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At least 505 records · Page 28

Bio-based oxalic acid production in Issatchenkia orientalis enables sustainable rare earth recovery

The growing demand for rare earth elements (REEs) in clean energy and high-tech industries underscores the need for sustainable recovery methods and a reliable supply of processing chemicals. Here, we establish a microbial platform using the acid-tolerant yeast Issatchenkia orientalis SD108 to produce bio-oxalic acid for REE recovery. By introducing an oxaloacetate cleavage pathway and applying metabolic engineering, the engineered strain produces 39.53 g·L -1 oxalic acid at pH 4.0 in fed-batch fermentation. The crude fermentation broth, used without purification, efficiently precipitates over 99% neodymium (Nd), 99% dysprosium (Dy), and 98% lanthanum (La) from individual REE chloride solutions. Recovery from a low-grade ore leachate achieves over 99% total recovery. X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) confirm that REE oxalates precipitated with bio-oxalic acid closely resemble those obtained using commercial oxalic acid. Techno-economic analysis (TEA) and life cycle assessment (LCA) further demonstrate that bio-oxalic acid can be produced at a competitive price of $1.79·kg -1 while reducing carbon intensity (CI) by 112% to 63.5% with and without electricity displacement, respectively, relative to the fossil-based benchmark. These results highlight bio-oxalic acid as a green, economically viable alternative to synthetic oxalate for sustainable REE recovery.

59 BASIC BIOLOGICAL SCIENCES↗

A 2-component blend of coconut oil-derived fatty acids as an oviposition deterrent against Drosophila suzukii (Drosophilidae: Diptera)

Abstract Coconut free fatty acid (CFFA), a mixture of 8 fatty acids derived from coconut oil, is an effective repellent and deterrent against a broad array of hematophagous insects. In this study, we evaluated the oviposition deterrent activity of CFFA on spotted-wing drosophila (SWD; Drosophila suzukii), a destructive invasive pest of berries and cherries, and identified bioactive key-deterrent compounds. In laboratory 2-choice tests, CFFA deterred SWD oviposition in a dose-dependent manner with the greatest reduction (99%) observed at a 20-mg dose compared with solvent control. In a field test, raspberries treated with 20-mg CFFA received 64% fewer SWD eggs than raspberries treated with the solvent control. In subsequent laboratory bioassays, 2 of CFFA components, caprylic and capric acids, significantly reduced SWD oviposition by themselves, while 6 other components had no effect. In choice and no-choice assays, we found that a blend of caprylic acid and capric acid, at equivalent concentrations and ratio as in CFFA, was as effective as CFFA, while caprylic acid or capric acid individually were not as effective as the 2-component blend or CFFA at equivalent concentrations, indicating the 2 compounds as the key oviposition deterrent components for SWD. The blend was also as effective as CFFA for other nontarget drosophilid species in the field. Given that CFFA compounds are generally regarded as safe for humans, CFFA and its bioactive components have potential application in sustainably reducing SWD damage in commercial fruit operations, thereby reducing the sole reliance on insecticides.

Entomology↗

Proteome-wide analysis of protein stability in Escherichia coli under acid stress

Knowledge of protein acid sensitivity remains sparse and is largely derived from low-throughput, enzyme-specific assays. We used a scalable framework to map acid stability across the Escherichia coli proteome to assess the acid stability of 1,675 unique proteins, estimating pH 50 values for over 90% of them. The parameter pH50 was defined as the pH value at which only 50% of the initial protein remains in solution following acid treatment. Proteome-wide pH 50 values ranged from 2.28 to 6.33 (median 5.11). Approximately 9% of detected proteins remained stable across all tested pH conditions. Our results align with published data and the assay of citrate synthase (GltA) performed here. Protein acid stability differed significantly by subcellular localization: periplasmic proteins were relatively more abundant in the acid-stable group, cytoplasmic proteins were abundant at pH 50 values 4.5–5.5, and inner membrane proteins at higher pH 50 between 5.5 and 6.0. Outer membrane proteins were too few to draw strong conclusions regarding enrichment within specific pH 50 groups. Notably, the periplasmic binding protein of the molybdate ABC transporter (ModA), was enriched after incubation at low pH. Estimated pH 50 values showed no correlation with protein isoelectric point and molecular weight. Together, this work provides the first proteome-wide map of protein acid stability and establishes a general framework for studying different chemical stressors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Enhanced phagocytosis and complement-mediated killing of Mannheimia haemolytica serotype 1 following in-frame CMP-sialic acid synthetase ( neuA ) gene deletion

