Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Hydroxyls”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 487 records · Page 27
All sourcesNASA NTRSDOE OSTI
NASA NTRS2004

Effect of Oxygen-containing Functional Groups on Protein Stability in Ionic Liquid Solutions

The ability of functionalized ionic liquids (ILs) to provide an environment of increased stability for biomolecules has been studied. Serum albumin is an inexpensive, widely available protein that contributes to the overall colloid osmotic blood pressure within the vascular system. Albumin is used in the present study as a marker of biomolecular stability in the presence of various ILs in a range of concentrations. The incorporation of hydroxyl functionality into the methylimidazolium-based cation leads to increased protein stability detected by fluorescence spectroscopy and circular dichroic (CD) spectrometry.

Turner, Megan B.↗
NASA NTRS1999

Nucleic acid duplexes incorporating a dissociable covalent base pair

We have used molecular modeling techniques to design a dissociable covalently bonded base pair that can replace a Watson-Crick base pair in a nucleic acid with minimal distortion of the structure of the double helix. We introduced this base pair into a potential precursor of a nucleic acid double helix by chemical synthesis and have demonstrated efficient nonenzymatic template-directed ligation of the free hydroxyl groups of the base pair with appropriate short oligonucleotides. The nonenzymatic ligation reactions, which are characteristic of base paired nucleic acid structures, are abolished when the covalent base pair is reduced and becomes noncoplanar. This suggests that the covalent base pair linking the two strands in the duplex is compatible with a minimally distorted nucleic acid double-helical structure.

Non-NASA Center↗
NASA NTRS1999

A complex ligase ribozyme evolved in vitro from a group I ribozyme domain

Like most proteins, complex RNA molecules often are modular objects made up of distinct structural and functional domains. The component domains of a protein can associate in alternative combinations to form molecules with different functions. These observations raise the possibility that complex RNAs also can be assembled from preexisting structural and functional domains. To test this hypothesis, an in vitro evolution procedure was used to isolate a previously undescribed class of complex ligase ribozymes, starting from a pool of 10(16) different RNA molecules that contained a constant region derived from a large structural domain that occurs within self-splicing group I ribozymes. Attached to this constant region were three hypervariable regions, totaling 85 nucleotides, that gave rise to the catalytic motif within the evolved catalysts. The ligase ribozymes catalyze formation of a 3',5'-phosphodiester linkage between adjacent template-bound oligonucleotides, one bearing a 3' hydroxyl and the other a 5' triphosphate. Ligation occurs in the context of a Watson-Crick duplex, with a catalytic rate of 0.26 min(-1) under optimal conditions. The constant region is essential for catalytic activity and appears to retain the tertiary structure of the group I ribozyme. This work demonstrates that complex RNA molecules, like their protein counterparts, can share common structural domains while exhibiting distinct catalytic functions.

NASA Discipline Exobiology↗
NASA NTRS1999

Multi-site modulation of flux during monolignol formation in loblolly pine (Pinus taeda)

Loblolly pine (Pinus taeda L.) cell suspension cultures secrete monolignols when placed in 8% sucrose/20 mM KI solution, and these were used to identify phenylpropanoid pathway flux-modulating steps. When cells were provided with increasing amounts of either phenylalanine (Phe) or cinnamic acid, cellular concentrations of immediate downstream products (cinnamic and p-coumaric acids, respectively) increased, whereas caffeic and ferulic acid pool sizes were essentially unaffected. Increasing Phe concentrations resulted in increased amounts of p-coumaryl alcohol relative to coniferyl alcohol. However, exogenously supplied cinnamic, p-coumaric, caffeic, and ferulic acids resulted only in increases in their intercellular concentrations, but not that of downstream cinnamyl aldehydes and monolignols. Supplying p-coumaryl and coniferyl aldehydes up to 40, 000-320,000-fold above the detection limits resulted in rapid, quantitative conversion into the monolignols. Only at nonphysiological concentrations was transient accumulation of intracellular aldehydes observed. These results indicate that cinnamic and p-coumaric acid hydroxylations assume important regulatory positions in phenylpropanoid metabolism, whereas cinnamyl aldehyde reduction does not serve as a control point. Copyright 1999 Academic Press.

