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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 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Thermal and photoinduced chemistry of the aromatic Criegee intermediate, benzaldehyde oxide: Implications for indoor air quality

Essential oils contain a complex mixture of volatile organic compounds, ranging from terpenes to aromatics. When released into the indoor air environment or into the atmosphere, they may undergo oxidation to generate complex reactive intermediates that affect indoor air quality. Cinnamaldehyde is one such aromatic molecule that is abundant in essential oils. When released into the indoor air environment, it may undergo oxidation to form a carbonyl oxide (Criegee intermediate) with an aromatic substituent: benzaldehyde oxide. In this manuscript, we present a high-level quantum chemical study that shows that, unlike smaller atmospherically relevant Criegee intermediates, benzaldehyde oxide is expected to undergo solar photolysis on timescales that are competitive with its ground state unimolecular and bimolecular chemistry. We show that aromatic substitution leads to a drastic bathochromic shift in the spectroscopically relevant excited states, revealing that photolysis in the indoor or outdoor environment should not be neglected when modeling the climate and air quality implications of Criegee intermediates with extended conjugation. Here, we predict a range of products that may be important for forming lower volatility compounds via tropospherically relevant photochemistry. To motivate future experimental validation of our results, we propose a viable synthetic procedure of the relevant precursor for generating and stabilizing benzaldehyde oxide.

atmospheric photochemistry↗
DOE OSTI2020

Amphiphile Organization in Organic Solutions: An Alternative Explanation for Small-Angle X-ray Scattering Features in Malonamide/Alkane Mixtures

In this work, the role of different intermolecular interactions in the aggregation of amphiphiles in an organic solvent is studied for systems of relevance to liquid-liquid extraction (LLE), a chemical process used to selectively recover metals from complex mixtures. Of specific interest is the role, or lack thereof, of hydrogen bonding, which is often assumed to be a main driver of the organic phase structural organization that has been linked to separation efficacy. Toward that end, a series of malonamide extractants in n-dodecane have been studied in the absence of any extracted aqueous solutes, including water. The series of extractants includes N,N'-dimethyl-N,N'-dibutyltetradecylmalonamide (DMDBTDMA), two of its homologs, and N,N'-dimethyl-N,N'-dioctylhexylethoxymalonamide (DMDOHEMA). This simplified model LLE system enables systematic investigation of the role of dipole-dipole and alkyl tail steric interactions in amphiphile aggregation. Small-angle X-ray scattering (SAXS) profiles computed from molecular dynamics trajectories are in good agreement with experimental SAXS data. Molecular dynamics simulations show that malonamide aggregation results from dipole-driven self-association and lacks characteristic aggregate sizes. Mid-q correlation peaks in the SAXS profiles emerge at high concentration for each malonamide. In those densely packed solutions, the correlation peaks are observed to result from alkyl tail-induced spacing between electron-rich polar head groups, with peak positions determined by the different alkyl tail lengths present in the malonamide molecule. This explanation of the SAXS correlation peaks contrasts with the prevailing literature, which attributes mesoscale features observed in small-angle scattering to the formation of microemulsions. Instead, this work finds that these features are present in the absence of water or any reverse micellar organization of the malonamides. As such, molecular-scale malonamide self-association and packing, rather than microemulsion-based colloidal-scale descriptions, is a more appropriate framework for these LLE systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1997

Gas Chromatographic Detectors for Exobiology Flight Experiments

Exobiology flight experiments require highly sensitive instrumentation for in situ chemical analysis of the volatile chemical species that occur in the atmospheres and surfaces of various bodies within the solar system. The complex mixtures encountered place a heavy burden on the analytical instrumentation to detect and identify all species present. Future missions to Mars', comets, or planetary moons such as Europa, will perform experiments with complex analyses. In addition, instrumentation for such missions must perform under severely restricted conditions with limited resources. To meet these analytical requirements, improved methods and highly sensitive yet smaller instruments must continually be developed with increasingly greater capabilities. We describe here efforts to achieve this objective, for past and future missions, through the development of new or the improvement of existing sensitive, miniaturized gas chromatographic detectors.

