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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 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
NASA NTRS1972

Detection of non-protein amino acids in the presence of protein amino acids. II.

Studies conducted with the JEOL 5AH amino acid analyzer are described. This instrument makes possible the programming of the chromatographic process. Data are presented showing the separations of seventeen non-protein amino acids in the presence of eighteen protein amino acids. It is pointed out that distinct separations could be obtained in the case of a number of chemically similar compounds, such as ornithine and lysine, N-amidino alanine and arginine, and iminodiacetic acid and S-carboxymethyl cysteine and aspartic acid.

Shapshak, P.↗
NASA NTRS1983

Complexes of polyadenylic acid and the methyl esters of amino acids

A study of amino acid methyl esters binding to polyadenylic acid supports the theory that the genetic code originated through weak but selective affinities between amino acids and nucleotides. NMR, insoluble complex analysis, and ultraviolet spectroscopy are used to illustrate a correlation between the hydrophybicities of A amino acids and their binding constants, which, beginning with the largest, are in the order of Phe (having nominally a hydrophobic AAA anticodon), Ile, Leu, Val and Gly (having a hydrophilic anticodon with no A). In general, the binding constants are twice the values by Reuben and Polk (1980) for monomeric AMP, which suggests that polymer amino acids are interacting with only one base. No real differences are found betwen poly A binding for free Phe, Phe methyl ester or Phe amide, except that the amide value is slightly lower.

Khaled, M. A.↗
NASA NTRS1985

Amino acids of the Murchison meteorite. II - Five carbon acyclic primary beta-, gamma-, and delta-amino alkanoic acids

The five-carbon acyclic primary beta, gamma, and delta amino alkanoic acids of the Murchison meteorite are studied using gas chromatography-mass spectrometry and ion exchange chromatography. The chromatograms reveal that alpha is the most abundant monoamino alkanoic acid followed by gamma and beta, and an exponential increase in the amount of amino acid is observed as the carbon number increases in the homologous series. The influence of frictional heating, spontaneous thermal decomposition, and radiation of the synthesis of amino acids is examined. The data obtained support an amino acid synthesis process involving random combination of single-carbon precursors.

Cronin, J. R.↗
NASA NTRS1987

Dicarboxylic acids generated by thermal alteration of kerogen and humic acids

Significant amounts (up to 2 percent of organic geopolymers) of low-molecular-weight (LMW) dicarboxylic acids (C2-C10) have been detected during thermal alteration (270 C, 2 h) of kerogens and humic acids isolated from young or ancient lithified sediments. Their distribution is characterized by the predominance of oxalic acid followed by succinic, fumaric, and methylsuccinic acids. These acids are probably released by the breakdown of macromolecular structures, which have incorporated biogenic organic compounds, including diacids, during early digenesis in sediments. Because of their reactivity, LMW diacids may play geochemically important roles under natural conditions.

Kawamura, Kimitaka↗
NASA NTRS1992

A comparison of chromic acid and sulfuric acid anodizing

Because of federal and state mandates restricting the use of hexavalent chromium, it was deemed worthwhile to compare the corrosion protection afforded 2219-T87 aluminum alloy by both Type I chromic acid and Type II sulfuric acid anodizing per MIL-A-8625. Corrosion measurements were made on large, flat 2219-T87 aluminum alloy sheet material with an area of 1 cm(exp 2) exposed to a corrosive medium of 3.5-percent sodium chloride at pH 5.5. Both ac electrochemical impedance spectroscopy and the dc polarization resistance techniques were employed. The results clearly indicate that the corrosion protection obtained by Type II sulfuric acid anodizing is superior, and no problems should result by substituting Type II sulfuric acid anodizing for Type I chromic acid anodizing.

