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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 163 records · Page 9
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Quantifying Phospholipids in Organic Samples Using a Hydrophilic Interaction Liquid Chromatography–Inductively Coupled Plasma High-Resolution Mass Spectrometry (HILIC-ICP-HRMS) Method

Here, in this study, a novel method using hydrophilic interaction liquid chromatography (HILIC) coupled with inductively coupled plasma high-resolution mass spectrometry (ICP-HRMS) was introduced for the quantification of phospholipids in oil samples. The method employed a bridged ethyl hybrid (BEH) stationary phase HILIC column with a tetrahydrofuran (THF)/water mobile phase, enhancing the solubility and detection of phospholipids. During the study, a gradient/matrix effect on ICP-HRMS sensitivity was observed and successfully compensated for experimentally, ensuring reliable quantification results. This approach has proven effective for a wide range of different oil samples including vegetable oils, animal fats, and phospholipid supplements. Notably, this method allowed the direct quantification of phospholipids in oil samples, bypassing the need for prior sample preparation methods, such as solid phase extraction (SPE), thereby streamlining the analytical process. The precision, accuracy, and reduced need for extensive sample preparation offered by this method mark a significant advancement in lipids analysis. Its robustness and broad applicability have substantial implications for industries such as food and renewable energy production, where both efficient and accurate lipid identification and quantification are crucial.

09 BIOMASS FUELS↗
DOE OSTI2021

Absolute quantitation of propranolol from 200-μm regions of mouse brain and liver thin tissues using laser ablation-dropletProbe-mass spectrometry

Rationale: The ability to quantify drugs and metabolites in tissue with sub-mm resolution is a challenging but much needed capability in pharmaceutical research. To fill this void, a novel surface sampling approach combining laser ablation with the commercial dropletProbe automated liquid surface sampling system (LA-dropletProbe) was developed and presented here.Methods: Parylene C-coated 200 × 200 μm tissue regions of mouse brain and kidney thin tissue sections were analyzed for propranolol by laser ablation of tissue directly into a preformed liquid junction. Propranolol was detected by high performance liquid chromatography with positive ion mode electrospray ionization tandem mass spectrometry. Quantitation was achieved via application of a stable isotope-labeled internal standard and an external calibration curve.Results: Absolute concentration of propranolol determined from 200 × 200 µm tissue regions were compared to propranolol concentrations obtained from 2.3-mm-diameter tissue punches of adjacent, non-coated sections using standard bulk tissue extraction protocols followed by regular HPLC-MS/MS analysis. Average concentration of propranolol in both organs determined by the two employed methods agreed within ±12%. Furthermore, the relative abundance of phase II hydroxypropranolol glucuronide metabolites were recorded and found to be consistent with previous results.Conclusions: This work illustrates that depositing a thin parylene C layer onto thin tissue prior to analysis, which seals the surface and prevents direct liquid extraction of the drug from the tissue, coupled to the novel LA-dropletProbe surface sampling system is a viable approach for sub-mm resolution quantitative drug distribution analysis.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Synthesis and Characterization of Lignin-grafted-poly(ε-caprolactone) from Different Biomass Sources

Modification of lignin with poly(ε-caprolactone) is a promising approach to valorize industrial low-value lignins and to advance the bioeconomy. We have synthesized lignin grafted poly(ε-caprolactone) (lignin-g-PCL) copolymers via ring-opening polymerization of ε-caprolactone with different types of lignins of varying botanical sources (G-type pine lignin, S/G-type poplar lignin, and C-type Vanilla seeds lignin) and lignin extraction methods (Kraft and ethanol organosolv pulping). The lignin-g-PCL copolymer showed remarkably improved compatibility and dispersion in acetone, chloroform, and toluene in comparison to non-modified lignins. The structure and thermal properties of the lignin-g-PCL were investigated using Fourier-transform infrared spectroscopy (FTIR), 31 P nuclear magnetic resonance (NMR), 2D heteronuclear single quantum correlation (HSQC) NMR, gel permeation chromatography (GPC), and differential scanning calorimetry (DSC). Furthermore, we have found that all the technical lignins were reactive to the copolymerization reaction regardless of their plant source and isolation methods. The molecular weights of the synthesized lignin-g-PCL copolymers were positively correlated with the content of aliphatic lignin hydroxyls, suggesting that the copolymerization reaction tends to occur preferentially at the aliphatic hydroxyls rather than the phenolic hydroxyls of lignin. Thermal analyses of the lignin-g-PCL copolymers were studied, and in general, a reduction of melting temperature and crystallinity percentage in comparison to the neat PCL was observed. However, the thermal behavior of lignin-g-PCL copolymers varied depending on the lignin feedstocks employed in the copolymerization reaction.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Advanced Method Optimization with Categorical and Constrained Continuous Parameters

