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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.

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At least 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
NASA NTRS1992

Utilization of peptide carrier system to improve intestinal absorption: targeting prolidase as a prodrug-converting enzyme

The feasibility of targeting prolidase as a peptide prodrug-converting enzyme has been examined. The enzymatic hydrolysis by prolidase of substrates for the peptide transporter L-alpha-methyldopa-pro and several dipeptide analogues without an N-terminal alpha-amino group (phenylpropionylproline, phenylacetylproline, N-benzoylproline, and N-acetylproline) was investigated. The Michaelis-Menten parameters Km and Vmax for L-alpha-methyldopa-pro are 0.09 +/- 0.02 mM and 3.98 +/- 0.25 mumol/min/mg protein, respectively. However, no hydrolysis of the dipeptide analogues without an N-terminal alpha-amino group is observed, suggesting that an N-terminal alpha-amino group is required for prolidase activity. These results demonstrate that prolidase may serve as a prodrug-converting enzyme for the dipeptide-type prodrugs, utilizing the peptide carrier for transport of prodrugs into the mucosal cells and prolidase, a cytosolic enzyme, to release the drug. However, a free alpha-amino group appears to be necessary for prolidase hydrolysis.

NASA Discipline Regulatory Physiology↗
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 NTRS2015

Martian Superoxide and Peroxide O2 Release (OR) Assay: A New Technology for Terrestrial and Planetary Applications

This study presents an assay for the detection and quantification of soil metal superoxides and peroxides in regolith and soil. The O2 release (OR) assay is based on the enzymatic conversion of the hydrolysis products of metal oxides to O2, and their quantification by an O2 electrode based on the stoichiometry of the involved reactions: The intermediate product O2 from the hydrolysis of metal superoxides is converted by cytochrome c to O2, and also by superoxide dismutase (SOD) to 1/2 mol O2 and 1/2 mol H2O2, which is then converted by catalase (CAT) to 1/2 mol O2. The product H2O2 from the hydrolysis of metal peroxides and hydroperoxides is converted to 1/2 mol O2 by CAT. The assay-method was validated in a sealed sample chamber using a liquid-phase Clark-type O2 electrode with known concentrations of O2 and H2O2, and with commercial metal superoxide and peroxide mixed with Mars analogue Mojave and Atacama Desert soils. Carbonates and perchlorates, both present on Mars, do not interfere with the assay. The assay lower limit of detection, using luminescence quenching/optical sensing O2-electrodes, is 1 nmol O2 cm(exp. -3) or better. The activity of the assay enzymes SOD and cytochrome c was unaffected up to 6 Gy exposure by gamma-radiation, while CAT retained 100% and 40% of its activity at 3 and 6 Gy, respectively, demonstrating the suitability of these enzymes for planetary missions, e.g., in Mars or Europa.

soil metal superoxides and peroxides↗
NASA NTRS2022

CryoEM Structures of the Nitrogenase Complex During Catalytic Turnover

The enzyme nitrogenase couples adenosine triphosphate (ATP) hydrolysis to the multi-electron reduction of atmospheric dinitrogen into ammonia. Despite extensive research, the mechanistic details of ATP-dependent energy transduction and dinitrogen reduction by nitrogenase are not well understood, requiring new strategies to monitor its structural dynamics during catalytic action. Here we report the cryogenic electron microscopic interrogation of the nitrogenase complex under enzymatic turnover conditions, which has enabled the structural characterization of the nitrogenase reaction intermediates at high resolution for the first time. Our structures show that asymmetry governs all aspects of nitrogenase mechanism including ATP hydrolysis, protein-protein interactions, and catalysis. Furthermore, they reveal several previously unobserved, mechanistically relevant conformational changes near the catalytic iron-molybdenum cofactor that are correlated with the nucleotide-hydrolysis state of the enzyme.

Hannah L. Rutledge↗
NASA NTRS2022

Structures of the Nitrogenase Complex Prepared Under Catalytic Turnover Conditions

The enzyme nitrogenase couples adenosine triphosphate (ATP) hydrolysis to the multielectron reduction of atmospheric dinitrogen into ammonia. Despite extensive research, the mechanistic details of ATP-dependent energy transduction and dinitrogen reduction by nitrogenase are not well understood, requiring new strategies to monitor its structural dynamics during catalytic action. Here, we report cryo–electron microscopy structures of the nitrogenase complex prepared under enzymatic turnover conditions. We observe that asymmetry governs all aspects of the nitrogenase mechanism, including ATP hydrolysis, protein-protein interactions, and catalysis. Conformational changes near the catalytic iron-molybdenum cofactor are correlated with the nucleotide-hydrolysis state of the enzyme.