ABSTRACT Mannheimia haemolyticais the most significant bacterial pathogen associated with the bovine respiratory disease complex. Although sialic acid is a known virulence factor in other members of Pasteurellaceae, such asHistophilus somniandPasteurella multocida, the significance of sialic acid to the virulence ofM. haemolyticais currently unknown. Therefore, the role of sialic acid as a virulence determinant ofM. haemolyticawas investigated by constructing an in-frameneuA[CMP-N-acetylneuraminic acid (Neu5Ac/sialic) synthetase] mutant, which was shown by high-performance anion exchange chromatographic analysis (HPAEC) to be devoid of sialic acid on the lipopolysaccharide (LPS). Both theneuAmutant and wild-type parent strains exhibited similar growth rates in the growth curve assay. Real-time qPCR and ELISA evaluation showed no differences in proinflammatory cytokine expressions (IL-1β, IL-6, and IL-8) between theneuAmutant and parent strain when peripheral blood mononuclear cells were incubated with LPS. Interestingly, theneuAmutant was three to four logs more sensitive to a whole-blood bacterial killing assay than the parent strain. Similar results were also observed in plasma and serum bacterial killing assays. Flow cytometry analyses showed higher uptake ofneuAmutant by phagocytes, compared to the parent strain, in the whole-blood phagocytosis assay; however, no difference in reactive oxygen species production in neutrophils or monocytes was detected for either strain. Taken together, these results indicate that sialylation ofM. haemolyticaLPS plays a vital role in reducing complement-mediated and phagocytic killing. IMPORTANCE The Gram-negative coccobacillusMannheimia haemolyticais a natural inhabitant of the upper respiratory tract in ruminants and the most common bacterial agent involved in bovine respiratory disease complex development. Key virulence factors harbored byM. haemolyticaare leukotoxin, lipopolysaccharide, capsule, adhesins, and neuraminidase which are involved in evading innate and adaptive immune responses. In this study, we have shown that CMP-sialic acid synthetase (neuA) is necessary for the incorporation of sialic acid onto the membrane, and inactivation ofneuAresults in increased phagocytosis and complement-mediated killing ofM. haemolytica,thus demonstrating that sialylation contributes to the virulence ofM. haemolytica.

Microbiology↗

Effects of 9.5 Years of Whole-Soil Warming on the Fatty Acid and n-Alkanes Composition in Bulk Soil and Density Fractions at Blodgett Experimental Forest, California, USA