Traditional approaches to analytical method optimization (e.g., univariate and “guess-and-check”) can be time-consuming, costly, and often fail to identify true optima within the parameter space. Previous work defined and implemented a generalized technique for method optimization for continuous method parameters, but a knowledge gap remains for the incorporation of categorical variables into these advanced method optimization schemes. This work presents and validates a generalized optimization approach that incorporates both continuous and categorical variables while also utilizing a multivariate, multiobjective optimization scheme with Karush–Kuhn–Tucker conditions to bound the optimization space to solutions within the physical limitations of the parameter space. Method optimization from a case study using GC–MS for the analysis of 11 analytical standards with objectives to minimize peak width and maximize peak height resulted in a 3 orders of magnitude improvement in the average peak height and a 2 orders of magnitude improvement in the average peak width compared to the least optimal (but reasonable) instrumental parameters utilized in this study. This approach to optimization allows for a customizable method optimization in which users can include both continuous and categorical variables to achieve objectives specific to their analytical goals. This approach significantly reduces the labor and cost associated with traditional method development approaches and can be applied in a variety of scientific fields across a range of laboratory techniques (e.g., instrument method development, sample preparation, and extraction techniques).

Amorphous materials↗
DOE OSTI2021

Measuring Plant Metabolite Abundance in Spearmint ( Mentha spicata L.) with Raman Spectra to Determine Optimal Harvest Time

A fast field-deployable method utilizing Raman spectroscopy to determine the optimal harvest time of plants to extract the highest abundance of target metabolites is presented. Rosmarinic acid is a metabolite extracted from spearmint (Mentha spicata L.). Leaves from commercial “Native” and proprietary clonal line “KI110” spearmint were measured as a function of cell type and age to determine rosmarinic acid abundance. A linear regression model with leave-one-out cross-validation (R 2 CV = 0.61, RMSECV = 11.1 mg/g) was developed between selected Raman peak areas and rosmarinic acid concentrations determined by high-performance liquid chromatography (HPLC). A principal component analysis (PCA) model was also developed to determine rosmarinic acid abundance. The method may be suited to the analysis of many agriculturally relevant plant species and metabolites with distinct Raman peaks.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Advanced Analytical Methodologies Enable Feedstock Screening and Correlation to Pyrolysis Yields and Catalytic Upgrading

Pyrolysis of lignocellulosic biomass can serve as a powerful pathway for the generation of renewable fuels and industrial products. However, procurement of some biomass may be costly, especially when there is competition for alternative uses. Forestry and agricultural byproducts may serve as valuable pyrolysis feedstocks due to their high availability and low cost. Although waste products may fill demand for affordable pyrolysis feedstocks, they are often high in ash and extractives which contribute to unfavorable changes in pyrolysis vapor composition, as well as end products. The work presented here investigates the correlations between various pine anatomical fractions to understand their effect on pyrolysis oil composition for forest residues. Analytical pyrolysis coupled to direct analysis by molecular beam mass spectrometry (MBMS) provides real-time monitoring of pyrolysis vapor composition, even for compounds that are not amenable to gas chromatography. Statistical analysis of MBMS data from the fast pyrolysis (FP) of clean pine, cambium, twigs and branches, needles, bark, and a forest residue samples revealed that bark and needles made the greatest differences in the vapor composition of forest residues during pyrolysis and were enriched in resin acids, furfural derivatives, and ions that have been previously observed from catalysis corresponding to ash content. These results were also compared to catalytic fast pyrolysis (CFP) using a platinum on titania catalyst, and correlations between FP and CFP products were observed for the anatomical fractions. The forest residues and corresponding anatomical fractions from a stand of 23-year-old pine will be converted by fast pyrolysis in a bench-scale 2-inch fluidized-bed reactor, and statistical correlations between the bench-scale products and analytical-scale pyrolysis vapors will be shown. This work highlights the power of advanced analytical methodologies in determining the contributions of vapor components to catalytic pyrolysis outcomes for mixed feedstocks and demonstrates the use of analytical methodologies to better screen feedstocks prior to pyrolysis.