Hannah L. Rutledge↗
NASA NTRS2000

Ozonation and alkaline-peroxide pretreatment of wheat straw for Cryptococcus curvatus fermentation

Crop residues in an Advanced Life Support System (ALS) contain many valuable components that could be recovered and used. Wheat is 60% inedible, with approximately 90% of the total sugars in the residue cellulose and hemicellulose. To release these sugars requires pretreatment followed by enzymatic hydrolysis. Cryptococcus curvatus, an oleaginous yeast, uses the sugars in cellulose and hemicellulose for growth and production of storage triglycerides. In this investigation, alkaline-peroxide and ozonation pretreatment methods were compared for their efficiency to release glucose and xylose to be used in the cultivation of C. curvatus. Leaching the biomass with water at 65 degrees C for 4 h prior to pretreatment facilitated saccharification. Alkaline-peroxide and ozone pretreatment were almost 100% and 80% saccharification efficient, respectively. The sugars derived from the hydrolysis of alkaline-peroxide-treated wheat straw supported the growth of C. curvatus and the production of edible single-cell oil.

Non-NASA Center↗
NASA NTRS2003

Development of a pilot system for converting sweet potato starch into glucose syrup

Sweet potato has been chosen as one of NASA's crops to support human beings in future space missions. One of the possible uses is to make syrup that can be used as a general sweetener. In this work a simple engineering system for converting sweet potato starch into glucose syrup was studied on a laboratory scale. The system comprises the following main units: a blender, continuous stirred tank reactor (CSTR), centrifugal and vacuum filters, deionization column and vacuum evaporator. The system was tested by carrying out conversion processes from fresh sweet potato roots. The roots were pealed, sliced, homogenized, heated and hydrolyzed by diastase of malt and Dextrozyme C (Novo Nordisk BioChem, North America, Inc.) enzymes in the CSTR. After hydrolysis the slurry was filtered, de-ionized and concentrated to get glucose syrup. The performance of the system was evaluated based on the quality of the conversion. The main factor was the level of reducing sugars except for the deionization where ash content and color were the main factors. Through careful control of the system units, good heating performance in the CSTR was obtained and the hydrolysis process attained sufficient conversion. The filtration process that incorporated the centrifuge was faster than when it was by-passed to the vacuum filter but losses in sugars were higher. Deionization removed more than 90% of the ash and reduced pigmentation, with probable insignificant losses in sugars during the deionization process. Recovery levels when the centrifuge was used and when it was by-passed could reach about 65% and 78%, respectively. These correspond to reducing sugar concentration of 259 and 310 mg/ml in 150-ml syrups from 300 g of sweet potatoes in each process. However, from concentration trials, syrups with volumes of 100 and 70 ml with the respective dextrose equivalence of 281 and 213 mg/ml were obtained. The syrups obtained were brownish in color and the process that employed centrifugal filtration gave a product with color that resembled the original color of the sweet potatoes. Further work is required to improve the overall system performance.

Non-NASA Center↗
NASA NTRS1984

Determination of the gram-positive bacterial content of soils and sediments by analysis of teichoic acid components

Many gram-positive bacteria form substituted polymers of glycerol and ribitol phosphate esters known as teichoic acids. Utilizing the relative specificity of cold concentrated hydrofluoric acid in the hydrolysis of polyphosphate esters it proved possible to quantitatively assay the teichoic acid-derived glycerol and ribitol from gram-positive bacteria added to various soils and sediments. The lipids are first removed from the soils or sediments with a one phase chloroform-methanol extraction and the lipid extracted residue is hydrolyzed with cold concentrated hydrofluoric acid. To achieve maximum recovery of the teichoic acid ribitol, a second acid hydrolysis of the aqueous extract is required. The glycerol and ribitol are then acetylated after neutralization and analyzed by capillary gas-liquid chromatography. This technique together with measures of the total phospholipid, the phospholipid fatty acid, the muramic acid and the hydroxy fatty acids of the lipopolysaccharide lipid A of the gram-negative bacteria makes it possible to describe the community structure environmental samples. The proportion of gram-positive bacteria measured as the teichoic acid glycerol and ribitol is higher in soils than in sediments and increases with depth in both.