Kojiro, Daniel R.↗
NASA NTRS2011

The Use of ATLAS Data to Quantify Surface Radiative Budgets in Four US Cities

The additional heating of the air over the city is the result of the replacement of naturally vegetated surfaces with those composed of asphalt, concrete, rooftops and other manmade materials. The temperatures of these artificial surfaces can be 20 to 40 C higher than vegetated surfaces. This produces a dome of elevated air temperatures 5 to 8 C greater over the city, compared to the air temperatures over adjacent rural areas. This effect is called the "urban heat island". Urban landscapes are a complex mixture of vegetated and non-vegetated surfaces. It is difficult to take enough temperature measurements over a large city area to. The use of remotely sensed data from airborne scanners is ideal to characterize the complexity of urban albedo and radiant surface temperatures. The National Aeronautics and Space Administration (NASA) Airborne Thermal and Land Applications Sensor (ATLAS) operates in the visual and IR bands was used to collect data from Salt Lake City, UT, Sacramento, CA, Baton Rouge, LA. And San Juan, Puerto Rico with the main objective of investigating the Urban Heat Island (UHI). In this presentation we will examine the techniques of analyzing remotely sensed data for measuring the effect of various urban surfaces on their contribution to the urban heat island effect.

Luvall, Jeffrey↗
DOE OSTI2022

Quantification of gas concentrations in NO/NO 2 /C 3 H 8 /NH 3 mixtures using machine learning

We employ machine learning to decode the composition of unknown gas mixtures from the output of an array of four electrochemical sensors. The sensors use metal oxide electrodes paired with a ceramic electrolyte, yttria-stabilized zirconia (YSZ), to produce voltage responses to the presence of gases in complex mixtures. The voltages from the sensor array serve as inputs to a machine learning pipeline which first carries out multi-class classification of mixtures into types based on which gases are present at non-zero concentrations, and subsequently predicts gas concentrations given the mixture type. Thus, our model is able to take a single reading from the sensor array in response to gas mixtures involving NO, NO 2 , C 3 H 8 , and NH 3 , and output a highly accurate prediction of which gases are present in the mixture, along with the concentrations of each constituent gas. Of note, our computational framework can be easily expanded to include additional gases and additional mixture types, allowing it to be used in numerous automotive, industrial and environmental monitoring settings.

47 OTHER INSTRUMENTATION↗
NASA NTRS1982

Analysis of volatile metabolites in biological fluids as indicators of prodromal disease condition

The volatile profile cannot be defined as a single class of substances, rather it is a broad spectrum of materials of different polarities characterized by having a boiling-point in the low to medium range (up to approximately 300 C) and the fact that the compounds are suitable for gas chromatography without derivatization. The organic volatile profiles are very complex mixtures of metabolic byproducts, intermediates, and terminal products of enzymatic degradations composed mainly of alcohols, ketones, aldehydes, pyrazines, sulfides, isothiocyanates, pyrroles, and furans. The concentration of organic volatiles in biological fluids covers a wide range with many important components present at trace levels. The complexity of the organic volatile fraction requires the use of capillary columns for their separation.

Zlatkis, A.↗
NASA NTRS1976

Monitoring complex trace-gas mixtures by long-path laser absorption spectrometry

Laser-based spectrophotometric methods, which have been proposed for the detection of trace concentrations of gaseous contaminants, include Raman and passive radiometry. The paper discusses a simple long-path laser absorption method which is capable of resolving complex mixtures of closely related trace contaminants at ppm levels. A number of species were selected which are most likely to accumulate in closed environments, such as submarines or long-duration manned space flights. Absorption coefficients at CO2 laser wavelengths were measured, accurate to + 3 per cent or better, for each of these species. This data base was then used to determine the presence and concentration of the contaminants in prepared mixtures of 12 to 15 gases. Computer programs have been developed which will permit a real-time analysis of the monitored atmosphere. Minimum detectable concentrations for individual species are generally in the ppm range, and are not seriously degraded by interferences even in complex mixtures. Estimates of the dynamic range of this monitoring technique for various system configurations and comparison with other methods of analysis are discussed

