fuels. Some examples including benzvalene and cubane, exhibit an increase in heat of combustion as the density of the fuel increases. Many conventional hydrocarbon fuels, such as JP-5 and JP-10, show a decrease in heat of combustion as density of the fuel increases. Strained hydrocarbons can therefore increase the range of the missile by increasing the combustion efficiency per volume of fuel. The goal of this research is to investigate hypergolic behavior of strained hydrocarbons by adding an amine functional group which has been found to hypergolic with nitric acid oxidizers. N,N-Dimethyl-[3]-triangulane-7-methylamine (l), cyclopropylamines (2), cyclobutylamines (3), propylamines (4), and butylamines (5) were synthesized and investigated. The amino group should react with oxygen, providing the initiation step for ring decomposition. The highly exothermic reactions will accumulate energy and potentially lead to spontaneous ignition of the fuel. Triangulanes possess high strain energy, while the less strained cyclopropane and cyclobutanes are more volatile and may show shorter ignition times.

Eccles, Wendy↗

New High-Temperature Membranes Developed for Proton Exchange Membrane Fuel Cells

Fuel cells are receiving a considerable amount of attention for potential use in a variety of areas, including the automotive industry, commercial power generation, and personal electronics. Research at the NASA Glenn Research Center has focused on the development of fuel cells for use in aerospace power systems for aircraft, unmanned air vehicles, and space transportation systems. These applications require fuel cells with higher power densities and better durability than what is required for nonaerospace uses. In addition, membrane cost is a concern for any fuel cell application. The most widely used membrane materials for proton exchange membrane (PEM) fuel cells are based on sulfonated perfluorinated polyethers, typically Nafion 117, Flemion, or Aciplex. However, these polymers are costly and do not function well at temperatures above 80 C. At higher temperatures, conventional membrane materials dry out and lose their ability to conduct protons, essential for the operation of the fuel cell. Increasing the operating temperature of PEM fuel cells from 80 to 120 C would significantly increase their power densities and enhance their durability by reducing the susceptibility of the electrode catalysts to carbon monoxide poisoning. Glenn's Polymers Branch has focused on developing new, low-cost membranes that can operate at these higher temperatures. A new series of organically modified siloxane (ORMOSIL) polymers were synthesized for use as membrane materials in a high-temperature PEM fuel cell. These polymers have an organic portion that can allow protons to transport through the polymer film and a cross-linked silica network that gives the polymers dimensional stability. These flexible xerogel polymer films are thermally stable, with decomposition onset as high as 380 C. Two types of proton-conducting ORMOSIL films have been produced: (1) NASA-A, which can coordinate many highly acid inorganic salts that facilitate proton conduction and (2) NASA-B, which has been produced and which incorporates strongly acidic (proton donating) functional groups into the polymer backbone. Both of these polymer films have demonstrated significantly higher proton conductivity than Nafion at elevated temperatures and low relative humidities. An added advantage is that these polymers are very inexpensive to produce because their starting materials are commodity chemicals that are commercially available in large volumes.

Kinder, James D.↗

Expanding the Capabilities of the JPL Electronic Nose for an International Space Station Technology Demonstration

An array-based sensing system based on polymer/carbon composite conductometric sensors is under development at JPL for use as an environmental monitor in the International Space Station. Sulfur dioxide has been added to the analyte set for this phase of development. Using molecular modeling techniques, the interaction energy between SO2 and polymer functional groups has been calculated, and polymers selected as potential SO2 sensors. Experiment has validated the model and two selected polymers have been shown to be promising materials for SO2 detection.

electronic noses↗

Utility of DF-1 for Radioprotection in Lymphocytes

The development of degenerative changes in the vasculature, such as atherosclerosis, is a known consequence of exposure to ionizing radiation, and is thus a concern for astronaut health following long duration space flight. Cellular damage caused by radiation is due to free radical generation and DNA damage. The goal of this project was to assess the ability of a C60-derivative, DF-1, to mitigate cellular damage resulting from radiation exposure in primary human lymphocytes. DF-1 is a water-soluble C60 fullerene encapsulated in dendrimeric functional groups that is proposed to exhibit antioxidant properties. Human lymphocytes are radiosensitive and travel throughout the body potentially causing bystander effects in any tissues they contact. These cells were subjected to varying doses of gamma radiation in the presence or absence of DF-1. Cells were collected at 48 hours post-irradiation for chromosomal aberration studies and at 72 hours post-irradiation for micronuclei studies. These studies showed that the irradiated cells contained more chromosomal aberrations and micronuclei than the control cells. Addition of the DF-1 reduced the amount of observed DNA damage in the irradiated cells. Growth curves were measured for the lymphocytes exposed to 0 and 4 Gray gamma irradiations, and we observed less growth in the cells irradiated at 4 Gy. 2,7-dichlorofluorescein diacetate was used to detect reactive oxygen species production, and increased production of ROS was observed in the irradiated lymphocytes. Human lymphocytes were subjected to varying doses of gamma or photon radiation in the presence and absence of DF-1 and a known radioprotectant, amifostine. After irradiation, the production of reactive oxygen species, growth curves and cell viability were measured. These cells were also collected to quantify chromosomal aberrations and micronuclei formation. We predict that irradiated cells will show the most damage and that DF-1 will provide protective effects similar to those of amifostine, an established radioprotectant.

Reynolds, Julia↗

High cycle life secondary lithium battery

A secondary battery (10) of high energy density and long cycle is achieved by coating the separator (18) with a film (21) of cationic polymer such as polyvinyl-imidazoline. The binder of the positive electrode (14) such as an ethylene-propylene elastomer binder (26) containing particles (28) of TiS.sub.2 chalcogenide can also be modified to contain sulfone functional groups by incorporating liquid or solid sulfone materials such as 0.1 to 5 percent by weight of sulfolane into the binder. The negative lithium electrode (14), separator (18) and positive electrode (16) are preferably spirally wound and disposed within a sealed casing (17) containing terminals (32, 34). The modified separator and positive electrode are more wettable by the electrolytes in which a salt is dissolved in a polar solvent such as sulfolane.

Yen, Shiao-Ping S.↗