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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 703 records · Page 39
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Solid-Phase Synthesis of Three-Armed Star-Shaped Peptoids and Their Hierarchical Self-Assembly

Due to the branched structure feature and unique properties, a variety of star-shaped polymers have been designed and synthesized. Despite those advances, solid-phase synthesis of star-shaped sequence-defined synthetic polymers that exhibit hierarchical self-assembly remains a significant challenge. Hence, we present an effective strategy for the solid-phase synthesis of three-armed star-shaped peptoids, in which ethylenediamine was used as the centric star pivot. Based on the sequence of monomer addition, a series of AA'A''-type and ABB'-type peptoids were synthesized and characterized by UPLC-MS (ultra-high performance liquid chromatography-mass spectrometry). By taking advantage of the easy-synthesis and large side-chain diversity, we synthesized star-shaped peptoids with tunable functions. We further demonstrated the aqueous self-assembly of some representative peptoids into biomimetic nanomaterials with well-defined hierarchical structures, such as nanofibers and nanotubes. These results indicate that star-shaped peptoids offer the potential in self-assembly of biomimetic nanomaterials with tunable chemistries and functions.

Solid-phase synthesis, star-shaped peptoids, aqueo↗
DOE OSTI2018

Defining the mechanistic binding of viral particles to a multi‐modal anion exchange resin

A multi‐tiered approach to determine the binding mechanism of viral clearance utilizing a multi‐modal anion exchange resin was applied to a panel of four viral species that are typically used in validating viral clearance studies (i.e., X‐MuLV, MVM, REO3, and PrV). First, virus spiked buffer‐only experiments were conducted to evaluate the virus's affinity for single mode and multi‐modal chromatography resins under different buffer conditions in a chromatography column setting. From these results we hypothesize that the mechanisms of binding of the viruses involve binding to both the hydrophobic and anionic functional groups. This mechanistic view agreed with the general surface characteristics of the different virus species in terms of isoelectric point and relative hydrophobicity values. This hypothesized mechanistic binding was then tested with commercially relevant, in‐process materials, in which competitive binding occurred between the load components (e.g., viruses, target product, and impurities) and the resin. © 2018 American Institute of Chemical Engineers Biotechnol. Prog. , 34:1019–1026, 2018

Brown, Matthew R.↗
DOE OSTI2017

Effect of Autohydrolysis Pretreatment Conditions on Sugarcane Bagasse Structures and Product Distribution Resulting from Pyrolysis

Pyrolysis has been increasingly perceived as a promising technology to produce biofuel precursors (bio-oil) from agricultural residuals; however, there is a significant quality gap between a bio-oil and the fuels used for transportation. In this paper, we autohydrolyzed pretreated sugarcane bagasse at three different conditions (180 °C–10 min, 180 °C–40 min, 200 °C–40 min), then we investigated the effect of this pretreatment on a subsequent pyrolysis stage. High-pressure ion-exchange chromatography (HPIC) and the 13 C cross-polarization/magic angle spinning (CP/MAS) solid-state nuclear magnetic resonance (NMR) revealed that the autohydrolysis pretreatment significantly disrupted the hemicellulose fractions in the sugarcane bagasse and caused the breakage of lignin ether linkages in the sugarcane bagasse feedstocks. As the 31 P NMR results indicated, the autohydrolysis pretreatment removed carboxylic acid groups up to 66.7 %, which could significantly address the corrosion problem of bio-oils. Heteronuclear single quantum correlation (HSQC) analysis suggested that the autohydrolysis pretreatment effectively lowered the presence of the oxygenated aromatic compounds in the bio-oils. Finally, gel permeation chromatography (GPC) analysis of the bio-oils indicated that the oils from severely pretreated sugarcane bagasse pyrolyzed at a low temperature (i.e., 400 °C) contained lower-molecular-weight components similar to those present gasoline products.

