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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 19 records

Contrasting effects of glutamate and branched-chain amino acid metabolism on acid tolerance in a Castellaniella isolate from acidic groundwater

Groundwater acidification co-occurring with nitrate pollution is a common, global environmental health hazard. Denitrifying bacteria have been leveraged for the in situ removal of nitrate in groundwater. However, co-existing stressors—such as low pH—reduce the efficacy of biological removal processes. Castellaniella sp. str. MT123 is a complete denitrifier that was isolated from acidic, nitrate-contaminated groundwater. The strain grows robustly by nitrate respiration at pH < 6.0, completely reducing nitrate to dinitrogen gas. Genomic analyses of MT123 revealed few previously characterized acid tolerance genes. Thus, we utilized a combination of proteomics, metabolomics, and competitive mutant fitness to characterize the genetic mechanisms of MT123 acclimation to growth under mildly acidic conditions. We found that glutamate accumulation is critical in the acid acclimation of MT123, possibly through consumption of intracellular protons via glutamate decarboxylation to GABA. This is despite the fact that MT123 lacks the canonical glutamate decarboxylase-glutamate/GABA antiporter system implicated in acid tolerance in other bacteria. In contrast, branched-chain amino acid (BCAA) accumulation was detrimental to cell growth at lower pHs, possibly through indirect mechanisms impacting the cellular glutamate pool. Genetic analysis previously linked MT123 to a population of Castellaniella that bloomed—concurrent to nitrate removal—during a biostimulation effort to reduce groundwater nitrate concentrations at MT123’s location of origin. Thus, our analyses provide novel insight into mechanisms of acclimation to acidic conditions in a strain with significant potential for nitrate bioremediation.

59 BASIC BIOLOGICAL SCIENCES↗

Adsorption Equilibrium, Kinetics, and Column Breakthrough Data for Aqueous Solutions of Binary-Acid and Ternary-Acid Mixtures of Acetic Acid, Butyric Acid, and Lactic Acid on IRN-78 Ion-Exchange Resin at Initial pH Levels of ∼3–7 and at 25–55 °C

This work is part of an effort to develop thermophysical property data and models supporting adsorptive process development for organic acid separation from a dilute aqueous solution of fermentation broth. It presents systematic experimental measurements for aqueous-phase adsorption equilibrium, kinetics, and column breakthrough for three binary-acid aqueous mixtures (acetic acid + lactic acid, butyric acid + lactic acid, and acetic acid + butyric acid) and one ternary-acid aqueous mixture (acetic acid + butyric acid + lactic acid) on Amberlite IRN-78 ion-exchange resin. The equilibrium measurements covered broad ranges of the initial acid concentration (100–400 mmol/L), initial pH (∼3–7), and temperature (25–55 °C). The equilibrium data for the binary-acid and ternary-acid aqueous mixtures indicate selective adsorption of lactic acid at initial pH levels of ∼3 and 4, while acetic acid and butyric acid are selectively adsorbed at initial pH levels of 5, 6, and 7. The subsequent kinetics and column breakthrough experiments were performed at 200 mmol/L with equimolar ratios, an initial pH of 6, and 25 °C. In conclusion, the measurements provide essential data sets for rigorous thermodynamic modeling and process simulation of adsorptive separation processes for organic acid separation from fermentation broth.

Adsorption↗

Synthesis of Acid Hydrazides from Carboxylic Acids in Continuous Flow

A concise methodology for the synthesis of acid hydrazides from carboxylic acids via a continuous flow process in yields ranging from 65 to 91% is described. Using short residence times of between 13 and 25 mins, the conditions proved amenable to a variety of mono- and diacids, including aliphatic, aromatic, and heteroaromatic functionalities. Furthermore, to demonstrate scalability, a large-scale (200 g) synthesis of azelaic dihydrazide was conducted over a continuous run of 9 h with an 86% overall yield, equating to a 22 g/h output.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Oxidation of indole-3-acetic acid and oxindole-3-acetic acid to 2,3-dihydro-7-hydroxy-2-oxo-1H indole-3-acetic acid-7'-O-beta-D-glucopyranoside in Zea mays seedlings