analytical↗
DOE OSTI2021

Saccharide analysis of onion outer epidermal walls

Abstract Background Epidermal cell walls have special structural and biological roles in the life of the plant. Typically they are multi-ply structures encrusted with waxes and cutin which protect the plant from dehydration and pathogen attack. These characteristics may also reduce chemical and enzymatic deconstruction of the wall for sugar analysis and conversion to biofuels. We have assessed the saccharide composition of the outer epidermal wall of onion scales with different analytical methods. This wall is a particularly useful model for cell wall imaging and mechanics. Results Epidermal walls were depolymerized by acidic methanolysis combined with 2M trifluoracetic acid hydrolysis and the resultant sugars were analyzed by high-performance anion-exchange chromatography with pulsed amperometric detection (HPAEC-PAD). Total sugar yields based on wall dry weight were low (53%). Removal of waxes with chloroform increased the sugar yields to 73% and enzymatic digestion did not improve these yields. Analysis by gas chromatography/mass spectrometry (GC/MS) of per- O -trimethylsilyl (TMS) derivatives of the sugar methyl glycosides produced by acidic methanolysis gave a high yield for galacturonic acid (GalA) but glucose (Glc) was severely reduced. In a complementary fashion, GC/MS analysis of methyl alditols produced by permethylation gave substantial yields for glucose and other neutral sugars, but GalA was severely reduced. Analysis of the walls by 13 C solid-state NMR confirmed and extended these results and revealed 15% lipid content after chloroform extraction (potentially cutin and unextractable waxes). Conclusions Although exact values vary with the analytical method, our best estimate is that polysaccharide in the outer epidermal wall of onion scales is comprised of homogalacturonan (~ 50%), cellulose (~ 20%), galactan (~ 10%), xyloglucan (~ 10%) and smaller amounts of other polysaccharides. Low yields of specific monosaccharides by some methods may be exaggerated in epidermal walls impregnated with waxes and cutin and call for cautious interpretation of the results.

09 BIOMASS FUELS↗
DOE OSTI2022

Nanolignin-based high internal phase emulsions for efficient protection of curcumin against UV degradation

As an emulsifier, lignin exhibits excellent UV resistance on drug-loaded emulsion systems for drug delivery. However, due to the structural variation and complexity of lignins from various origins, their UV shielding performance varies with the techniques for lignin extraction, which impacts properties and the protection efficiency of lignin-based HIPEs (high internal phase emulsions). In this work, lignin nanoparticles, prepared from three lignin preparations of Eucalyptus, were used in HIPEs delivery systems to protect curcumin from degradation by UV radiation. Structures of the lignin preparations were characterized using 2D HSQC (heteronuclear single-quantum coherence) NMR (nuclear magnetic resonance), 31 P NMR, and GPC (gel permeation chromatography). The residual curcumin level after 36h UV exposure in the nanolignin-based HIPEs was over 72%, much higher than that (< 10% after 24 h UV exposure) in the oil phase without lignin, indicating that the nanolignin-based HIPEs with enhanced UV shielding ability protect curcumin better. Of the three lignin preparations, AL (alkali lignin), with the lowest molecular weight, highest contents of phenolic hydroxyl and carboxyl groups, and highest S/G ratio, displayed the best anti-UV radiation ability and the most uniform nanoparticle size.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Bioremediation of heavy oily sludge: a microcosms study