Original data of molecular data (fatty acids and n-alkanes) including concentrations and calculated molecular proxies in a whole-soil warming experiment at the Blodgett Forest Research Station after 9.5 years of warming. The study site has a Mediterranean climate with annual average temperature of 12.5 ℃ and annual average precipitation of 1774 mm. The study site is characterized by a mesic Ultic Alfisol formed from granitic parent material, corresponding to a Dystric Cambisol under the World Reference Base for Soil Resources (WRB) classification system. Experimental warming is applied throughout the soil profile to a depth of 1 m using vertically embedded heating cables that raise soil temperature by 4 °C relative to ambient conditions. Soil samples were collected on 1 May 2023, after the experiment had been operating continuously for about 9.5 years since its initiation in January 2014.The data has been processed from raw data and cross-validated by other peers. The dataset includes: - Bulk_Fattyacid_9.5-year_Soil_Warming_Blodgett, California, USA: fatty acid concentrations and proxies including Carbon Preference Index (CPI) and Average Chain Length (ACL) of bulk soil organic carbon; - Fractions_Fattyacid_9.5-year_Soil_Warming_Blodgett, California, USA: fatty acid concentrations and proxies including CPI and ACL of free particulate organic matter (fPOM) and mineral-associated organic matter (MAOM); - Bulk_Alkanes_9.5-year_Soil_Warming_Blodgett, California, USA: n-alkanes concentrations and proxies including CPI and ACL of bulk soil organic carbon; - Fractions_Alkanes_9.5-year_Soil_Warming_Blodgett, California, USA: n-alkanes concentrations and proxies including CPI and ACL of fPOM and MAOM; - n-Alkanes_All_Monomer_Concentration_9.5-year_Soil_Warming_Blodgett, California, USA: concentration of all the n-alkane monomers identified and integrated for bulk soil, fPOM and MAOM; - Fattyacid_All_Monomer_Concentration_9.5-year_Soil_Warming_Blodgett, California, USA: concentration of all the fatty acid monomers including diacids identified and integrated for bulk soil, fPOM, and MAOM. All data are provided in CSV format and can be viewed using Microsoft Excel. We specifically look at fatty acids (FA) and n-alkanes in bulk soil, fPOM and MAOM and calculated molecular proxies such as CPI and ACL to understand the source of oragnic carbon (with ACL) and degree of decomposition (CPI) of each soil fraction. Due to lack of long-chain fatty acids (carbon number ⩾ 20), microorganism-derived organic carbon is characterized by shorter ACL in comparison to plant-derived organic carbon. Fresh SOC is characterized by even-over-odd dominance for fatty acids and odd-over-even dominance for n-alkanes. Therefore, CPI indicates whether soil organic carbon (SOC) represents fresh input (CPI > 10) or is strongly decomposed (close to 1). The research questions should be then, after 9.5-year warming: 1. whether the relative contribution between microorganism-derived and plant-derived SOC in each soil fraction? 2. whether fPOM became more decomposed whereas MAOM remained relatively persistent in each soil fraction across the soil depth?

Carbon↗

Pyrolysis of amino acids - Mechanistic considerations

Pyrolysis of several structurally different amino acids in a column at 500 C showed differences in the mechanisms and final products. The aliphatic protein amino acids decompose mainly by simple decarboxylation and condensation reactions, while the beta amino acids undergo deamination to unsaturated acids. Alpha amino acids with alpha alkyl substituents undergo an unusual intramolecular SN1 reaction with the formation of an intermediate alpha lactone which decomposes to yield a ketone. The alpha alkyl substituents appear to stabilize the developing negative charge formed by partial heterolytic cleavage of the alpha carbon - NH3 bond. The gamma and delta amino acids give 2-pyrrolidinone and 2-piperidone respectively, while the epsilon acids yield mixed products.

Ratcliff, M. A., Jr.↗

Selective photodestruction of alpha-amino acids

A problem encountered in the analysis of amino acids in chemical evolution experiments and in extracts of meteorites is the large number present. A method for selectively destroying the alpha-amino acids, with only the beta- and gamma-amino acids remaining in the solution, is described. The amino acids used were racemic, with one milliliter of solution containing 0.0000025 mol of each acid irradiated in a 1-cm quartz cell having 254-nm monochromatic light in the presence of CuCl2. Excess H2S was added to precipitate the Cu (2+) as CuS. A gas chromatographic analysis was used to observe that irradiation with 254-nm light in the presence of Cu (2+) destroyed all the amino acids except the beta and the gamma types. It is concluded that with such a procedure, complex mixtures of amino acids can be simplified to make identification by GC mass spectrometry easier.

Levi, N.↗

Quantification of monocarboxylic acids in the Murchison carbonaceous meteorite

The abundances of some of the straight- and branched-chain isomers of the monocarboxylic acids found in the Murchison carbonaceous chondrite are determined. Monocarboxylic acids extracted from a crushed sample of Murchison interior were quantified by means of gas chromatography and mass spectroscopy after a spiking solution of deuterated analogues of 11 carboxylic acids had been added. Monocarboxylic acid abundances are found to range between 1.83 and 0.01 micromole/g, which is significantly higher than Murchison amino acid concentrations, and to decrease with increasing carbon number for both branched and unbranched molecules. The results are interpreted to support the abiotic extraterrestrial synthesis of monocarboxylic acids. Possible mechanisms leading to the equal synthesis of branched and each unbranched carboxylic acid with the same carbon number are considered, noting that the Fischer-Tropsch Type mechanism by itself is incapable of accounting for the observed distributions.