09 BIOMASS FUELS↗
DOE OSTI2020

Comparative study on the novel umami‐active peptides of the whole soybeans and the defatted soybeans fermented soy sauce

Abstract BACKGROUND Two kinds of soy sauce produced via fermentation of the whole soybeans and the defatted soybeans (soy sauce termed ‘SSS’ and ‘SSD’, respectively) were subjected to the treatment using aqueous ethanol solutions with high concentrations. Then tasty peptides were separated from SSS and SSD by sensory guided fractionation, using macroporous resin and reverse‐phase high‐performance liquid chromatography (RP‐HPLC), and identified by ultra‐performance liquid chromatography quadrupole time‐of‐flight tandem mass spectrometry (UPLC‐Q‐TOF‐MS/MS). Results The result showed that umami‐active fractions and ≤ 3 kDa peptides were mainly concentrated in the supernatants resulted from the treatment with 60% ethanol and the precipitates resulted from the treatment with 80% ethanol. The contents of ammonia nitrogen, non‐salt solids, bitter amino acids, amino acids in peptides and the proportion of ≤ 3 kDa peptides in SSS were higher than those in SSD. Sixteen and fourteen tasty peptides were separated from SSS and SSD, among them five dipeptides (γ‐Glu‐Glu, Glu‐Glu, γ‐Glu‐Cys, γ‐Glu‐Leu, Glu‐Leu and Ile‐Glu) with a glutamic acid residue were identified both in SSS and SSD, which have been reported as umami/kokumi‐active peptides in soy sauce. Several peptides identified from SSS (Thr‐Gly‐Cys, Gly‐Leu‐Glu, Val‐Glu‐Ala‐Leu and Gly‐Gly‐Gly‐Glu) and SSD (Asp‐Arg, Asp‐Ala‐Glu, Glu‐Val‐Cys and Gly‐Gly‐Gly‐Glu) are tasty and/or umami‐active peptides but have not been reported as tasty peptides in the past. Conclusion Most of the peptides separated from SSD and SSS could impart an umami‐enhancing effect on soy sauce, and the marginally more kokumi and bitterness hydrophobic peptides were found in SSS than SSD. © 2020 Society of Chemical Industry

Zhu, Xiping↗
DOE OSTI2022

Broccoli seed extract rich in polysaccharides and glucoraphanin ameliorates DSS ‐induced colitis via intestinal barrier protection and gut microbiota modulation in mice

Abstract BACKGROUND Broccoli has received widespread attention because of its anti‐inflammatory and antioxidant effects. The present study aimed to explore the composition of broccoli seed extract (BSE) and its effect on colitis induced by dextran sulfate sodium (DSS). RESULTS BSE mainly comprises glucoraphanin and polysaccharides composed of arabinose, galactose, glucose and mannose. Animal experiments suggested that BSE intervention effectively reversed body weight loss, suppressed the levels of proinflammatory interleukin‐6, tumor necrosis factor‐α and interleukin‐1β, and elevated the levels of anti‐inflammatory interleukin‐10 and the activities of superoxide dismutase and glutathione in DSS‐induced colitis mice. According to histopathologic and immunohistochemical analysis of colon tissue, BSE intervention may repair the intestinal barrier by upregulating mRNA levels and the expression of tight junction proteins (claudin‐1, occludin and zonula occludens‐1). Gas chromatography–mass spectrometry (MS) analysis demonstrated that cecal short‐chain fatty acids in mice with BSE administration were significantly increased compared with the model group. Sulforaphane and sulforaphane‐ N ‐acetylcysteine were only detected in BSE group mice by ultra‐performance liquid chromatography‐MS analysis. In addition, BSE intervention evidently increased the abundance of Alistipeds , Coriobacteriaceae UCG‐002 and Bifidobacterium and decreased the abundance of Escheichia‐Shinella , Lachnospiraceae others , Parabacteroides , Ruminococcaceae others and Turicibacter , which possibly promoted carbohydrate metabolism and short‐chain fatty acid production. CONCLUSION The present study aimed to elucidate the effect of BSE on colitis and found that BSE, as a novel food ingredient, has great potential for the improvement of colitis. © 2022 Society of Chemical Industry.