Oily sludge is a residue from the petroleum industry composed of a mixture of sand, water, metals, and high content of hydrocarbons (HCs). The heavy oily sludge used in this study originated from Colombian crude oil with high density and low American Petroleum Institute (API) gravity. The residual waste from heavy oil processing was subject to thermal and centrifugal extraction, resulting in heavy oily sludge with very high density and viscosity. Biodegradation of the total petroleum hydrocarbons (TPH) was tested in microcosms using several bioremediation approaches, including: biostimulation with bulking agents and nutrients, the surfactant Tween 80, and bioaugmentation. Select HC degrading bacteria were isolated based on their ability to grow and produce clear zones on different HCs. Degradation of TPH in the microcosms was monitored gravimetrically and with gas chromatography (GC). The TPH removal in all treatments ranged between 2 and 67%, regardless of the addition of microbial consortiums, amendments, or surfactants within the tested parameters. The results of this study demonstrated that bioremediation of heavy oily sludge presents greater challenges to achieve regulatory requirements. Additional physicochemical treatments analysis to remediate this recalcitrant material may be required to achieve a desirable degradation rate.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2026

Oil in Alaska North Slope Gas Hydrate Reservoir: Micro-CT and Flow Simulation Insights into Permeability

Gas hydrate-bearing sands on the Alaska North Slope (ANS) host minor volumes of crude oil whose impact on formation permeability has never been quantified relative to a gas hydrate reservoir system. Here, we combine in situ pressure-core microcomputed-tomography (μ-CT), thermogravimetric analysis (TGA), gas-chromatography–mass-spectrometry (GC–MS), scanning-electron microscopy coupled with energy-dispersive spectroscopy (SEM-EDS), and Stokes-flow simulation to (i) quantify oil saturation, (ii) infer its source, and (iii) evaluate its influence on permeability after gas-hydrate dissociation. μ-CT and SEM-EDS imaging identify the host sediment as silty, with some grain-coating clay present. Eight representative 3003-voxel subvolumes extracted from a preserved pressure core (Core 15P-3c, from the B1 sand (unit B), HYDRATE 02 Geo Data Well (GDW), 886.96–887.29 m measured depth, MD) exhibit porosities of 0.34–0.37 and an average oil saturation of 0.09 ± 0.03, in comparison to an independent TGA-based estimate of 0.16. GC-MS fingerprints obtained from an adjacent depressurized core (Core 17P-1, 891.37–891.44 m MD), together with oil pore habit revealed by μ-CT, suggest that the oil is partly native but also includes contributions from mineral oil-based drilling fluid contamination. Further analysis of oil–porewater interactions and flushing tests confirms that native oil saturation in the analyzed samples ranges from 0.04 to 0.08 with an average of approximately 0.06, and the oil is highly immobile. Flow simulations demonstrate that the native oil saturation of ≈0.06 reduces permeability by approximately 50% due to both pore blockage and increased flow-path tortuosity. These findings reveal the potential presence of native oil within the ANS gas hydrate reservoir and suggest that future simulation models may need to account for its impact on permeability to improve long-term performance predictions of gas and water production.

02 PETROLEUM↗
DOE OSTI2022

Comparison and validation of the QuEChERSER mega-method for determination of per- and polyfluoroalkyl substances in foods by liquid chromatography with high-resolution and triple quadrupole mass spectrometry