Lawless, J. G.↗

Amino acids and hydrocarbons approximately 3,800-Myr old in the Isua rocks, southwestern Greenland

Results of an analysis of amino acids and hydrocarbons found in the Isua banded iron formation, which contains the oldest known rocks on earth, are discussed. Similarities are pointed out between the relative amino acid abundances of the Isua rocks and those of lichens found on their surfaces, and a lack of substantial racemization indicated by the low D/L ratios in the 3800-million year old rock samples is noted. Experimental results showing the possibility of amino acid diffusion from lichens into the rocks are presented. Comparisons of the Isua rock amino acid D/L ratios with those reported for samples from other regions indicates that none of the Isua amino acids are older than a few tens of thousands to a few hundred thousand years. Analyses of the saturated hydrocarbons of the Isua samples reveals no odd carbon number preference, which may indicate antiquity, however laboratory experiments have shown that amino acids and aromatic and saturated aliphatic hydrocarbons could not have survived the metamorphic history of the Isua rocks. The evidence presented thus suggests that the amino acids and hydrocarbons found are not of the age of the sediments.

Nagy, B.↗

Acid phosphatase and protease activities in immobilized rat skeletal muscles

The effect of hind-limb immobilization on selected Iysosomal enzyme activities was studied in rat hing-limb muscles composed primarily of type 1. 2A, or 2B fibers. Following immobilization, acid protease and acid phosphatase both exhibited signifcant increases in their activity per unit weight in all three fiber types. Acid phosphatase activity increased at day 14 of immobilization in the three muscles and returned to control levels by day 21. Acid protease activity also changed biphasically, displaying a higher and earlier rise than acid phosphatase. The pattern of change in acid protease, but not acid phosphatase, closely parallels observed muscle wasting. The present data therefore demonstrate enhanced proteolytic capacity of all three fiber types early during muscular atrophy. In addition, the data suggest a dependence of basal hydrolytic and proteolytic activities and their adaptive response to immobilization on muscle fiber composition.

Witzmann, F. A.↗

The search for and identification of amino acids, nucleobases and nucleosides in samples returned from Mars

An investigation of the returned Mars samples for biologically important organic compounds, with emphasis on amino acid, the puring and pyrimidine bases, and nucleosides is proposed. These studies would be conducted on subsurface samples obtained by drilling past the surface oxidizing layer with emphasis on samples containing the larges quantities of organic carbon as determined by the rover gas chromatographic mass spectrometer (GCMS). Extraction of these molecules from the returned samples will be performed using the hydrothermal extraction technique described by Cheng and Ponnamperuma. More rigorous extraction methods will be developed and evaluated. For analysis of the extract for free amino acids or amino acids present in a bound or peptidic form, aliquots will be analyzed by capillary GCMS both before and after hydrolysis with 6N hydrochloric acid. Establishment of the presence of amino acids would then lead to the next logical step which would be the use of chiral stationary gas chromatography phases to determine the enatiomeic composition of the amino acids present, and thus potentially establish their biotic or abiotic origin. Confirmational analyses for amino acids would include ion-exchange and reversed-phase liquid chromatographic analysis. For analyses of the returned Mars samples for nucleobases and nucleosides, affinity and reversed-phase liquid chromatography would be utilized. This technology coupled with scanning UV detection for identification, presents a powerful tool for nucleobase and nucleoside analysis. Mass spectrometric analysis of these compounds would confirm their presence in samples returned form Mars.

Gehrke, Charles W.↗

Low to middle tropospheric profiles and biosphere/troposphere fluxes of acidic gases in the summertime Canadian taiga

We report features of acidic gases in the troposphere from 9 to 5000 m altitude above ground over the Canadian taiga in the summer of 1990. The measurements were conducted at a 30-m meteorological tower and from the NASA Wallops Electra aircraft as part of the joint U.S.-Canadian Arctic Boundary Layer Expedition (ABLE) 3B Northern Wetland Studies (NOWES). We sampled air for acidic gases using the mist chamber collector coupled with subsequent analysis using ion chromatography. At the tower we collected samples at two heights during a 13-day period, including diurnal studies. Using eddy flux and profile data, we estimated the biosphere/troposphere fluxes of nitric, formic, and acetic acids and sulfur dioxide. For the organic acids, emissions from the taiga in the afternoon hours and deposition during the predawn morning hours were observed. The flux intensities alone were however not high enough to explain the observed changes in mixing ratios. The measured deposition fluxes of nitric acid were high enough to have a significant influence on its mixing ratio in the boundary layer. On three days we measured vertical profiles of nitric, formic, and acetic acids through the lower to midtroposphere. We found that the chemical composition of the troposphere was extremely heterogenous. Pronounced layers of polluted air were readily apparent from our measurements. Local photochemical production and episodic long-range transport of trace components, originating from biomass burning and possibly industrial emissions, appear to have a strong influence on the composition of the troposphere and biosphere/troposphere fluxes of acidic gases at this site.