Wu, Jiaying↗
DOE OSTI2023

Establishing the accuracy of position–specific carbon isotope analysis of propane by GC–pyrolysis–GC–IRMS

Rationale: Position-specific (PS) δ 13 C values of propane have proven their ability to provide valuable information on the evolution history of natural gases. Two major approaches to measure PS δ 13 C values of propane are isotopic 13 C nuclear magnetic resonance (NMR) and gas chromatography-pyrolysis-gas chromatography-isotope ratio mass spectrometry (GC-Py-GC-IRMS). Measurement accuracy of the isotopic 13 C NMR has been verified, but the requirements of large sample size and long experimental time limit its applications. GC-Py-GC-IRMS is a more versatile method with a small sample size, but its accuracy has not been demonstrated. Methods: We measured the PS δ 13 C values of propane from nine natural gases using both 13 C NMR and GC-Py-GC-IRMS, then evaluated the accuracy of the GC-Py-GC-IRMS method. Results: The results show that large carbon isotope fractionations occurred for both terminal and central carbons within propane during pyrolysis. The isotope fractionations during the pyrolysis are reproducible at optimum conditions, but vary between the two GC-Py-GC-IRMS systems tested, affected by experimental conditions (e.g., pyrolysis temperature, flow rate, and reactor conditions). Conclusions: It is necessary to evaluate and calibrate each GC-Py-GC-IRMS system using propane gases with accurately determined PS δ 13 C values. Finally, this study also highlights a need for PS isotope standards for propane and other molecules (e.g., butane and acetic acid).

03 NATURAL GAS↗
DOE OSTI2019

Effects of ball milling on the structure of cotton cellulose

Cellulose is typically characterized as a mixture of crystalline and amorphous material. A large part of the general understanding of the chemical, biochemical and physical properties of cellulosic materials is thought to depend on the consequences of the ratio of these components. For example, amorphous materials are said to be more reactive and have less tensile strength but comprehensive understanding and definitive analysis remain elusive. Ball milling has been used for decades to increase the ratio of amorphous material. The present work used 13 techniques to follow the changes in cotton fibers (nearly pure cellulose) after ball milling for 15, 45 and 120 min. X-ray diffraction results were analyzed with the Rietveld method; DNP (dynamic nuclear polarization) natural abundance 2D NMR studies in the next paper in this issue assisted with the interpretation of the 1D analyses in the present work. A conventional NMR model’s paracrystalline and inaccessible crystallite surfaces were not needed in the model used for the DNP studies. Sum frequency generation (SFG) spectroscopy also showed profound changes as the cellulose was decrystallized. Optical microscopy and field emission-scanning electron microscopy results showed the changes in particle size; molecular weight and carbonyl group analyses by gel permeation chromatography confirmed chemical changes. Specific surface areas and pore sizes increased. Fourier transform infrared (FTIR) and Raman spectroscopy also indicated progressive changes; some proposed indicators of crystallinity for FTIR were not in good agreement with our results. Thermogravimetric analysis results indicated progressive increase in initial moisture content and some loss in stability. Although understanding of structural changes as cellulose is amorphized by ball milling is increased by this work, continued effort is needed to improve agreement between the synchrotron and laboratory X-ray methods used herein and to provide physical interpretation of the SFG results.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Direct determination of cellulosic glucan content in starch-containing samples