NASA Discipline Plant Biology↗
NASA NTRS1999

A liposomal model that mimics the cutaneous production of vitamin D3. Studies of the mechanism of the membrane-enhanced thermal isomerization of previtamin D3 to vitamin D3

We reported previously that the rate of previtamin D3 (preD3) <==> vitamin D3 isomerization was enhanced by about 10 times in the skin compared with that in organic solvents. To elucidate the mechanism by which the rate of this reaction is enhanced in the skin, we developed a liposomal model that mimicked the enhanced isomerization of preD3 to vitamin D3 that was described in human skin. Using this model we studied the effect of changing the polarity of preD3 as well as changing the chain length and the degree of saturation of liposomal phospholipids on the kinetics of preD3 <==> vitamin D3 isomerization. We found that a decrease in the hydrophilic interaction of the preD3 with liposomal phospholipids by an esterification of the 3beta-hydroxy of preD3 (previtamin D3-3beta-acetate) reduced the rate of the isomerization by 67%. The addition of a hydroxyl on C-25 of the hydrophobic side chain (25-hydroxyprevitamin D3), which decreased the hydrophobic interaction of preD3 with the phospholipids, reduced the rate by 87%. In contrast, in an isotropic n-hexane solution, there was little difference among the rates of the conversion of preD3, its 3beta-acetate, and 25-hydroxy derivatives to their corresponding vitamin D3 compounds. We also determined rate constants (k) of preD3 <==> vitamin D3 isomerization in liposomes containing phosphatidylcholines with different carbon chain lengths. The rates of the reaction were found to be enhanced as the number of carbons (Cn) in the hydrocarbon chain of the phospholipids increased from 10 to 18. In conclusion, these results support our hypothesis that amphipathic interactions between preD3 and membrane phospholipids stabilize preD3 in its "cholesterol like" cZc-conformer, the only conformer of preD3 that can convert to vitamin D3. The stronger these interactions were, the more preD3 was likely in its cZc conformation at any moment and the faster was the rate of its conversion to vitamin D3.

NASA Discipline Regulatory Physiology↗
NASA NTRS1994

Biomass Burning and the Production of Greenhouse Gases

Biomass burning is a source of greenhouse gases, carbon dioxide, methane, and nitrous oxide. In addition, biomass burning is a source of chemically active gases, including carbon monoxide, nonmethane hydrocarbons, and nitric oxide. These gases, along with methane, lead to the chemical production of tropospheric ozone (another greenhouse gas) as well as control the concentration of the hydroxyl radical, which regulates the lifetime of almost every atmospheric gas. Following biomass burning, biogenic emissions of nitrous oxide, nitric oxide, and methane are significantly enhanced. It is hypothesized that enhanced postburn biogenic emissions of these gases are related to fire-induced changes in soil chemistry and/or microbial ecology. Biomass burning, once believed to be a tropical phenomenon, has been demonstrated by satellite imagery to also be a regular feature of the world's boreal forests. One example of biomass burning is the extensive 1987 fire that destroyed more than 12 million acres of boreal forest in the People's Republic of China and across its border in the Soviet Union. Recent estimates indicate that almost all biomass burning is human-initiated and that it is increasing with time. With the formation of greenhouse and chemically active gases as direct combustion products and a longer-term enhancement of biogenic emissions of gases, biomass burning may be a significant driver for global change.

Levine, Joel S.↗
NASA NTRS1998

A method for the 32P labeling of peptides or peptide nucleic acid oligomers

A novel approach to the radioactive labeling of peptides and PNA oligomers is described. It is based on the conjugation of a deoxynucleoside 3'-phosphate with the terminal amine of the substrate, followed by phosphorylation of the 5'-hydroxyl group of the nucleotide using T4 polynucleotide kinase and [gamma-32P]ATP.

Non-NASA Center↗
NASA NTRS1996

Positive selection moments identify potential functional residues in human olfactory receptors

Correlated mutation analysis and molecular models of olfactory receptors have provided evidence that residues in the transmembrane domains form a binding pocket for odor ligands. As an independent test of these results, we have calculated positive selection moments for the alpha-helical sixth transmembrane domain (TM6) of human olfactory receptors. The moments can be used to identify residues that have been preferentially affected by positive selection and are thus likely to interact with odor ligands. The results suggest that residue 622, which is commonly a serine or threonine, could form critical H-bonds. In some receptors a dual-serine subsite, formed by residues 622 and 625, could bind hydroxyl determinants on odor ligands. The potential importance of these residues is further supported by site-directed mutagenesis in the beta-adrenergic receptor. The findings should be of practical value for future physiological studies, binding assays, and site-directed mutagenesis.