Ribitol/analogs & derivatives↗
NASA NTRS1995

An efficient prebiotic synthesis of cytosine and uracil

In contrast to the purines, the routes that have been proposed for the prebiotic synthesis of pyrimidines from simple precursors give only low yields. Cytosine can be synthesized from cyanoacetylene and cyanate; the former precursor is produced from a spark discharge in a CH4/N2 mixture and is an abundant interstellar molecule. But this reaction requires relatively high concentrations of cyanate (> 0.1 M), which are unlikely to occur in aqueous media as cyanate is hydrolysed rapidly to CO2 and NH3. An alternative route that has been explored is the reaction of cyanoacetaldehyde (formed by hydrolysis of cyanoacetylene) with urea. But at low concentrations of urea, this reaction produces no detectable quantities of cytosine. Here we show that in concentrated urea solution--such as might have been found in an evaporating lagoon or in pools on drying beaches on the early Earth--cyanoacetaldehyde reacts to form cytosine in yields of 30-50%, from which uracil can be formed by hydrolysis. These reactions provide a plausible route to the pyrimidine bases required in the RNA world.

Non-NASA Center↗
NASA NTRS1972

Compounds of the organogenic elements in Apollo 11 and 12 lunar samples - A review.

Investigations of low molecular weight compounds of the organogenic elements on lunar samples are reviewed. The three general techniques of vacuum pyrolysis, acid hydrolysis, and crushing have been employed by most investigators. Vacuum pyrolysis of lunar fines produce a variety of gaseous species which are either: (1) indigenous, (2) solar wind products and/or (3) chemical reaction products of mineral phases found in the lunar samples. Acid hydrolysis of lunar fines using deuterium-labeled acids yields evidence for indigenous methane and ethane. Methane and ethane found in the lunar fines are largely derived from the solar wind with only trace amounts indigenous to the samples. Crushing experiments with lunar fines and breccias produce methane, ethane, hydrogen, nitrogen, hydrogen sulfide and the rare gases.

Gibson, E. K., Jr.↗
NASA NTRS1973

Techniques for the analysis of gases sequentially released from lunar samples

Description of two methods for the analysis of light gases that are sequentially evolved from 2 to 10 mg of lunar sample. A hydrofluoric acid hydrolysis of lunar material is achieved by repeated exposure of the sample to hydrogen fluoride. In the second technique, gases are evolved from lunar samples by the stepwise heating of these samples to 1400 C. The gases evolved by either hydrolysis or pyrolysis are analyzed in a gas chromatographic system using a helium ionization detector. The sensitivities of this detector for the gases, as analyzed, range from 20 picograms/sec for hydrogen to 0.2 picogram/sec for carbon dioxide.

Desmarais, D. J.↗
NASA NTRS1974

Carbon, nitrogen and sulfur in lunar fines 15012 and 15013 - Abundances, distributions and isotopic compositions

Lunar fines 15012,16 and 15013,3 were analyzed by stepwise pyrolysis and acid hydrolysis as well as complete combustion in oxygen to determine carbon, nitrogen and sulfur. In addition, hydrogen was analysed during pyrolysis as well as during hydrolysis. By comparison of the distribution frequencies of C, N, S, H2 and Fe with He-4, considered to have arisen from solar wind contribution, it is concluded that nitrogen and hydrogen have largely a solar origin. Carbon has a significant solar contribution, and metallic iron may have resulted from solar wind interaction with ferrous minerals on the lunar surface. Sulfur probably has a predominantly lunar origin. There is no direct evidence for meteorotic contribution to these samples. Solar wind interaction also has a marked effect on the stable isotope distribution of C-13/C-12, N-15/N-14, and S-34/S-32. In all cases, the heavy isotope was most enriched in the smallest grain-size fraction.

Chang, S.↗
NASA NTRS1975

Oligonucleotide synthesis catalyzed by the Zn/2+/ ion

Results of experiments are reported in which Zn(2+) ion catalyzed the formation of oligonucleotides from nucleoside phosphorimidazolides in aqueous solution, even in the absence of a template. Specifically, the imidazolides (ImpU or ImpA) polymerized to form ImpApA, and pApA, pApApA, and pApApApA, or the analogous uracil compounds. In addition, the expected hydrolysis products of the hydrolysis of ImpA were formed (pA, imidazole). Judging from the ratio of pA(n) over pA (with and without zinc ion), this ion increased the efficiency of phosphodiester-bond formation by up to 10 times. Possible mechanisms for the reaction are tentatively proposed.