Danford, M. D.↗
NASA NTRS1998

Prebiotic Amino Acid Thioester Synthesis: Thiol-Dependent Amino Acid Synthesis from Formose substrates (Formaldehyde and Glycolaldehyde) and Ammonia

Formaldehyde and glycolaldehyde (substrates of the formose autocatalytic cycle) were shown to react with ammonia yielding alanine and homoserine under mild aqueous conditions in the presence of thiol catalysts. Since similar reactions carried out without ammonia yielded alpha-hydroxy acid thioesters, the thiol-dependent synthesis of alanine and homoserine is presumed to occur via amino acid thioesters-intermediates capable of forming peptides. A pH 5.2 solution of 20 mM formaldehyde, 20 mM glycolaldehyde, 20 mM ammonium chloride, 23 mM 3-mercaptopropionic acid, and 23 mM acetic acid that reacted for 35 days at 40 C yielded (based on initial formaldehyde) 1.8% alanine and 0.08% homoserine. In the absence of thiol catalyst, the synthesis of alanine and homoserine was negligible. Alanine synthesis required both formaldehyde and glycolaldehyde, but homoserine synthesis required only glycolaldehyde. At 25 days the efficiency of alanine synthesis calculated from the ratio of alanine synthesized to formaldehyde reacted was 2.1%, and the yield (based on initial formaldehyde) of triose and tetrose intermediates involved in alanine and homoserine synthesis was 0.3 and 2.1%, respectively. Alanine synthesis was also seen in similar reactions containing only 10 mM each of aldehyde substrates, ammonia, and thiol. The prebiotic significance of these reactions that use the formose reaction to generate sugar intermediates that are converted to reactive amino acid thioesters is discussed.

Weber, Arthur L.↗
NASA NTRS1999

Formation of Amino Acid Thioesters for Prebiotic Peptide Synthesis: Catalysis By Amino Acid Products

The origin of life can be described as a series of events in which a prebiotic chemical process came increasingly under the control of its catalytic products. In our search for this prebiotic process that yielded catalytic takeover products (such as polypeptides), we have been investigating a reaction system that generates peptide-forming amino acid thioesters from formaldehyde, glycolaldehyde, and ammonia in the presence of thiols. As shown below, this model process begins by aldol condensation of formaldehyde and glycolaldehyde to give trioses and releases. These sugars then undergo beta-dehydration yielding their respective alpha-ketoaldehydes. Addition of ammonia to the alpha-ketoaldehydes yields imines which can either: (a) rearrange in the presence of thesis to give amino acid thioesters or (be react with another molecule of aldehyde to give imidazoles. This 'one-pot' reaction system operates under mild aqueous conditions, and like modem amino acid biosynthesis, uses sugar intermediates which are converted to products by energy-yielding redox reactions. Recently, we discovered that amino acids, such as the alanine reaction product, catalyze the first and second steps of the process. In the presence of ammonia the process also generates other synthetically useful products, like the important biochemical -- pyruvic acid.

Weber, Arthur L.↗
NASA NTRS1987

Preparation of 7-hydroxy-2-oxoindolin-3-ylacetic acid and its [13C2], [5-n-3H], and [5-n-3H]-7-O-glucosyl analogues for use in the study of indol-3-ylacetic acid catabolism

An improved synthesis of 7-hydroxy-2-oxoindolin-3-ylacetic acid via the base-induced condensation reaction between oxalate esters and 7-benzyloxyindolin-2-one is described. 7-Benzyloxyindolin-2-one was prepared in four steps and 50% overall yield from 3-hydroxy-2-nitrotoluene. The yield of the title compound from 7-benzyloxyindolin-2-one was 56%. This route was used to prepare 7-hydroxy-2-oxoindolin-3-yl[13C2]acetic acid in 30% yield from [13C2]oxalic acid dihydrate. The method could not be extended to the preparation of the corresponding [14C2]-compound. However, an enzyme preparation from Zea mays roots catalysed the conversion of carrier-free [5-n-3H]indol-3-ylacetic acid with a specific activity of 16.7 Ci mmol-1 to a mixture of 7-hydroxy-2-oxo[5-n-3H]indolin-3-ylacetic acid and its [5-n-3H]-7-O-glucoside in ca. 3 and 40% radiochemical yield respectively. The glucoside was converted into the 7-hydroxy compound in 80% yield by means of beta-glucosidase.