Non-NASA Center↗
NASA NTRS1995

Modeling of a possible conformational change associated with the catalytic mechanism in the hammerhead ribozyme

Here we describe a possible model of the cleavage mechanism in the hammerhead ribozyme. In this model, the 2' hydroxyl of C17 is moved into an appropriate orientation for an in-line attack on the G1.1 phosphate through a change in its sugar pucker from C3' endo to C2' endo. This conformational change in the active site is caused by a change in the uridine turn placing the N2 and N3 atoms of G5 of the conserved core in hydrogen bonding geometry with the N3 and N2 atoms on the conserved G16.2 residue. The observed conformational change in the uridine turn suggests an explanation for the conservation of G5. In the crystal structure of H.M. Pley et al., Nature 372, 68-74 (1994), G5 is situated 5.3A away from G16.2. However, the uridine turn is sufficiently flexible to allow this conformational change with relatively modest changes in the backbone torsion angles (average change of 14.2 degrees). Two magnesium ions were modeled into the active site with positions analogous to those described in the functionally similar Klenow fragment 3'-5' exonuclease (L.S. Beese and T.A. Steitz, EMBO J. 10, 25-33 (1991)), the Group I intron (T.A. Steitz and J.A. Steitz, P.N.A.S. U.S.A. 90, 6498-6502 (1993); R.F. Setlik et al., J. Biomol. Str. Dyn. 10, 945-972 (1993)) and other phosphotransferases. Comparison of this model with one in which the uridine turn conformation was not changed showed that although the changes in the C17 sugar pucker could be modeled, insufficient space existed for the magnesium ions in the active site.

Non-NASA Center↗
NASA NTRS1995

Identification of the in vivo truncation sites at the C-terminal region of alpha-A crystallin from aged bovine and human lens

Total alpha-A crystallin was purified from young versus old lens, followed by digestion with cyanogen bromide. Laser desorption mass spectrometry of the C-terminal fragment demonstrated age-dependent loss of one and five amino acids from the C-terminus of alpha-A crystallin from both bovine and human lens. These results demonstrate specific peptide bonds of alpha-A crystallin are cleaved during the aging process of the normal lens. The C-terminal region is cleaved in two places between the two hydroxyl-containing amino acids present in the sequence -P-S(T)-S-.

Non-NASA Center↗
NASA NTRS1991

Nucleotides as nucleophiles: reactions of nucleotides with phosphoimidazolide activated guanosine

An earlier study of the reaction of phosphoimidazolide activated nucleosides (ImpN) in aqueous phosphate buffers indicated two modes of reaction of the phosphate monoanion and dianion. The first mode is catalysis of the hydrolysis of the P-N bond in ImpN's which leads to imidazole and nucleoside 5'-monophosphate. The second represents a nucleophilic substitution of the imidazole to yield the nucleoside 5'-diphosphate. This earlier study thus served as a model for the reaction of ImpN with nucleoside monophosphates (pN) because the latter can be regarded as phosphate derivatives. In the present study we investigated the reaction of guanosine 5'-phosphate-2-methylimidazolide, 2-MeImpG, in the presence of pN (N = guanosine, adenosine and uridine) in the range 6.9 less than or equal to pH less than or equal to 7.7. We observed that pN's do act as nucleophiles to form NppG, and as general base to enhance the hydrolysis of the P-N bond in 2-MeImpG, i.e. pN show the same behavior as inorganic phosphate. The kinetic analysis yields the following rate constants for the dianion pN2-: knpN = 0.17 +/- 0.02 M-1 h-1 for nucleophilic attack and khpN = 0.11 +/- 0.07 M-1 h-1 for general base catalysis of the hydrolysis. These rate constants which are independent of the nucleobase compare with kp.2 = 0.415 M-1 h-1 and khp2. = 0.217 M-1 h-1 for the reactions of HPO4(2-). In addition, this study shows that under conditions where pN presumably form stacks, the reaction mechanism remains unchanged although in quantitative terms stacked pN are somewhat less reactive. Attack by the 2'-OH and 3'-OH groups of the ribose moiety in amounts greater than or equal to 1% is not observed; this is attributed to the large difference in nucleophilicity in the neutral pH range between the phosphate group and the ribose hydroxyls. This nucleophilicity rank is not altered by stacking.

NASA Discipline Exobiology↗
NASA NTRS2004

High Temperature Decomposition of Hydrogen Peroxide

Nitric oxide (NO) is oxidized into nitrogen dioxide (NO2) by the high temperature decomposition of a hydrogen peroxide solution to produce the oxidative free radicals, hydroxyl and hydropemxyl. The hydrogen peroxide solution is impinged upon a heated surface in a stream of nitric oxide where it decomposes to produce the oxidative free radicals. Because the decomposition of the hydrogen peroxide solution occurs within the stream of the nitric oxide, rapid gas-phase oxidation of nitric oxide into nitrogen dioxide occurs.