Radiolabeled oxindole-3-acetic acid was metabolized by roots, shoots, and caryopses of dark grown Zea mays seedlings to 2,3-dihydro-7-hydroxy-2-oxo-1H indole-3-acetic acid-7'-O-beta-D-glycopyranoside with the simpler name of 7-hydroxyoxindole-3-acetic acid-glucoside. This compound was also formed from labeled indole-3-acetic acid supplied to intact seedlings and root segments. The glucoside of 7-hydroxyoxindole-3-acetic acid was also isolated as an endogenous compound in the caryopses and shoots of 4-day-old seedlings. It accumulates to a level of 4.8 nanomoles per plant in the kernel, more than 10 times the amount of oxindole-3-acetic acid. In the shoot it is present at levels comparable to that of oxindole-3-acetic acid and indole-3-acetic acid (62 picomoles per shoot). We conclude that 7-hydroxyoxindole-3-acetic acid-glucoside is a natural metabolite of indole-3-acetic acid in Z. mays seedlings. From the data presented in this paper and in previous work, we propose the following route as the principal catabolic pathway for indole-3-acetic acid in Zea seedlings: Indole-3-acetic acid --> Oxindole-3-acetic acid --> 7-Hydroxyoxindole-3-acetic acid --> 7-Hydroxyoxindole-3-acetic acid-glucoside.

Zea mays/metabolism↗

Thermodynamic modeling of aqueous acetic acid, butyric acid, and lactic acid solutions

Based on the activity coefficient – fugacity coefficient approach, a rigorous thermodynamic modeling study is presented for accurate correlation of vapor-liquid equilibrium data of aqueous solutions of acetic acid (293 to 391 K), butyric acid (325 to 436 K), lactic acid (378 to 409 K), and acetic acid + butyric acid binary mixture (358 to 421 K). In addition, the pH data of the three aqueous, single carboxylic acid solutions were measured at 298 to 328 K and successfully correlated. Given that these aqueous carboxylic acid solutions exhibit various degrees of association behavior in both vapor and liquid phases, the thermodynamic models considered for this study include the Redlich-Kwong equation of state (RK-EoS) and the Hayden-O’Connell equation of state (HOC-EoS) for the vapor phase fugacity coefficients and the electrolyte non-random two-liquid model (eNRTL) and the association electrolyte non-random two-liquid model (AeNRTL) for the liquid phase activity coefficients. The combination of the HOC-EoS for the vapor phase and the AeNRTL model for the liquid phase is found to provide the best correlation results, consistent with the fact that the HOC-EoS and the AeNRTL model explicitly account for association behaviors in the vapor phase and the liquid phase, respectively.

09 BIOMASS FUELS↗

On the abiotic formation of amino acids. I - HCN as a precursor of amino acids detected in extracts of lunar samples. II - Formation of HCN and amino acids from simulated mixtures of gases released from lunar samples

Two studies on the abiotic formation of amino acids are presented. The first study demonstrates the role of hydrogen cyanide as a precursor of amino acids detected in extracts of lunar samples. The formation of several amino acids, including glycine, alanine, aspartic acid, and glutamic acid, under conditions similar to those used for the analysis of lunar samples is demonstrated. The second study investigates the formation of hydrogen cyanide as well as amino acids from lunar-sample gas mixtures under electrical discharge conditions. These results extend the possibility of synthesis of amino acids to planetary bodies with primordial atmospheres less reducing than a mixture of methane, ammonia, hydrogen and water.

Yuasa, S.↗

Adsorption Equilibrium, Kinetics, and Column Breakthrough Data of Acetic Acid, Butyric Acid, and Lactic Acid on IRN-78 Ion-exchange Resin at Initial pH ~3 – 7 and Temperature 25 – 55 °C

This work presents systematic aqueous-phase adsorption equilibrium, kinetics, and column breakthrough measurements with three key biointermediates that are common compounds in many bioprocesses. Adsorption equilibrium experiments were carried out with acetic acid, butyric acid, and lactic acid on a commercial ion-exchange resin, Amberlite IRN-78, at wide ranges of acid concentration (8-500 mmol/L), initial pH (similar to 3-7), and temperature (25-55 degrees C), simulating the effluent characteristics from different fermenter operations. The kinetics and column breakthrough experiments were conducted at an initial pH of 6 and a concentration of 200 mmol/L. The equilibrium study shows a higher loading at the initial pH < pK(a) and a lower loading at the initial pH > pK(a). Overall removal varies between 16 and 99% depending on the initial pH, temperature, and organic acid concentration and type. The study further indicates monolayer adsorption at the equilibrium pH > 10 and multilayer adsorption at the equilibrium pH < 6. The thermodynamic modeling of adsorption isotherm data was carried out using Langmuir and Freundlich isotherms. IRN-78 presents fast adsorption kinetics as the maximum loading was attained in <= 10 min and nearly the same breakthrough time for all three organic acids involved in this study.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Radiolysis of Sulfuric Acid, Sulfuric Acid Monohydrate, and Sulfuric Acid Tetrahydrate and Its Relevance to Europa