Instances of food contamination with per- and polyfluoroalkyl substances (PFAS) continue to occur globally, but sample preparation and analytical methods are quite limited and often monitor for a small percentage of known PFAS. This study aimed to evaluate, validate, and compare performance of two instruments with the recently developed “quick, easy, cheap, effective, rugged, safe, efficient, and robust” (QuEChERSER) sample preparation mega-method – a method developed to monitor chemicals over a broad range of physicochemical properties. Initial evaluation of the QuEChERSER mega-method for determination of PFAS in food demonstrated recoveries, matrix interferences, and co-extractive removal comparable to (or better than) US Food and Drug Administration (FDA) and USDA Food Safety and Inspection Service (FSIS) methods. Subsequent validation of QuEChERSER in beef, catfish, chicken, pork, liquid eggs, and powdered eggs on a high-resolution mass spectrometer achieved acceptable recoveries (70–120%) and precision (RSDs ≤20%) for all 33 target analytes at the 1 and 5 ng g –1 levels and 67–88% of analytes at the 0.1 ng g –1 level, depending on the matrix. Additional validation was performed by tandem mass spectrometry on a triple quadrupole instrument. This approach provided no non-detects and better recoveries at the 0.1 ng g –1 level than the HRMS method but exhibited more variability at 1 and 5 ng g –1 spiking levels. Analysis of NIST SRMs 1946 and 1947 gave accuracies of 70–117%. Furthermore, these results demonstrate the capability of combining PFAS analysis with a mega-method previously validated for 350 analytes, while collecting non-target data for future retrospective analysis of emerging alternatives with a high-resolution mass spectrometry method.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Automated Coupling of Nanodroplet Sample Preparation with Liquid Chromatography–Mass Spectrometry for High-Throughput Single-Cell Proteomics

Single-cell proteomics can provide critical biological insight into the cellular heterogeneity that is masked by bulk-scale analysis. Here, we have developed a nanoPOTS (nanodroplet processing in one pot for trace samples) platform and demonstrated its broad applicability for single-cell proteomics. However, because of nanoliter-scale sample volumes, the nanoPOTS platform is not compatible with automated LC-MS systems, which significantly limits sample throughput and robustness. To address this challenge, we have developed a nanoPOTS autosampler allowing fully automated sample injection from nanowells to LC-MS systems. We also developed a sample drying, extraction, and loading workflow to enable reproducible and reliable sample injection. The sequential analysis of 20 samples containing 10 ng tryptic peptides demonstrated high reproducibility with correlation coefficients of >0.995 between any two samples. The nanoPOTS autosampler can provide analysis throughput of 9.6, 16, and 24 single cells per day using 120, 60, and 30 min LC gradients, respectively. As a demonstration for single-cell proteomics, the autosampler was first applied to profiling protein expression in single MCF10A cells using a label-free approach. At a throughput of 24 single cells per day, an average of 256 proteins was identified from each cell and the number was increased to 731 when the Match Between Runs algorithm of MaxQuant was used. Using a multiplexed isobaric labeling approach (TMT-11plex), ~77 single cells could be analyzed per day. We analyzed 152 cells from three acute myeloid leukemia cell lines, resulting in a total of 2558 identified proteins with 1465 proteins quantifiable (70% valid values) across the 152 cells. These data showed quantitative single-cell proteomics can cluster cells to distinct groups and reveal functionally distinct differences.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Mass Spectrometry Adduct Calculator

We describe the Mass Spectrometry Adduct Calculator (MSAC), an automated Python tool to calculate the adduct ion masses of a parent molecule. Here, adduct refers to a version of a parent molecule [M] that is charged due to addition or loss of atoms and electrons resulting in a charged ion, e.g. [M+H] + . MSAC includes a database of 2,341 potential ions and their mass-to-charge ratios (m/z) as extracted from the NIST/EPA/NIH Mass Spectral Library (NIST17), the Global Natural Products Social Molecular Networking Public Spectral Libraries (GNPS), and MassBank of North America (MoNA). The calculator relies on user-selected subsets of the combined database to calculate expected m/z for adducts of molecules supplied as formulas This tool is intended to help researchers create identification libraries to collect evidence for the presence of molecules in mass spectrometry data. While the included adduct database focuses on adducts typically detected during liquid chromatography-mass spectrometry analyses, users may supply their own lists of adducts and charge states for calculating expected m/z. We also analyzed statistics on adducts from spectra contained in the three selected mass spectral libraries. MSAC is freely available at https://github.com/pnnl/MSAC.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Assessing Structural, Thermal, and Functional Characteristics of Marigold Flower Protein as a Sustainable Food Ingredient