A simple and highly selective analytical procedure is presented for the determination of cellulosic glucan content in samples that contain both cellulose and starch. This method eliminates the unacceptably large compounding errors of current two-measurement methods. If both starch and cellulose are present before analytical hydrolysis, both will be hydrolyzed to glucose causing bias and inaccuracy in the method. To prevent this interference, the removal of starch prior to cellulosic quantification is crucial. The method presented here is a concise in-series procedure with minimal measurements, eliminating large compounding errors. Sample preparation consists of a starch extraction employing enzymatic hydrolysis followed by a simple filtration and wash. The samples are then subjected to a two-stage acid hydrolysis. The concentration of glucose is determined by ion exchange high-performance liquid chromatography with a Pb 2+ column and a refractive index detector. The cellulosic glucan content is calculated based on the initial dry weight of the starting material. Data for the native biomass materials studied show excellent reproducibility, with coefficients of variance of 3.0% or less associated with the method. This selectivity for cellulosic glucan by the procedure was validated with several analytical techniques such as liquid chromatography coupled with mass spectrometry (LC–MS), Raman spectroscopy, and nuclear magnetic resonance.

09 BIOMASS FUELS↗
DOE OSTI2015

Production and isolation of homologs of flerovium and element 115 at the Lawrence Livermore National Laboratory Center for Accelerator Mass Spectrometry

Here, new procedures have been developed to isolate no-carrier-added (NCA) radionuclides of the homologs and pseudo-homologs of flerovium (Hg, Sn) and element 115 (Sb), produced by 12–15 MeV proton irradiation of foil stacks with the tandem Van-de-Graaff accelerator at the Lawrence Livermore National Laboratory Center for Accelerator Mass Spectrometry (CAMS) facility. The separation of 113 Sn from nat In foil was performed with anion-exchange chromatography from hydrochloric and nitric acid matrices. A cation-exchange chromatography method based on hydrochloric and mixed hydrochloric/hydroiodic acids was used to separate 124 Sb from nat Sn foil. A procedure using Eichrom TEVA resin was developed to separate 197 Hg from Au foil. These results demonstrate the suitability of using the CAMS facility to produce NCA radioisotopes for studies of transactinide homologs.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2021

Grazer-induced changes in molecular signatures of cyanobacteria

Algal biomass production is an emerging renewable source of fuels, nutrients, manufacturing materials, and pharmaceuticals. Industrial-scale production is predominantly performed in open raceway ponds that are inexpensive to build, operate, and maintain compared to closed bioreactors. However, these open pond systems suffer from increased opportunities for biological contamination from predators, pathogens, and competitors, which result in reduced biomass quality and yields and often the complete destruction of the crop over a short period of time. Early detection of contaminants is a necessary step of integrated pest management for triggering and informing interventions to prevent crop losses. To develop a sensitive method of detection utilizing mass spectrometry (MS), we used three methods – imaging mass spectrometry (imaging MS), liquid chromatography MS/MS (LC-MS/MS) combined with molecular networking, and gas chromatography MS/MS (GC–MS/MS) – to observe and identify molecular signatures from a model predator-prey system of the heterolobosean amoeba HGG1 preying on the filamentous cyanobacterium Anabaena sp. PCC 7120. Imaging MS enabled the association of molecules with the crop, the predator, or the activity of protozoan grazing, while LC-MS/MS-based molecular networking identified a subset of the grazing-specific signals as the chlorophyll breakdown products pyropheophytin, pheophorbide A, and pyropheophorbide. Application of MS techniques to other amoebacyanobacterial predator-prey pairs allowed categorization of grazing signatures as universal or specific to the species of prey, predator, or the prey-predator pairing, indicating that MS-based techniques can distinguish crops from competitors and potentially identify predators. Finally, GCMS/MS was shown to be capable of monitoring novel volatile organic compounds (VOCs), including those predicted to be released through chlorophyll breakdown, in the headspace over algal cultures under predation. Furthermore, these results demonstrate that the combination of multiple MS technologies creates a predictive framework to identify and catalog relevant molecular signatures for informing crop protection strategies.