Clyde F. Parrish↗
NASA NTRS1995

Cooperative Testing of Rocket Injectors That Use Gaseous Oxygen and Hydrogen

Gaseous oxygen and hydrogen propellants used in a special engine energy cycle called Full-Flow Staged Combustion are believed to significantly increase the lifetime of a rocket engine's pumps. The cycle can also reduce the operating temperatures of the engine. Improving the lifetime of the hardware reduces its overall maintenance and operations costs, and is critical to reducing costs for the joint NASA/industry Reusable Launch Vehicle (RLV). The work in this project will demonstrate the performance and lifetime of one-element and many-element combustors with gaseous O2/H2 injectors. This work supporting the RLV program is a cooperative venture of the NASA Lewis Research Center, the NASA Marshall Space Flight Center, Rocketdyne, and the Pennsylvania State University. Information about gas-gas rocket injector performance with O2/H2 is very limited. Because of this paucity of data, new testing is needed to improve the knowledge base for testing and designing new injectors for the RLV and to improve computer models that predict the combusting gas flows of new injector designs. Therefore, detailed observations and measurements of the combusting flow from many-element injectors in a rocket engine are being sought. These observations and measurements will be done with three different tools: schlieren photography, ultraviolet imaging, and Raman spectroscopy. The schlieren system will take photos of the density differences in combusting flow, the ultraviolet movies will determine the location of the hydroxyl (OH) radical in the combustion flow, and the Raman spectroscopic measurements will provide the combustion temperature and amount of water (H2O), hydrogen (H2), and oxygen (O2) in the combustor. Marshall is providing overall program management, design and computational fluid dynamics (CFD) analyses, as well as funding for the work at Penn State. An existing, windowed combustor and several injectors will be provided by Rocketdyne--two injectors for the initial screening tests and one with an optimized design based on the best design found in the screening tests. Lewis will provide a nozzle and several injectors for the screening test program. The configuration of the injectors will be based on a design chosen by all the participants, and their elements will be based on the coaxial and impinging flow. Lewis also will provide the instrumentation for the flow-field measurements: schlieren, ultraviolet imaging, and Raman spectroscopy. In addition, thermocouples will measure heat flow on the injector face. Other traditional measurements of rocket performance will be made as well: chamber pressure, mass flow of each propellant, purge flow, and the barrier cooling gas flow. Penn State will conduct single-element testing with the injector elements from both the Rocketdyne and the jointly designed injectors. A wide variety of traditional and nontraditional injector designs will be tested in this program. The results will be valuable in computational fluid dynamics code validation and overall rocket combustion efficiency measurements. Correlations between combustion efficiency, laser measurements of species, and ultraviolet and visible light photography will also be made. Thus far, several different single-element injectors have been tested at Penn State and Lewis. The experimental setup of a rocket engine with a viewing window is shown. The combusting flow is shown. The results are helping engineers design the many element injectors.

Source record↗
NASA NTRS2005

Abundance and Speciation of Water and Sulfate at Gusev Crater and Meridiani Planum

A major science goal of the Mars Exploration Rover (MER) mission is to search for evidence of water activity, and direct mineralogical evidence for aqueous activity has been reported for Meridiani Planum in the form of the iron sulfate hydroxide mineral jarosite and at Gusev crater in the form of goethite. The Spirit and Opportunity rovers have each collected 110+ Moessbauer (MB) and 75+ Alpha Particle X-Ray Spectrometer (APXS) spectra from Gusev crater and Meridiani Planum [1 - 4]. In this abstract, we use mineralogical and elemental data, primarily from the Moessbauer and APXS instruments, to infer the speciation and estimate the abundance of sulfate and water (as either the H2O molecule or the hydroxyl anion) at Gusev crater and Meridiani Planum. Throughout the abstract, we adopt a format for mineral formulas that shows water explicitly rather than the usual practice of structure-based formulas (e.g., for goethite we write Fe2O3xH2O instead of FeOOH).