Green, B. D.↗
DOE OSTI2022

Mass spectrometry-based technologies for probing the 3D world of plant proteins

Abstract Over the past two decades, mass spectrometric (MS)-based proteomics technologies have facilitated the study of signaling pathways throughout biology. Nowhere is this needed more than in plants, where an evolutionary history of genome duplications has resulted in large gene families involved in posttranslational modifications and regulatory pathways. For example, at least 5% of the Arabidopsis thaliana genome (ca. 1,200 genes) encodes protein kinases and protein phosphatases that regulate nearly all aspects of plant growth and development. MS-based technologies that quantify covalent changes in the side-chain of amino acids are critically important, but they only address one piece of the puzzle. A more crucially important mechanistic question is how noncovalent interactions—which are more difficult to study—dynamically regulate the proteome’s 3D structure. The advent of improvements in protein 3D technologies such as cryo-electron microscopy, nuclear magnetic resonance, and X-ray crystallography has allowed considerable progress to be made at this level, but these methods are typically limited to analyzing proteins, which can be expressed and purified in milligram quantities. Newly emerging MS-based technologies have recently been developed for studying the 3D structure of proteins. Importantly, these methods do not require protein samples to be purified and require smaller amounts of sample, opening the wider proteome for structural analysis in complex mixtures, crude lysates, and even in intact cells. These MS-based methods include covalent labeling, crosslinking, thermal proteome profiling, and limited proteolysis, all of which can be leveraged by established MS workflows, as well as newly emerging methods capable of analyzing intact macromolecules and the complexes they form. In this review, we discuss these recent innovations in MS-based “structural” proteomics to provide readers with an understanding of the opportunities they offer and the remaining challenges for understanding the molecular underpinnings of plant structure and function.

Plant Sciences↗
DOE OSTI2025

Inverse mapping of properties to composition through generative modeling for designing molten salts

Generative modeling (GM) has been increasingly used for the inverse design and optimization of materials, yet its application to molten salt mixtures remains unexplored despite how a successful approach to the inverse design of molten salts would contribute to efficiently exploiting their customizability and unlocking their advantages in applications, such as energy production and energy storage. This work presents a workflow for the inverse design of molten salts with targeted density values, addressing the challenge of representing these complex mixtures in GM. A dataset of critically evaluated molten salt densities is used to train a variational autoencoder coupled with a predictive deep neural network, which then can be used to generate new molten salt compositions with desired density values. The effectiveness of the approach is demonstrated by designing mixtures with distinct densities and validating the predicted values using ab initio molecular dynamics simulations.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2025

Coordinated Cation Transport in Ti 3 C 2 T x MXene Membranes

Membrane nanofiltration is an attractive strategy for the selective recovery of high-demand metals from wastewater and brine. Effective sieving of ions in aqueous environments will require precise control over membranes’ nanochannel size and chemistry. Ti 3 C 2 T x MXene is an environmentally stable 2D material that can be processed into laminar membranes containing nanoscale interlayer spaces. The MXene interlayer environment depends on the ion species and amount of water intercalated between MXene sheets, and it is the major factor governing permeation and selectivity through MXene membranes. Coordinated ion–ion and ion-interlayer dynamics in the presence of complex mixtures can impact ion permeability and selectivity. Herein, we observe strong competitive effects between different cations (Li + , Na + , and Ca 2+ ) in binary mixtures, resulting in reduced selectivity when compared with single-salt permeability ratios. X-ray diffraction, molecular dynamics, and density functional theory simulations support the conclusion that cations with stronger attraction to MXene flakes can preferentially occupy the MXene nanochannels and hinder other ions via charge or size exclusion. In conclusion, elucidation of ion transport behavior in MXene under complex conditions will allow for more rational design of efficient ion-sieving membranes.