We report laboratory studies on the 0.8 MeV proton irradiation of ices composed of sulfuric acid (H2SO4), sulfuric acid monohydrate (H2SO4 H2O), and sulfuric acid tetrahydrate (H2SO4 4H2O) between 10 and 180 K. Using infrared spectroscopy, we identify the main radiation products as H2O, SO2, (S2O3)x, H3O+, HSO4(exp -), and SO4(exp 2-). At high radiation doses, we find that H2SO4 molecules are destroyed completely and that H2SO4 H2O is formed on subsequent warming. This hydrate is significantly more stable to radiolytic destruction than pure H2SO4, falling to an equilibrium relative abundance of 50% of its original value on prolonged irradiation. Unlike either pure H2SO4 or H2SO4 H2O, the loss of H2SO4 4H2O exhibits a strong temperature dependence, as the tetrahydrate is essentially unchanged at the highest irradiation temperatures and completely destroyed at the lowest ones, which we speculate is due to a combination of radiolytic destruction and amorphization. Furthermore, at the lower temperatures it is clear that irradiation causes the tetrahydrate spectrum to transition to one that closely resembles the monohydrate spectrum. Extrapolating our results to Europa s surface, we speculate that the variations in SO2 concentrations observed in the chaotic terrains are a result of radiation processing of lower hydration states of sulfuric acid and that the monohydrate will remain stable on the surface over geological times, while the tetrahydrate will remain stable in the warmer regions but be destroyed in the colder regions, unless it can be reformed by other processes, such as thermal reactions induced by diurnal cycling.

Loeffler, M. J.↗

Low irradiances affect abscisic acid, indole-3-acidic acid, and cytokinin levels of wheat (Triticum aestivum L.) tissues

Wheat (Triticum aestivum L.) plants were grown under four irradiance levels: 1,400, 400, 200, and 100 micromol m-2 s-1. Leaves and roots were sampled before, during, and after the boot stage, and levels of abscisic acid (ABA), indole-3-acetic acid (IAA), zeatin, zeatin riboside, dihydrozeatin, dihydrozeatin riboside, isopentenyl adenine, and isopentenyl adenosine were quantified using noncompetitive indirect ELISA systems. Levels of IAA in leaves and roots of plants exposed to 100 micromol m-2 s-1 of irradiance were 0.7 and 2.9 micromol kg-1 dry mass (DM), respectively. These levels were 0.2 and 1.0 micromol kg-1 DM, respectively, when plants were exposed to 1,400 micromol m-2 s-1. Levels of ABA in leaves and roots of plants exposed to 100 micromol m-2 s-1 were 0.65 and 0.55 micromol kg-1 DM, respectively. They were 0.24 micromol kg-1 DM (both leaves and roots) when plants were exposed to 1,400 micromol m-2 s-1. Levels of isopentenyl adenosine in leaves (24.3 nmol kg-1 DM) and roots (29.9 nmol kg-1 DM) were not affected by differences in the irradiance regime. Similar values were obtained in a second experiment. Other cytokinins could not be detected (<10 nmol kg 1 DM) in either experiment with the sample sizes used (150-600 mg DM for roots and shoots, respectively).