Non-NASA Center↗
NASA NTRS1999

Energetics and kinetics of the prebiotic synthesis of simple organic acids and amino acids with the FeS-H2S/FeS2 redox couple as reductant

The thermodynamics of the FeS-H2S/FeS2 redox couple and a select number of reactions critical to the synthesis of simple carboxylic acids and amino acids have been evaluated as a function of temperature. This thermodynamic evaluation shows that the reducing power of the FeS-H2S/FeS2 redox couple decreases drastically with temperature. By contrast the equilibria describing the reduction of CO2 and the formation of simple carboxylic acids and amino acids require an increasingly higher reducing power with temperature. Given these two opposite trends, the thermodynamic driving force for CO2 reduction and amino acid formation with the FeS-H2S/FeS2 redox couple as reductant diminishes with increasing temperature. An evaluation of the mechanism of CO2 reduction by the FeS-H2S/FeS2 couple suggests that the electron transfer from pyrrhotite to CO2 is hindered by a high activation energy, even though the overall reaction is thermodynamically favorable. By comparison the electron transfer from pyrrhotite to either CS2, CO, or HCOOH are far more facile. This theoretical analysis explains the results of experimental work by Keefe et al. (1995), Heinen and Lauwers (1996) and Huber and Wachtershauser (1997). The implication is that a reaction sequence involving the reduction of CO2 with the FeS-H2S/FeS2 couple as reductant is unlikely to initiate a proposed prebiotic carbon fixation cycle (Wachtershauser, 1988b; 1990b, 1990a, 1992, 1993).

Non-NASA Center↗
NASA NTRS1992

Preferential hydrophobic interactions are responsible for a preference of D-amino acids in the aminoacylation of 5'-AMP with hydrophobic amino acids

We have studied the chemistry of aminoacyl AMP to model reactions at the 3' terminus of aminoacyl tRNA for the purpose of understanding the origin of protein synthesis. The present studies relate to the D, L preference in the esterification of 5'-AMP. All N-acetyl amino acids we studied showed faster reaction of the D-isomer, with a generally decreasing preference for D-isomer as the hydrophobicity of the amino acid decreased. The beta-branched amino acids, Ile and Val, showed an extreme preference for D-isomer. Ac-Leu, the gamma-branched amino acid, showed a slightly low D/L ratio relative to its hydrophobicity. The molecular basis for these preferences for D-isomer is understandable in the light of our previous studies and seems to be due to preferential hydrophobic interaction of the D-isomer with adenine. The preference for hydrophobic D-amino acids can be decreased by addition of an organic solvent to the reaction medium. Conversely, peptidylation with Ac-PhePhe shows a preference for the LL isomer over the DD isomer.

Non-NASA Center↗
NASA NTRS2017

Smectite Formation in the Presence of Sulfuric Acid: Implications for Acidic Smectite Formation on Early Mars

The excess of orbital detection of smectite deposits compared to carbonate deposits on the martian surface presents an enigma because smectite and carbonate formations are both favored alteration products of basalt under neutral to alkaline conditions. We propose that Mars experienced acidic events caused by sulfuric acid (H2SO4) that permitted phyllosilicate, but inhibited carbonate, formation. To experimentally verify this hypothesis, we report the first synthesis of smectite from Mars-analogue glass-rich basalt simulant (66 wt% glass, 32 wt% olivine, 2 wt% chromite) in the presence of H2SO4 under hydrothermal conditions (approximately 200 degC). Smectites were analyzed by X-ray diffraction, Mossbauer spectroscopy, visible and near-infrared reflectance spectroscopy and electron microprobe to characterize mineralogy and chemical composition. Solution chemistry was determined by Inductively Coupled Plasma Mass Spectrometry. Basalt simulant suspensions in 11-42 mM H2SO4 were acidic with pH less than or equal to 2 at the beginning of incubation and varied from acidic (pH 1.8) to mildly alkaline (pH 8.4) at the end of incubation. Alteration of glass phase during reaction of the basalt simulant with H2SO4 led to formation of the dioctahedral smectite at final pH approximately 3 and trioctahedral smectite saponite at final pH approximately 4 and higher. Anhydrite and hematite formed in the final pH range from 1.8 to 8.4 while natroalunite was detected at pH 1.8. Hematite was precipitated as a result of oxidative dissolution of olivine present in Adirondack basalt simulant. Formation of secondary phases, including smectite, resulted in release of variable amounts of Si, Mg, Na and Ca while solubilization of Al and Fe was low. Comparison of mineralogical and solution chemistry data indicated that the type of smectite (i.e., dioctahedral vs trioctahedral) was likely controlled by Mg leaching from altering basalt and substantial Mg loss created favorable conditions for formation of dioctahedral smectite. We present a model for global-scale smectite formation on Mars via acid-sulfate conditions created by the volcanic outgassing of SO2 in the Noachian and early Hesperian.