2D Materials↗
DOE OSTI2021

Repository scale classification and decomposition of tandem mass spectral data

Various studies have shown associations between molecular features and phenotypes of biological samples. These studies, however, focus on a single phenotype per study and are not applicable to repository scale metabolomics data. Here we report MetSummarizer, a method for predicting (i) the biological phenotypes of environmental and host-oriented samples, and (ii) the raw ingredient composition of complex mixtures. We show that the aggregation of various metabolomic datasets can improve the accuracy of predictions. Since these datasets have been collected using different standards at various laboratories, in order to get unbiased results it is crucial to detect and discard standard-specific features during the classification step. We further report high accuracy in prediction of the raw ingredient composition of complex foods from the Global Foodomics Project.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Microfluidic In-Situ Spectrophotometric Approaches to Tackle Actinides Analysis in Multiple Oxidation States

The study and development of present and future processes for the treatment/recycling of spent nuclear fuels require many steps, from design in the laboratory to setting up on an industrial scale. In all of these steps, analysis and instrumentation are key points. For scientific reasons (small-scale studies, control of phenomena, etc.) but also with regard to minimizing costs, risks, and waste, such developments are increasingly carried out on milli- or microfluidic devices. The logic is the same for the chemical analyses associated with their follow-up and interpretation. Due to this, over the last few years, opto–microfluidic analysis devices adapted to the monitoring of different processes (dissolution, liquid–liquid extraction, precipitation, etc.) have been increasingly designed and developed. In this work, we prove that photonic lab-on-a-chip (PhLoC) technology is fully suitable for all actinides concentration monitoring along the plutonium uranium refining extraction (plutonium, uranium, reduction, extraction, or Purex) process. Several PhLoC microfluidic platforms were specifically designed and used in different nuclear research and development (R&D) laboratories, to tackle actinides analysis in multiple oxidation states even in mixtures. The detection limits reached (tens of µmol·L −1 ) are fully compliant with on-line process monitoring, whereas a range of analyzable concentrations of three orders of magnitude can be covered with less than 150 µL of analyte. Finally, this work confirms the possibility and the potential of coupling Raman and ultraviolet–visible (UV–Vis) spectroscopies at the microfluidic scale, opening the perspective of measuring very complex mixtures.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
NASA NTRS1993

Contamination on LDEF: Sources, distribution, and history

An introduction to contamination effects observed on the Long Duration Exposure Facility (LDEF) is presented. The activities reported are part of Boeing's obligation to the LDEF Materials Special Investigation Group. The contamination films and particles had minimal influence on the thermal performance of the LDEF. Some specific areas did have large changes in optical properties. Films also interfered with recession rate determination by reacting with the oxygen or physically shielding underlying material. Generally, contaminant films lessen the measured recession rate relative to 'clean' surfaces. On orbit generation of particles may be an issue for sensitive optics. Deposition on lenses may lead to artifacts on photographic images or cause sensors to respond inappropriately. Particles in the line of sight of sensors can cause stray light to be scattered into sensors. Particles also represent a hazard for mechanisms in that they can physically block and/or increase friction or wear on moving surfaces. LDEF carried a rather complex mixture of samples and support hardware into orbit. The experiments were assembled under a variety of conditions and time constraints and stored for up to five years before launch. The structure itself was so large that it could not be baked after the interior was painted with chemglaze Z-306 polyurethane based black paint. Any analysis of the effects of molecular and particulate contamination must account for a complex array of sources, wide variation in processes over time, and extreme variation in environment from ground to launch to flight. Surface conditions at certain locations on LDEF were established by outgassing of molecular species from particular materials onto adjacent surfaces, followed by alteration of those species due to exposure to atomic oxygen and/or solar radiation.