Non-NASA Center↗

Wettability Alteration with Weak Acid-Assisted Surfactant Flood

Oil-wetness and heterogeneity are two key reasons for low oil recovery by waterflooding in carbonate reservoirs. Surfactants have been effective in altering the oil-wet matrix to a more water-wet condition and initiating spontaneous imbibition. Because it takes time for the surfactant to alter wettability, oil recovery from the tight matrix is slow and sometimes not economically feasible. Acids have the potential of dissolving minerals, which may alter wettability. In this study, the enhanced oil recovery (EOR) performance of an acid-assisted surfactant solution, a novel technique, was evaluated for low-temperature applications. A set of acids and their acetates were tested. Bulk rock-acid reaction, wettability alteration (WA) tests, and spontaneous imbibition measurements were conducted at reservoir temperature (35°C) to identify effective candidates. Coreflood tests were then performed to evaluate the selected acid-surfactant formulations. Before and after a coreflood test, the core was scanned using micro-computed tomography (CT) to investigate pore structure alteration. Bulk reaction measurements showed that weak acids, especially acetic acid (AA), have the desired low reaction rates at 35°C. WA tests showed that AA can remove the crude oil off the rock surface and alter wettability through mineral dissolution. The surfactant can reduce contact angles from 160° to 58°; adding acid into the surfactant can further reduce it to 52°. Spontaneous imbibition experiments showed the synergy between the acid and the surfactant; the AA-surfactant solution had the highest oil recovery (62.6%) among acid-surfactant formulations. The acid improves the WA efficiency by the surfactant through surface mineral dissolution and lower ζ-potential. The imbibition transports the acid-surfactant solutions into the matrix, which minimizes face dissolution. Coreflood tests show that the AA-surfactant flood can increase the oil recovery rate and recover about 8% more oil compared to the surfactant flood. Micro-CT showed that a few mineral particles were transported along the core and partially plugged pore throats, which reduced permeability and diverted flow leading to improved oil recovery. Here, the transport of the acid in reservoirs and the potential plugging issues have to be carefully evaluated in future studies.

58 GEOSCIENCES↗

Oxidative Deboronation of Boronic Acids by Hydrogen Peroxide in Planta Generates Borate for Cross-Linking of Rhamnogalacturonan II

Vascular plants require boron to cross-link the rhamnogalacturonan-II (RG-II) domain of pectin to form functional cell walls. Boronic acids, which form reversible esters with cis-diols like borate, have been proposed to influence RG-II cross-linking, though the mechanism remains unclear. We used suspension-cultured rose cells adapted to grow without boron to investigate the effect of boronic acids on RG-II dimerization. When grown with phenylboronic acid (PBA) as the sole boron source, nearly all RG-II was crosslinked, whereas methylboronic acid (MBA) only partially restored cross-linking. In contrast, in vitro assays showed that homogeneous RG-II monomers did not dimerize with alkyl or aryl boronic acids unless supplemented with hydrogen peroxide (H2O2), which oxidatively converts boronic acids to boric acid. Real-time NMR spectroscopy and density functional theory calculations provided insight into the reaction mechanism and energetics of oxidation respectively. Together, our data show that exogenous boronic acids are a source of boric acid for plants, and that the deboronation reaction generates aryl or alkyl alcohol byproducts that can undergo further chemical modification in planta. The fate and potential roles of these byproducts in planta remain to be determined.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Low Total Abundances and a Predominance of n-ω-Amino Acids in Enstatite Chondrites: Implications for Thermal Stability of Amino Acids in the Inner Solar System

Investigating the organic contents of enstatite chondrite meteorites may offer insights into both early inner solar system and early Earth chemistry. Enstatite chondrite meteorites have highly reduced and anhydrous compositions, and their bulk isotopic compositions closely resemble terrestrial values, suggesting that their parent body asteroids accreted within the inner protoplanetary disk and were a primary contributor during Earth’s late accretion (Javoy et al., 1995; Piani et al., 2020). Here, we present the first report of amino acids in enstatite chondrite meteorite samples. Three EH3 meteorites were analyzed (Dominion Range 14021, Larkman Nunatak 12001, and Larkman Nunatak 06252). The acid-hydrolyzed water extracts of the meteorites contained low abundances (1.5 – 215.9 pmol/g) of n-ω-amino acids (glycine, β-alanine, γ-amino-n-butyric acid (γ-ABA), δ-amino-n-valeric acid (δ-AVA), and ε-amino-n-caproic acid (ε-ACA)), but amino acids were not present above detection limits in the non-hydrolyzed samples. The low amino acid abundances and the predominance of n-ω-amino acids resembles amino acid distributions previously observed for thermally altered chondrites. These results suggest that the parent body asteroid was not conducive to the synthesis and/or preservation of α-amino acids, or free amino acids in general, and that EH3 chondrite-like material may not have been a primary contributor of diverse or abundant free amino acids to the early Earth.