Smectite↗
DOE OSTI2022

Gamma Radiation-Induced Degradation of Acetohydroxamic Acid (AHA) in Aqueous Nitrate and Nitric Acid Solutions Evaluated by Multiscale Modelling

Acetohydroxamic acid (AHA) has been proposed for inclusion in advanced, single-cycle, used nuclear fuel reprocessing solvent systems for the reduction and complexation of plutonium and neptunium ions. For this application, a detailed description of the degradation of AHA in dilute aqueous nitric acid is required. To this end, we present a comprehensive, multiscale computer model for the coupled radiolytic and hydrolytic degradation of AHA in aqueous sodium nitrate and nitric acid solutions. Rate coefficients for the reactions of AHA and HA with the oxidizing nitrate radical were measured for the first time using pulsed electron radiolysis and used as inputs in the kinetic model. The computer model results are validated by comparison to experimental data from steady state gamma irradiations, for which the agreement is excellent. Here, the presented model accurately predicts the yields of the major degradation products of AHA: acetic acid, hydroxylamine, nitrous oxide, and molecular hydrogen.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2020

A mass spectrometry-based high-throughput screening method for engineering fatty acid synthases with improved production of medium-chain fatty acids

Microbial cell factories have been extensively engineered to produce free fatty acids (FFAs), key components of crucial nutrients, soaps, industrial chemicals, and fuels. Yet, our ability to control the specificity of microbially synthesized FFAs is still limited for medium-chain fatty acids (MCFAs), which is mainly due to lack of high-throughput approaches for FFA analysis. Here we report a mass spectrometry (MS)-based method for rapid profiling of MCFAs in Saccharomyces cerevisiae by using membrane lipids as a proxy. Specially, matrix-assisted laser desorption/ionization time-of-flight (MALDI-ToF) MS was used to detect shorter acyl chain phosphatidylcholines from membrane lipids and the m/z peak ratio at 730 and 758 was used as an index for improved MCFA production. This yeast colony-based method can be performed at a rate of ~2 second per sample, which is much faster than the gold standard gas chromatography (GC)-MS (typically > 30 min per sample). To demonstrate the power of this method, we performed site-saturation mutagenesis of the yeast fatty acid synthase and identified 9 mutants that resulted in improved MCFA production relative to the wild-type strain. This colony-based MALDI-ToF MS screening method offers an alternative way for engineering microbial fatty acid compositions in a high-throughput manner.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Continuous recovery of phosphoric acid and Rare-Earths containing particles from phosphoric acid sludge using a decanter centrifuge

Recovery of rare earth elements (REEs) from various industrial and natural streams currently draws significant attention in efforts to meet the demands of the manufacturing industry. Among many industrial byproducts and waste streams, phosphoric acid sludge could be one of the most economically feasible resources for the recovery of REEs because solid particles in the sludge contain relatively concentrated REEs, up to 3,000 ppm, while the liquid component of the sludge is valuable phosphoric acid (P 2 O 5 ) that can be recovered and returned to the main product. Due to high viscosity and large solids content (e.g., 30–40 %), however, this byproduct stream requires multistep separation and purification processes. In this study, a single-step process involving a continuous-flow decanter centrifuge (CFDC) was employed to investigate its feasibility for continuous solid/liquid separation from real phosphoric acid sludge. High centrifugal forces generated from up to 1500 G gravity acceleration separate solid particles from the sludge, generating a liquid-rich stream and a solids-rich stream at the exit of the CFDC. A single pass of phosphoric-acid sludge through the CFDC yielded 95 % liquid recovery and 90 % recovery of REEs-containing solids from 20 to 34 wt% solids-containing sludge. Finally, a reduced order model developed for the CFDC operation showed good agreement with experimental data, and preliminary technoeconomic analysis revealed potential process feasibility.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Assessing feasible H2–CO2 sources in the US as Feedstocks for Sustainable Aviation Fuel Precursors: Acetic Acid and Ethanol Production via Hydrogenotrophic Pathways