Pippin, Gary↗
NASA NTRS2019

Carbon Nanostructures in Biological Sensors for Space and Terrestrial Applications

Biosensing devices comprised of carbon nanotubes and nanofibers have been developed for astronaut crew point-of-care. Their inherent nanometer scale, high conductivity, wide potential window, good biocompatibility and well-defined surface chemistry make them ideal candidates as biosensor electrodes. Here, we report two studies using carbon nanotube and carbon nanofiber electrodes for biomedical applications. First, a 3x3 electrode device, with each electrode containing 40,000 carbon nanofiber nanoelectrodes was fabricated on silicon using traditional microfabrication processing. The device was demonstrated as a multiplexed immunosensor for simultaneous, label-free detection of cardiac troponin-I, C-reactive protein and myoglobin. Antibodies specific to cardiac troponin-I, C-reactive protein and myoglobin were covalently bound to the CNF surface and were characterized using electrochemical impedance spectroscopy and differential pulse voltammetry. Each step of the modification process resulted in changes in resistance to charge transfer due to the changes at the electrode surface upon antibody immobilization and binding to the specific cardiac protein. The real-time label free detection of the three cardiac markers from pure components and mixtures was demonstrated with high sensitivity, down to 0.2 ng/mL, and good selectivity. Detection in human blood serum did not present false positives from non-specific protein adsorption. More recently, this detection scheme has been applied to inkjet printed carbon nanotube electrodes on Kapton and paper. Printed devices have several unique advantages including simple and inexpensive fabrication. The results demonstrate that these sensors can serve a miniaturized, low cost device for detection of proteins in complex mixtures making this platform a good candidate for early stage diagnosis of myocardial infarction. Future inkjet printed devices can be fabricated have the added advantage in their suitability to be manufactured in an in-space, microgravity environment.

carbon nanotubes↗
NASA NTRS2019

Carbon Nanomaterials for Biosensing Applications

Biosensing devices comprised of carbon nanotubes and nanofibers have been developed for astronaut crew point-of-care. Their inherent nanometer scale, high conductivity, wide potential window, good biocompatibility and well-defined surface chemistry make them ideal candidates as biosensor electrodes. Here, we report two studies using carbon nanotube and carbon nanofiber electrodes for biomedical applications. First, a 3x3 electrode device, with each electrode containing 40,000 carbon nanofiber nanoelectrodes was fabricated on silicon using traditional microfabrication processing. The device was demonstrated as a multiplexed immunosensor for simultaneous, label-free detection of cardiac troponin-I, C-reactive protein and myoglobin. Antibodies specific to cardiac troponin-I, C-reactive protein and myoglobin were covalently bound to the CNF surface and were characterized using electrochemical impedance spectroscopy and differential pulse voltammetry. Each step of the modification process resulted in changes in resistance to charge transfer due to the changes at the electrode surface upon antibody immobilization and binding to the specific cardiac protein. The real-time label free detection of the three cardiac markers from pure components and mixtures was demonstrated with high sensitivity, down to 0.2 ng/mL, and good selectivity. Detection in human blood serum did not present false positives from non-specific protein adsorption. More recently, this detection scheme has been applied to inkjet printed carbon nanotube electrodes on Kapton and paper. Printed devices have several unique advantages including simple and inexpensive fabrication. The results demonstrate that these sensors can serve a miniaturized, low cost device for detection of proteins in complex mixtures making this platform a good candidate for early stage diagnosis of myocardial infarction. Future inkjet printed devices can be fabricated have the added advantage in their suitability to be manufactured in an in-space, microgravity environment.

carbon nanotubes↗
NASA NTRS1982

A reexamination of the RB-SR isotopic systematics of lunar breccia 12013

Lunar breccia 12013 is one of the few rocks for which isotopic evidence has been interpreted as indicating a 4.5-AE age, and it is the only lunar rock which contains abundant granitic material that may date back to the initial lunar differentiation. An investigation of 12013 conducted by Quick et al. (1981) has led to the conclusion that 12013 is an extremely complex mixture of impact-generated melt and clastic components of uncertain affinities. It was found that the granitic component in 12013 need not be any older than 4.16-4.17 AE. In the present study a model is presented for the Rb-Sr evolution of 12013 which explains the isotopic data without resorting to a 4.5-AE age for any component. Attention is given to petrographic constraints, isotopic investigations, and an evaluation of the Rb-Sr isotopic data. It is concluded that lunar rock 12013 is an extremely complex polymict breccia in which the Rb-Sr isotopic systematics have been greatly influenced by mixing during breccia formation and by subsequent reequilibration.