09 BIOMASS FUELS↗
DOE OSTI2018

One 3-oxoacyl-(acyl-Carrier-protein) reductase functions as 17β-hydroxysteroid dehydrogenase in the estrogen-degrading Pseudomonas putida SJTE-1

Highlights: • A novel NAD-dependent 3-oxoacyl-(ACP) reductase induced by 17β-estradiol functions as the 17β-hydroxysteroid dehydrogenase. Pseudomonas putida SJTE-1 can utilize 17β-estradiol (E2) as its carbon source, while the enzymes for E2 transformation in this strain is still unclear. 17β-hydroxysteroid dehydrogenases (17β-HSD) can catalyze the reduction/oxidation at C{sub 17} site of steroid hormone specifically, critical for steroid transformation. Here a novel 3-oxoacyl-(acyl-carrier protein) (ACP) reductase (ANI02794.1) was identified as it could bβ-estradiol, and was proved to be capable of functioning as 17β-HSD. Sequences alignment showed it contained the two consensus regions and the conserved residues of short-chain dehydrogenase/reductase (SDR). Its encoding gene was cloned and over-expressed in Escherichia coli BL21(DE3) strain, and the recombinant protein was purified by the metal-ion affinity chromatography with the yield of 18 mg/L culture. HPLC (High Performance Liquid Chromatography) detection showed this enzyme could convert 17β-estradiol into estrone using NAD{sup +} as cofactor. Its K{sub m} value was 0.082 mM and its V{sub max} value was 0.81 mM/s; its transformation efficiency of 17β-estradiol into estrone was over 96.6% in five minutes. Its optimal temperature was 37 °C and optimal was pH 9.0; the divalent ions had different effects on the enzymatic activity. In conclusion, this 3-oxoacyl-ACP reductase functioned as 17β-HSD in P. putida SJTE-1 and played important role in its estrogen metabolism.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2021

Lipopolysaccharide associated with β-2,6 fructan mediates TLR4-dependent immunomodulatory activity in vitro

Levan, a β-2,6 fructofuranose polymer produced by microbial species, has been reported for its immunomodulatory properties via interaction with toll-like receptor 4 (TLR4) which recognises lipopolysaccharide (LPS). However, the molecular mechanisms underlying these interactions remain elusive. Here, we investigated the immunomodulatory properties of levan using thoroughly-purified and characterised samples from Erwinia herbicola and other sources. E. herbicola levan was purified by gel-permeation chromatography and LPS was removed from the levan following a novel alkali treatment developed in this study. E. herbicola levan was then characterised by gas chromatography–mass spectrometry and NMR. We found that levan containing LPS, but not LPS-depleted levan, induced TLR4-mediated cytokine production by bone marrow-derived dendritic cells and/or activated TLR4 reporter cells. These data indicated that the immunomodulatory properties of the levan toward TLR4-expressing immune cells were mediated by the LPS. This work also demonstrates the importance of LPS removal when assessing the immunomodulatory activity of polysaccharides.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2015

High-throughput platforms for metabolomics

We report that mass spectrometry has become a choice method for broad-spectrum metabolite analysis in both fundamental and applied research. This can range from comprehensive analysis achieved through time-consuming chromatography to the rapid analysis of a few target metabolites without chromatography. In this review article, we highlight current high-throughput MS-based platforms and their potential application in metabolomics. Although current MS platforms can reach throughputs up to 0.5. seconds per sample, the metabolite coverage of these platforms are low compared to low-throughput, separation-based MS methods. High-throughput comes at a cost, as it's a trade-off between sample throughput and metabolite coverage. As we will discuss, promising emerging technologies, including microfluidics and miniaturization of separation techniques, have the potential to achieve both rapid and more comprehensive metabolite analysis.