The environmental impact of carbon dioxide emissions is significant, and research is focused on mitigating these emissions and developing eco-friendly technologies in line with green chemistry principles. Waste-to-energy technologies play a crucial role in converting waste into renewable energy and valuable biofuels and bioproducts. This study specifically explores the utilization of waste gas emissions, particularly carbon dioxide, from various sources in the United States for the production of sustainable aviation fuel (SAF) precursors, such as ethanol and acetic acid. The study categorizes and quantifies the volumes of carbon dioxide emissions into three types: non-biogenic, biogenic, and biogenic emissions from ethanol production facilities. Stoichiometric calculations are applied to compare the amounts of carbon dioxide from each category with the available hydrogen production capacity, determining if sufficient hydrogen is present for converting carbon dioxide into SAF precursors. The study reveals two key findings. Firstly, there is a significant reserve of carbon dioxide, approximately 1648 million metric tons per year (MMTy), combining all three categories, which would require a substantial increase of approximately 35–40 times in the existing hydrogen production capacity of 4.988 MMTy. This increased hydrogen production has the potential to yield approximately 1067.82 MMTy of acetic acid and 189.19 MMTy of ethanol annually. Secondly, upon analyzing the quality and application of the three sources of carbon dioxide with the currently available hydrogen production capacity, it is found that biogenic carbon dioxide from ethanol plants is the most suitable choice for immediate production of SAF precursors. This would theoretically result in an annual production of 1.36 MMTy of ethanol and 1.772 MMTy of acetic acid. The other two sources of carbon dioxide can be considered potential reserves for future utilization when additional hydrogen production facilities are established. The study provides a foundation for assessing the aggregation potential required for acetic acid and ethanol production. By optimizing the use of waste gases as raw materials, the study not only enables the production of SAF precursors but also contributes to the passive reduction of greenhouse gas emissions.

Carbon Dioxide↗
DOE OSTI2020

Binding of Formic Acid on Anatase TiO2(101)

The adsorption of formic acid (FA) and the formation of formate species on metal oxide surfaces are of great interest in catalysis. Formic acid is used to probe the adsorption properties of surface sites and formates are common intermediates in many catalytic reactions. Here we focus on the interaction of FA with a prototypical anatase TiO2(101) surface by using a combination of scanning tunneling microscopy (STM), infrared reflection absorption spectroscopy (IRAS), electron stimulated desorption (ESD), and density functional theory (DFT) to assess the coverage dependent evolution of different FA-derived surface species at low temperatures (80–240 K). We find that isolated FA adsorbs at 80 K in both monodentate (MD) and bidentate (BD) configurations on top of undercoordinated Ti sites (Ti5c). The MD form is likely deprotonated and readily converts upon annealing to bridging BD on two neighboring Ti5c sites. DFT calculations show that molecularly-bound MD FA is metastable and readily converts into a deprotonated state in the proximity of subsurface oxygen vacancy. The stability of the MD species increases as the availability of the paired Ti5c sites for BD formation diminishes at high coverages. Upon surface saturation, a mixed configuration of alternating bidentate and monodentate species with coverage of 2/3 FA/Ti5c represents the most favorable configuration. This is in contrast with the adsorption of FA on rutile TiO2(110) and many other oxides, where bidentate formate species dominate. Y.W., A.D., G.A.K., R.R., N.G.P., and Z.D. were supported by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences (BES), Division of Chemical Sciences, Geosciences and Biosciences (CSGB) under FWP 47319. B.W. and A.S. acknowledge the support of DOE BES, CSGB Division under Award DESC0007347. The experimental studies were performed in EMSL, a national scientific user facility sponsored by the Department of Energy’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is a multiprogram national laboratory operated for DOE by Battelle. The authors also acknowledge computational resources from the TIGRESS high-performance computer center at Princeton University.

Wang, Yang↗