Ming, D. W.↗
NASA NTRS2005

Negative Searches for Evidence of Aqueous Alteration on Asteroid Surfaces

Small bodies in the Solar System preserve evidence of the processes occurring during early Solar System formation, unlike the larger planets that undergo continuous churning of their surfaces. We study these bodies to understand what processes affected different stages of Solar System formation. The action of aqueous alteration (the alteration of material by the interaction of that material with liquid formed by the melting of incorporated ice) of near-subsurface material has been inferred to occur on many asteroids based on the spectrophotometric evidence of phyllosilicates and iron alteration minerals. The definitive indication of aqueous alteration is the 3.0- micron absorption feature attributed to structural hydroxyl (OH) and interlayer and adsorbed water (H2O) in phyllosilicates (clays) (hereafter water of hydration). A weak absorption feature centered near 0.7 microns attributed to an Fe (2+) right arrow Fe (3+) charge transfer transition in oxidized iron in phyllosilicates has been observed in the reflectance spectra and photometry of approximately 50% of the main-belt C-class asteroids. An approximately 85% correlation between this 0.7- micron feature and the 3.0- micron water of hydration absorption feature was found among the low-albedo asteroids. The feature is usually centered near 0.68 microns in asteroid spectra, and ranges in wavelength from approximately 0.57 to 0.83 microns. Serendipitously, three of the Eight Color Asteroid Survey filters the v (0.550 microns), w (0.701 microns), and x (0.853 microns)-bracket this feature well, and can be used to determine the presence of this feature in the reflectance properties of an asteroid, and probe the aqueous alteration history of larger samples of asteroid data. Two efforts to search for evidence of aqueous alteration based on the presence of this 0.7- micron absorption feature are presented here.

Vilas, F.↗
NASA NTRS1998

Droplet Combustion Experiment

Liquid fuel combustion provides a major portion of the world's energy supply. In most practical combustion devices, liquid burns after being separated into a droplet spray. Essential to the design of efficient combustion systems is a knowledge of droplet combustion behavior. The microgravity environment aboard spacecraft provides an opportunity to investigate the complex interactions between the physical and chemical combustion processes involved in droplet combustion without the complications of natural buoyancy. Launched on STS-83 and STS-94 (April 4 and July 1, 1997), the Droplet Combustion Experiment (DCE) investigated the fundamentals of droplet combustion under a range of pressures (0.25 to 1 atm), oxygen mole fractions (<0.5), and droplet sizes (1.5 to 5 mm). Principal DCE flight hardware features were a chamber to supply selected test environments, the use of crew-inserted bottles, and a vent system to remove unwanted gaseous combustion products. The internal apparatus contained the droplet deployment and ignition mechanisms to burn single, freely deployed droplets in microgravity. Diagnostics systems included a 35-mm high-speed motion picture camera (see the following sequence of photos) with a backlight to photograph burning droplets and a camcorder to monitor experiment operations. Additional diagnostics included an ultraviolet-light-sensitive CCD (charge couple discharge) camera to obtain flame radiation from hydroxyl radicals (see the final figure) and a 35-mm SLR (single-lens-reflex) camera to obtain color still photographs of the flames.

Nayagam, Vedha↗
NASA NTRS2004

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↗
NASA NTRS2004

Nano-casted Metal Oxide Aerogels as Dual Purpose Structural Components for Space Exploration

NASA missions and space exploration rely on strong, ultra lightweight materials. Such materials are needed for building up past and present space vehicles such as the Sojourner Rover (1997) or the two MERs (2003), but also for a number of components and/or systems including thermal insulators, Solar Sails, Rigid Aeroshells, and Ballutes. The purpose of my internship here at Glenn Research Center is to make dual purpose materials; materials that in addition to being lightweight have electronic, photophysical and magnetic properties and, therefore, act as electronic components and sensors as well as structural components. One type of ultra lightweight material of great interest is aerogels, which have densities ranging from 0.003 g/cc to 0.8 g/cc . However, aerogels are extremely fragile and, as a result, have limited practical applications. Recently, Glenn Research Center has developed a process of nano-casting polymers onto the inorganic network of silica-based aerogels increasing the strength 300 fold while only increasing the density 3 fold. By combining the process of nano-casting polymers with inorganic oxide networks other than silica, we are actively pursuing lightweight dual purpose materials. To date, thirty different inorganic oxide aerogels have been prepared using either standard sol-gel chemistry or a non-alkoxide method involving metal chloride precursors and an epoxide; epichlorohydrin, propylene oxide or trimethylene oxide, as proton scavengers. More importantly, preliminary investigations show that the residual surface hydroxyl groups on each of these inorganic oxide aerogels can be successfully crosslinked with urethane. In addition to characterizing physical and mechanical properties such as density, strength and flexibility, each of these metal oxide aerogels are being characterized for thermal and electronic conductivity and magnetic and optical properties.

Vassilaras, Plousia E.↗