Sawai, H.↗
NASA NTRS1975

Cyanogen induced phosphorylation of D-fructose

It has been demonstrated that a phosphorylated sugar, identified as alpha-D-fructopyranose, can be formed as the result of cyanogen-induced phosphorylation of D-fructose at pH 8.8. The product was isolated from barium and cyclohexylammonium salts and identified on the basis of its chromatographic and electrophoretic properties, its lability to hydrolysis by alkaline phosphatase, the rate of its acid-catalyzed hydrolysis, and the results of periodate oxidation and optical rotatory measurements. These results support the suggestion that the cyanogen-induced phosphorylation of free sugars could be a possible process for formation of sugar phosphates under prebiotic conditions (Halman et al., 1969).

Degani, CH.↗
NASA NTRS1976

Amino acid precursors in lunar fines - Limits to the contribution of jet exhaust

A sample of lunar fines collected at a maximum distance, 6.5 km, from the descent engine on Apollo 17 has been analyzed for total amino acids obtainable by hydrolysis of aqueous extracts. The minimum amounts of amino acids, calculated for a disk of 6 km radius are 10,000 to 100,000 times those which could be contributed by the lunar module jet exhaust, on the basis of conservatively limiting assumptions. The amino acids thus obtained are not explainable as due to chemical or biological contamination; their source is accordingly inferred as lunar. Under the conditions of hydrolysis of lunar extracts, cyanide is found to be converted, almost exclusively to glycine, to an extent of 0.0001.

Fox, S. W.↗
NASA NTRS1978

HCN - A plausible source of purines, pyrimidines and amino acids on the primitive earth

Dilute (0.1 M) solutions of HCN condense to oligomers at pH 9.2, and hydrolysis of these oligomers yields 4,5-dihydroxypyrimidine, orotic acid, 5-hydroxyuracil, adenine, 4-aminoimidazole-5-carboxamide, and amino acids. It is suggested that the three main classes of nitrogen-containing biomolecules - purines, pyrimidines, and amino acids may have originated from HCN on the primitive earth. It is also suggested that the presence of orotic acid and 4-aminoimidazole-5-carboxamide might indicate that contemporary biosynthetic pathways for nucleotides evolved from the compounds released on hydrolysis of HCN oligomers.

Ferris, J.-P.↗
NASA NTRS1981

Development of silane-hydrolysate binder for UV-resistant thermal control coatings

Detailed characterizaton and formulation studies were performed on a methyltriakoxysilane hydrolysate as a binder for thermal control coatings. The binder was optimized by varying hydrolysis temperature, time, catalyst type, and water concentration. The candidate coating formulations, based on this binder with TiO2 pigment, were optimized via a detailed series of sprayed test panels that included the parameters of binder/pigment ratio, ethanol content, pigment particle size, coating thickness and cure conditions. A typical optimized coating was prepared by acetic acid catalyzed hydrolysis of methyltriethoxysilane with 3.25 mol-equivalents of water over a 24 hour period at room temperature. The resulting hydrolysate was directly mixed with pre-milled TiO2 (12 grams pigment/26 grams binder) to yield a sprayable consistency. Panels were sprayed to result in a nominal cure coating thickness of 2 mils. Cure was affected by air drying for 24 hr at room temperature plus 72 hr at 150 F. These coatings are typically extremely tough and abrasion-resistant, with an absorptance (alpha) of 0.20 and emittance (e) of 0.89. No significant coating damage was observed in the mandrel bend test, even after exposure to thermal cycling from -160 to 160 F. Vacuum exposure of the coatings for 930 hours at 1 equivalent UV sun resulted in no visible degradation and no significant increase in absorptance.

Patterson, W. J.↗
NASA NTRS1981

Structural studies on HCN oligomers

NMR spectral studies on the HCN oligomers suggest the presence of carboxamide and urea groupings. The release of CO2, H2O, HCN, CH3CN, HCONH2 and pyridine on pyrolysis is consistent with the presence of these groupings as well as carboxylic acid groups. No basic primary amine groupings could be detected with fluorescamine. Hydrazinolysis of the HCN oligomers releases 10% of the amino acids normally released by acid hydrolysis. The oligomers give a positive biuret test but this is not due to the presence of peptide bonds. There is no conclusive evidence for the presence of peptide bonds in the HCN oligomers. No diglycine was detected on partial hydrolysis of the HCN oligomers at pH 8.5 suggesting that HCN oligomers were not a source of prebiotic peptides.

Ferris, J. P.↗