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

Ultrahigh performance LC/FT-MS non-targeted screening for biomass burning organic aerosol with MZmine2 and MFAssignR

In recent years, ultrahigh performance liquid chromatography Fourier transform mass spectrometry (LC/FT-MS) based non-targeted screening (NTS) methods have become increasingly popular for comprehensive analysis of complex organic mixtures. However, applying these methods for environmental complex mixture analysis is challenging due to the extreme complexity of natural samples and a lack of standard samples or surrogates for environmental complex mixtures. Furthermore, limited molecular markers in the databases and insufficient data processing software workflows make the application of these methods more challenging for environmental complex mixtures. In this work, we implement a new NTS data processing workflow to process data collected from ultrahigh performance liquid chromatography and Fourier transform Orbitrap Elite Mass Spectrometry (LC/FT-MS) by combining MZmine2 and MFAssignR, two opensource data processing tools and commercial Mesquite liquid smoke as a surrogate for biomass burning organic aerosol. MZmine2.53 data extraction followed MFAssignR molecular formula assignment offered noise free and highly accurate 1733 individual molecular formulas presented in liquid smoke with 4906 molecular species, including isomers. The results of this new approach were consistent with the results of direct infusion FT-MS analysis confirming its reliability. Over 90% of the molecular formulas presented in mesquite liquid smoke were matched with the molecular formulas of ambient biomass burning organic aerosol. This suggests the potential use of commercial liquid smoke as a surrogate for biomass burning organic aerosol research. Furthermore, the presented method significantly improves the identification of the molecular composition of biomass burning organic aerosol by successfully addressing some of the limitations related to the data analysis and giving a semi quantitative insight into the analysis.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2017

Advances in microscale separations towards nanoproteomics applications

Microscale separations (e.g., liquid chromatography or capillary electrophoresis) coupled with mass spectrometry (MS) has become the primary tool for advanced proteomics, an indispensable technology for gaining understanding of complex biological processes. While significant advances have been achieved in MS-based proteomics, the current platforms still face a significant challenge in overall sensitivity towards nanoproteomics (i.e., with less than 1 g total amount of proteins available) applications such as cellular heterogeneity in tissue pathologies. Herein, we review recent advances in microscale separation techniques and integrated sample processing systems that improve the overall sensitivity and coverage of the proteomics workflow, and their contributions towards nanoproteomics applications.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2023

Isomeric effects on the reactivity of branched alkenes: An experimental and kinetic modeling study of methylbutenes

Here, a detailed experimental study of the low-to-intermediate temperature combustion of methylbutene isomers, i.e., branched C 5 alkenes, has been undertaken with multiple experimental facilities. Ignition delay times were measured at equivalence ratios 0.5–2.0, 685–1020 K and up to 45 bar condition from two rapid compression machines and showed slight deviation from an Arrhenius behavior for all three isomers, while their reactivity order differs as temperature changes. Sampled intermediates formed during the oxidation process of mixtures at 900–1150 K and 0.82 bar from a flow reactor and at 730 K and 20 bar from a rapid compression machine were analyzed using gas chromatography techniques. Trends in the formation and consumption of sampled intermediates were modeled using a kinetic model developed in this work for all three isomers. Rate of production and sensitivity analyses emphasize the role of double bond-specific reactions governing the global reactivity of these fuels. Additional studies of the addition reactions of HO 2 radicals to the double bond and to allylic radicals may improve the model performance.

2-Methyl-1-butene↗
DOE OSTI2013

Increasing Confidence of LC-MS Identifications by Utilizing Ion Mobility Spectrometry

Ion mobility spectrometry in conjunction with liquid chromatography separations and mass spectrometry offers a range of new possibilities for analyzing complex biological samples. To fully utilize the information obtained from these three measurement dimensions, informatics tools based on the accurate mass and time tag methodology were modified to incorporate ion mobility spectrometry drift times for peptides observed in human serum. A reference human serum database was created using 12,139 peptides, tracking the monoisotopic mass, liquid chromatography normalized elution time, and ion mobility spectrometry drift time(s) for each peptide. We demonstrate that the use of three dimensions for peak matching during the peptide identification process resulted in increased numbers of identifications and lower false discovery rates relative to the use of only the mass and normalized elution time dimensions.

Environmental Molecular Sciences Laboratory↗