Quick, J. E.↗
DOE OSTI2023

Comparing Top-Down Proteoform Identification: Deconvolution, PrSM Overlap, and PTM Detection

Generating top-down tandem mass spectra (MS/MS) for complex mixtures of proteoforms has become possible through improvements in fractionation, on-line separation, dissociation, and mass analysis. The algorithms to match tandem mass spectra to sequences have undergone a parallel evolution, with both spectral alignment and peak matching being paired with diverse methods for scoring proteoform-spectral matches (PrSMs). This study assesses state-of-the-art algorithms for top-down identification through three distinct challenges. The first is identifying a large yield of PrSMs while controlling false discovery rate (FDR) in identifying thousands of proteoforms from complex cell lysates via four software workflows: ProSight Proteome Discoverer, TopPIC, Informed Proteomics, and pTop. The second is the deconvolution of data from both Thermo Orbitrap-class and Bruker maXis Q-TOF instruments to produce consistent precursor charge and mass determinations while generating fragment mass lists to optimize identification. The third attempts to detect diverse post-translational modifications (PTMs) in proteoforms from cow milk and human ovarian tissue. The data demonstrate that existing software suites produce admirable sensitivity, in some cases identifying a third of collected tandem mass spectra with FDR controlled below 2%; the overlap in these PrSMs, however, illustrates real value in searching data with multiple search engines. Differences among identification workflows seem to result from each search algorithm incorporating its own deconvolution algorithm. By transmitting deconvolution data from multiple deconvolution routes (Thermo Xtract, Bruker Auto MSn, Mascot Distiller, TopFD, and FLASHDeconv) to the downstream TopPIC search algorithm, we were able to detect common causes of deconvolution disagreement. The detection of PTMs was very inconsistent among search algorithms, with some workflows suggesting as little as 1% of PrSMs from cow’s milk were singly-phosphorylated while other workflows found that 18% of PrSMs were singly-phosphorylated. Taken together, these results make a strong argument for top-down researchers to adopt a standard practice of analyzing each MS/MS experiment with at least two different search engines.

59 BASIC BIOLOGICAL SCIENCES↗
NASA NTRSDate not supplied

Determining Chlamydomonas reinhardtii resistance to ionizing radiation at a genome-wide scale

Spaceflight is a complex mixture of abiotic stresses that causes a myriad of cellular responses including increased genome-wide mutation load. The impact of spaceflight on mutation load is not well understood for most organisms and is especially critical to characterize for candidate microorganisms that could be part of biological life support systems. Prior research in our laboratory revealed an unexpectedly high level of mutation during spaceflight in the eukaryotic green algae, C. reinhardtii. Based on the spectrum of base changes observed, we concluded that the mutations were generated through a molecular mechanism unique to the spaceflight environment. Spaceflight is a complex set of stresses, and we are using an Earth-based analog to test ionizing radiation as a potential causative variable for the unique mutation spectrum observed in spaceflight. C. reinhardtii was grown exposed to chronic radiation from a Cesium-137 source. Four biological replicate cultures of wild-type cells were grown in gas permeable plastic tissue culture bags in liquid media following the design used on the International Space Station (ISS) during the previous space algae experiment. Radiation levels for this experiment approximate ionizing radiation observed on the moon, in low Earth orbit (LEO), and on Earth. Cells from each replicate were passaged to inoculate the next cycle of growth, then samples were taken from each culture to characterize cell morphology, quantify biomass, and extract DNA. Whole genome sequencing from each culture will be used to identify the frequency and types of mutations in each radiation level. In growth cycles 3 and 4, there was a significant increase in biomass accumulation under lunar radiation level compared to LEO or Earth radiation levels. These results such that ionizing radiation affected growth of C. reinhardtii.

Microbiology↗