The demand for sustainable and alternative protein sources has been on the rise, driving interest in the valorization of underutilized plants. This study evaluated Calendula officinalis (marigold), a common floral waste, as a sustainable alternative protein source for the food industry. The primary objective of this study was to investigate the physicochemical properties of protein fractions from Calendula officinalis flower to evaluate their potential as a novel protein ingredient. Extraction of the Calendula officinalis flower yielded 92.17% of the crude protein. A sequential extraction of albumin, globulin, glutelin, and prolamin from marigold flower revealed albumin as the dominant fraction (65.47%) and exhibited the highest protein functionality, including water-holding capacity (2.37 g/g), oil-holding capacity (2.49 g/g), and emulsifying capacity (65.22 mL/g). Compared with other protein fractions, glutelin showed a relatively high emulsifying and foaming capacity (EC: 59.13 mL/g; FC: 16.23%). Differential scanning calorimetry revealed high thermal stability for albumin (T p = 105.28 °C) and glutelin (T p = 97.6 °C). Sodium Dodecyl Sulfate–Polyacrylamide Gel Electrophoresis (SDS-PAGE) and Liquid Chromatography–Mass Spectrometry (LC-MS) confirmed the presence of abundant low-molecular-weight polypeptides (<37 kDa), which enhanced emulsification, while scanning electron microscopy revealed porous structures aligned with hydration properties. Antioxidant activity was higher in albumin and glutelin, linked to surface hydrophobicity. LC-MS/MS identified 33 short-chain proteins, including oxidoreductase proteins and lipid-transfer proteins. Findings highlight marigold flower proteins as a sustainable, functional ingredient for a diverse range of food applications.

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

Cosmogenic 10 Be in pyroxene: laboratory progress, production rate systematics, and application of the 10 Be– 3 He nuclide pair in the Antarctic Dry Valleys

Here, we present cosmogenic- 10 Be and cosmogenic- 3 He data from Ferrar dolerite pyroxenes in surficial rock samples and a bedrock core from the McMurdo Dry Valleys, Antarctica, with the goal of refining the laboratory methods for extracting beryllium from pyroxene, further estimating the 10 Be production rate in pyroxene and demonstrating the applicability of 10 Be– 3 He in mafic rock. The ability to routinely measure cosmogenic 10 Be in pyroxene will open new opportunities for quantifying exposure durations and Earth surface processes in mafic rocks. We describe scalable laboratory methods for isolating beryllium from pyroxene, which include a simple hydrofluoric acid leaching procedure for removing meteoric 10 Be and the addition of a pH 8 precipitation step to reduce the cation load prior to ion exchange chromatography. 10 Be measurements in pyroxene from the surface samples have apparent 3 He exposure ages of 1–6 Myr. We estimate a spallation production rate for 10 Be in pyroxene, referenced to 3 He, of 3.6 ± 0.2 atoms g –1 yr –1 . 10 Be and 3 He measurements in the bedrock core yield initial estimates for parameters associated with 10 Be and 3 He production by negative-muon capture ($f_{10}^{*}$ = 0.00183 and $f_{3}^{*}f_{C}f_{D}$ = 0.00337). Next, we demonstrate that the 10 Be– 3 He pair in pyroxene can be used to simultaneously resolve erosion rates and exposure ages, finding that the measured cosmogenic-nuclide concentrations in our surface samples are best explained by 2–8 Myr of exposure at erosion rates of 0–35 cm Myr –1 . Finally, given the low 10 Be in our laboratory blanks (average of 5.7 × 10 3 atoms), the reported measurement precision, and our estimated production rate, it should be possible to measure 2 g samples with 10 Be concentrations of 6 × 10 4 and 1.5 × 10 4 atoms g –1 with 5 % and 15 % uncertainty, respectively. With this level of precision, Last Glacial Maximum to Late Holocene surfaces can now be dated with 10 Be in pyroxene. Application of 10 Be in pyroxene, alone or in combination with 3 He, will expand possibilities for investigating glacial histories and landscape change in mafic rock.