Klemm, O.↗

Microgravity Compatible Reagentless Instrumentation for Detection of Dissolved Organic Acids and Alcohols in Potable Water

The Organic Acid and Alcohol Monitor (OAAM) program has resulted in the successful development of a computer controlled prototype analyzer capable of accurately determining aqueous organic acids and primary alcohol concentrations over a large dynamic range with high sensitivity. Formic, acetic, and propionic acid were accurately determined at concentrations as low as 5 to 10 micrograms/L in under 20 minutes, or as high as 10 to 20 mg/L in under 30 minutes. Methanol, ethanol, and propanol were determined at concentrations as low as 20 to 100 micrograms/L, or as high as 10 mg/L in under 30 minutes. Importantly for space based application, the OAAM requires no reagents or hazardous chemicals to perform these analyses needing only power, water, and CO2 free purge gas. The OAAM utilized two membrane processes to segregate organic acids from interfering ions. The organic acid concentration was then determined based upon the conductiometric signal. Separation of individual organic acids was accomplished using a chromatographic column. Alcohols are determined in a similar manner after conversion to organic acids by sequential biocatalytic and catalytic oxidation steps. The OAAM was designed to allow the early diagnosis of under performing or failing sub-systems within the Water Recovery System (WRS) baselined for the International Space Station (ISS). To achieve this goal, several new technologies were developed over the course of the OAAM program.

Akse, James R.↗

The Production of Amino Acids in Interstellar Ices: Implications for Meteoritic Organics

Indigenous amino acids have been detected in a number of meteorites, over 70 in the Murchison meteorite alone. It has been generally accepted that the amino acids in meteorites formed in liquid water on an asteroid or comet parent-body. However, the water in the Murchison meteorite, for example, was depleted of deuterium, making the distribution of deuterium in organic acids in Murchison difficult to explain. Similarly, occasional but consistent meteoritic biases for non-terrestrial L amino acids cannot be reasonably rationalized by liquid water parent-body reactions. We will present the results of a laboratory demonstration showing that the amino acids glycine, alanine, and serine should result from the UV (ultraviolet) photolysis of interstellar ice grains. This suggests that some meteoritic amino acids may be the result of interstellar ice photochemistry, rather than having formed by reactions in liquid water. We will describe some of the potential implications of these findings for the organic materials found in primitive meteorites, in particular how interstellar ice synthesis might more easily accommodate the presence and distribution of deuterium, and the meteoritic bias for L amino acids.

Sandford, A.↗

Extraterrestrial Amino Acids in Orgueil and Ivuna: Tracing the Parent Body of CI Type Carbonaceous Chondrites

Amino acid analyses using HPLC of pristine interior pieces of the CI carbonaceous chondrites Orgueil and Ivuna have found that beta-alanine, glycine, and gamma-amino-n-butyric acid (ABA) are the most abundant amino acids in these two meteorites, with concentrations ranging from approx. 600 to 2,000 parts per billion (ppb). Other alpha-amino acids such as alanine, alpha-ABA, alpha-aminoisobutyric acid (AIB), and isovaline are present only in trace amounts (less than 200 ppb). Carbon isotopic measurements of beta-alanine and glycine and the presence of racemic (D/L 1) alanine and beta-ABA in Orgueil suggest that these amino acids are extraterrestrial in origin. In comparison to the CM carbonaceous chondrites Murchison and Murray, the amino acid composition of the CIs is strikingly distinct, suggesting that these meteorites came from a different type of parent body, possibly an extinct comet, than did the CM carbonaceous chondrites.