Danielle N Simkus↗

Low total abundances and a predominance of n-ω-amino acids in enstatite chondrites: Implications for thermal stability of amino acids in the inner solar system

Investigating the organic contents of enstatite chondrite meteorites may offer insights into both early inner solar system and early Earth chemistry. Enstatite chondrite meteorites have highly reduced and anhydrous compositions, and their bulk isotopic compositions closely resemble terrestrial values, suggesting that their parent body asteroids accreted within the inner protoplanetary disk and were a primary contributor during Earth’s late accretion (Javoy, 1995; Piani et al., 2020). Here, we present the first report of amino acids in enstatite chondrite meteorite samples. Three EH3 meteorites were analyzed (Dominion Range [DOM] 14021, Larkman Nunatak [LAR] 12001, and Larkman Nunatak 06252). The acid-hydrolyzed water extracts of the meteorites contained low abundances (1.5–215.9 pmol per g) of n-ω-amino acids (glycine, β-alanine, γ-amino-n-butyric acid [γ- ABA], δ-amino-n-valeric acid [δ-AVA], and ϵ-amino-n-caproic acid [ϵ-ACA]), but amino acids were not present above detection limits in the nonhydrolyzed samples. The low amino acid abundances and the predominance of n-ω-amino acids resemble amino acid distributions previously observed for thermally altered chondrites. These results suggest that the parent body asteroid was not conducive to the synthesis and/or preservation of α-amino acids, or free amino acids in general, and that EH3 chondrite-like material may not have been a primary contributor of diverse or abundant free amino acids to the early Earth.

Danielle N. Simkus↗

Photoautotrophic organic acid production: Glycolic acid production by microalgal cultivation

Although microalgae produce value-added products, such as lipids, pigments, and polysaccharides using light and carbon dioxide, these intracellular products require costly downstream processes such as extraction and purification. Thus, extracellular products are desirable for economic production. While reported before, the secretion of glycolic acid by microalgal photorespiration has not received attention for industrial applications. Here we developed a two-stage continuous cultivation system to increase glycolic acid production using a glycolate dehydrogenase (GYD1) deficient mutant of Chlamydomonas reinhardtii which produces high concentrations of glycolic acid. Specifically, 3% CO 2 was supplied in the first-stage culture for the production of biomass and ambient air (0.03% CO 2 ) was supplied to the second stage for the production of glycolic acid. As a result, overall glycolic acid productivity reached 82.0 mg L -1 d -1 at a dilution rate of 0.34 d -1 . However, as the pH of the second stage decreased to 4.7 due to the increased glycolic acid production, we controlled the pH of the second stage at pH 6.0, resulting in 122.6 mg L -1 d -1 of glycolic acid productivity. Flux balance analysis revealed that the experimental glycolic acid production rate was 69% of the theoretical glycolic acid production rate. The deviation might be due to the toxicity of glycolic acid. When a techno-economic analysis was conducted based on the experimental results, the minimum glycolic acid production cost was estimated to be $31 kg -1 , indicating a potential for industrial production. Our findings suggest that microalgae can be utilized for the cost-effective industrial production of glycolic acid.

42 ENGINEERING↗

Inorganic acid-catalyzed hydrogen peroxide-acetic acid pretreatment for selective delignification of poplar

Effects of different inorganic acids as catalysts on the delignification ability of hydrogen peroxide-acetic acid (HPAA) pretreatment were unclear. Herein, the oxidizability of HCl, HBr, H 2 SO 4 , and H 3 PO 4 -catalyzed HPAA on the delignification of poplar were investigated. The ionized H + from inorganic acids catalyzed the synthesis of peracetic acid and improved the oxidizability of HPAA. The anion of inorganic acids caused ineffective decomposition of peroxides and inorganic acids. After the addition of poplar, the H 2 SO 4 -catalyzed HPAA pretreatment exhibited the lowest pH than other inorganic acids catalyzed systems. After the catalysis by inorganic acid, HPAA removed 78.1–91.4 % poplar lignin. Compared with other inorganic acids, the H + of H 2 SO 4 exhibited superior retention in HPAA pretreatment of poplar. After poplar pretreated with the same initial pH value of inorganic acid-catalyzed HPAA, the H 2 SO 4 -catalyzed HPAA showed the strongest delignification ability of poplar. The presence of free radicals in inorganic acid-catalyzed HPAA was unnecessary for the delignification of poplar. Furthermore, this paper elucidated that the ionized H + of inorganic acid mainly enhanced the oxidizability of HPAA for the selectively delignification of ability of HPAA pretreatment.

In-situ synthesis↗