58 GEOSCIENCES↗
DOE OSTI2025

Deuterium Extraction from Helium with a Vanadium Vacuum Permeator: Commissioning of the Tritium Extraction eXperiment (TEX)

Here, the Tritium Extraction eXperiment (TEX) is a forced-convection lead-lithium (PbLi) loop in the Safety and Tritium Applied Research (STAR) facility at Idaho National Laboratory (INL) with the purpose of providing validation data for the vacuum permeator tritium extraction concept. A vanadium tube of 1000 mm length, 12.7 mm outside diameter, and 0.50 mm wall thickness is installed in the test section of TEX. The installed vanadium tube is characterized to quantify impurity concentrations, surface chemistry, and microstructure to elucidate permeation phenomena observed in experimentation. Herein, the permeation properties of the vanadium tube are characterized by measuring deuterium permeation at 300 °C, 325 °C, and 350 °C at 100 kPa, 125 kPa, and 150 kPa total pressures with 5000 ppm deuterium in helium gas mixture in a once-through flow configuration. The hydrogen isotope permeation through the vanadium tube in the test section is measured with quadrupole mass spectrometers and the hydrogen isotope concentration in the feed and retentate gas stream is measured with gas chromatography. The transient permeation results are modeled with MELCOR-TMAP, a thermal-hydraulic tritium transport code, and compared well with literature data.

70 - PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2023

Antifungal and Phytotoxic Activities of Isolated Compounds from Helietta parvifolia Stems

The identification of natural and environmentally friendly pesticides is a key area of interest for the agrochemical industry, with many potentially active compounds being sourced from numerous plant species. In this study, we report the bioassay-guided isolation and identification of phytotoxic and antifungal compounds from the ethyl acetate extract of Helietta parvifolia stems. We identified eight compounds, consisting of two coumarins and six alkaloids. Among these, a new alkaloid, 2-hydroxy-3,6,7-trimethoxyquinoline-4-carbaldehyde (6), was elucidated, along with seven known compounds. The phytotoxicity of purified compounds was evaluated, and chalepin (4) was active against Agrostis stolonifera at 1 mM with 50% inhibition of seed germination and it reduced Lemna pausicotata (duckweed) growth by 50% (IC50) at 168 μM. Additionally, we evaluated the antifungal activity against the fungal plant pathogen Colletotrichum fragariae using a thin-layer chromatography bioautography assay, which revealed that three isolated furoquinoline alkaloids (flindersiamine (3), kokusagenine (7), and maculine (8)) among the isolated compounds had the strongest inhibitory effects on the growth of C. fragariae at all tested concentrations. Our results indicate that these active natural compounds, i.e., (3), (4), (7), and (8), could be scaffolds for the production of more active pesticides with better physicochemical properties.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Trocylation of 3-quinuclidinol, a key marker for the chemical warfare agent 3-quinuclidinyl benzilate, for its enhanced detection at low levels in complex soil matrices by electron ionization gas chromatography–mass spectrometry

Detection of 3-quinuclidinol (3Q), a marker for the chemical warfare agent 3-quinuclidinyl benzilate, is very difficult by gas chromatography–mass spectrometry (GC/MS), providing low, broad signals even when analyzed in isolated form. Therefore, a method that can convert 3Q into a substrate with enhanced detectability by GC/MS would be an important tool for its analysis. 2,2,2-Trichloroethoxycarbonyl chloride (TrocCl) was used in the derivatization of 3Q in three different soils of varying composition and total organic content (Virginia type A soil, Nebraska EPA standard soil and Ottawa sand) when present at a 10 μg g -1 concentration in each. A direct derivatization protocol and one involving the pre-extraction of the analyte were evaluated for their individual efficiencies and subsequent analysis using electron ionization GC/MS. The practical derivatization of 3Q, when present at low levels (10 μg g -1 ) in three different soil matrices, was found to be rapid (1 h) and to take place smoothly at ambient temperature (and as low as 4°C). The method detection limit was determined to be 30 ng mL -1 for the Virginia type A soil, 49 ng mL -1 for the Nebraska EPA standard soil and 72 ng mL -1 for the Ottawa sand sample. An expedient and practical derivatization method for 3Q, a chemical warfare degradation product difficult to detect by GC/MS, has been realized using trichloroethyl chloroformate. The reaction provides 3Q-Troc, a derivative with better detectability than 3Q by electron ionization GC/MS such as peak sharpness and a unique mass spectrum for its unambiguous identification.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