Meyer, Michael↗

Relative Amino Acid Concentrations as a Signature for Parent Body Processes of Carbonaceous Chondrites

Most meteorites are thought to have originated from objects in the asteroid belt. Carbonaceous chondrites, which contain significant amounts of organic carbon including complex organic compounds, have also been suggested to be derived from comets. The current model for the synthesis of organic compounds found in carbonaceous chondrites includes the survival of interstellar organic compounds and the processing of some of these compounds on the meteoritic parent body. The amino acid composition of five CM carbonaceous chondrites, two CIs, one CR, and one CV3 have been measured using hot water extraction-vapor hydrolysis, OPA/NAC derivatization and high-performance liquid chromatography (HPLC). Total amino acid abundances in the bulk meteorites as well as the amino acid concentrations relative to glycine = 1.0 for beta-alanine, alpha-aminoisobutyric acid and D-alanine were determined. Additional data for three Antarctic CM meteorites were obtained from the literature. All CM meteorites analyzed in this study show a complex distribution of amino acids and a high variability in total concentration ranging from approx. 15,300 to approx. 5800 parts per billion (ppb), while the CIs show a total amino acid abundance of approx. 4300 ppb. The relatively (compared to glycine) high AIB content found in all the CMs is a strong indicator that Strecker-cyanohydrin synthesis is the dominant pathway for the formation of amino acids found in these meteorites. The data from the Antarctic CM carbonaceous chondrites are inconsistent with the results from the other CMs, perhaps due to influences from the Antarctic ice that were effective during their residence time. In contrast to CMs, the data from the CI carbonaceous chondrites indicate that the Strecker synthesis was not active on their parent bodies.

Botta, Oliver↗

Determining D/L Ratios of Amino Acids Found in Ice Above Lake Vostok Using ESI/CIT Mass Spectroscopy

Astrobiology is an area where longevity of (micro) organisms is of great interest. Cryospheres are common phenomena in the solar system, particularly on satellites, comets and asteroids, as well as at least some of the planets. Recent data from the Mars Global Surveyor mission suggest the possibility of permafrost or perhaps even liquid water under the Martian surface [2]. These environments may be the areas in which the probability of finding life is the highest. This issue is of concern due to the probable evolution of planetary environments such as that of Mars from more hospitable to less hospitable conditions over the history of the solar system. In addition, evaluation of the possible transfer of living organisms between planets via impact ejecta [3] is dependent on knowledge of the maximum time periods over which microorganisms can remain dormant and subsequently revive and reproduce.Amino acid racemization dating, or aminostratigraphy, has been used for many years to date biological systems, and has been examined as a possible biosignature detection technique for Mars. We have suggested using amino acid racemization as one of the most indicative biosignatures [4]. Only life systems produce preferential synthesis of L-amino acids versus D-amino acids. Almost all amino acids in terrestrial organisms can be found only in the L-enantiomeric form.We studied the level of amino acid racemization, specifically of aspartic acid, in permafrost samples from eastern Siberia. Also we analyzed samples of ice from borehole drilled to lake Vostok, Antarctica.

A Tsapin↗

Nutritional value of protein hydrolysis products (oligopeptides and free amino acids) as a consequence of absorption and metabolism kinetics

When pigs were submitted to duodenal infusion of solutions containing a large percentage of small peptides (PEP) or free amino acids with the same pattern (AAL) amino acids appear in the portal blood more rapidly and more uniformly after infusion of PEP then after infusion of AAL, with the notable exception of methionine for which the opposite was true. These differences were lowered when a carbohydrate (maltose dextrin) was present in the solution, but nevertheless remained significant for the first hour after the infusion. The long-term (8-hour) uptake of free amino acids into the liver and the peripheral tissues differed in profile according to the nature of the duodenal infusion. Peripheral uptake was appreciably less well balanced after infusion of free amino acids (deficiency of threonine and phenylalanine) than after infusion of small peptides (deficiency of methionine). Accordingly, in the rat, under conditions of discontinuous enteral nutrition the mixture of small peptides was of greater nutritive value than the mixture of free amino acids. It thus appears that the absorption kinetics which results in important variations in the temporal distribution of free amino acids in the tissues may be at the origin of transitory imbalances in tissue amino acid uptake, and as a result of a lower nutritive value.

Intestinal Absorption/drug effects↗