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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 253 records · Page 14
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

1,3,5-Trichloro-2,4,6-Trinitrobenzene: The Elusive Impurity Standard

1,3,5-triamino-2,4,6-trinitrobenzene (TATB) is an insensitive high explosive synthesized in two steps; 1,3,5-trichloro-2,4,6-trinitrobenzene (TCTNB) is the only intermediate. Due to solubility limitations, TATB is often dissolved in dimethylsulfoxide (DMSO) for liquid chromatography-mass spectrometry (LC–MS) analyses; however, DMSO is capable of participating in a wide variety of reactions. Intending to use it as an impurity standard, TCTNB was dissolved in DMSO. A stark color change from colorless to yellow accompanied by wavelength and ion chromatogram changes occurred over 24 hours. Three compounds were identified as causing the color change. All three were present in both acetone and DMSO solutions, but, overtime the absorbance spectra of the DMSO solution changed indicating an underlying reaction occurs between these compounds and DMSO. The chemical formulas of impurities present in the TCTNB sample as well as reaction products are identified via quadrupole time of flight mass spectrometry. The chemical structures are also proposed. The combination of the solvent system, ionization technique, and halogenated/nitrated aromatic ring structures resulted in substitutions of both the chlorine and nitro groups to hydroxyl groups. Furthermore, three proposed structures were closely related to TCTNB, but only one was detected at a consistent mass and absorbance wavelength in both acetone and DMSO. This compound had undergone a chlorine to hydroxyl substitution and should be utilized for TCTNB detection.

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

Molecular Dynamics Simulation of the Structures, Dynamics, and Aggregation of Dissolved Organic Matter

Dissolved organic matter (DOM) plays a significant role in the transport and transformation of pollutants in the aquatic environment. However, the experimental characterization of DOM has been limited mainly to bulk properties, and the molecular-level interactions among various components of DOM remain to be fully characterized. In this study, we use molecular dynamics (MD) simulations to probe the structural properties of model DOM systems at atomic detail. The 200 ns simulations, validated by available experimental data, reveal processes and mechanisms by which chemical species (cations, peptides, lipids, lignin, carbohydrates, and some low-molecular-weight aliphatic and aromatic compounds) aggregate to form complex DOM. The DOM aggregates are dynamic, consisting of a hydrophobic core and amphiphilic exterior. The lipid tails and other hydrophobic fragments form the core, with hydrophilic and amphiphilic groups exposed to water, making DOM accessible to both polar and nonpolar species. Thus, the lipid component acts as a nucleator, whereas cations (especially Ca 2+ ) connect the molecular fragments on the surface by coordinating with the O-containing functional groups of DOM. The structural details revealed here provide new insights including surface accessible atoms, overall assemblage, and interactions among the molecules of DOM for understanding the kinetics and mechanisms through which DOM interacts with metal and other contaminants.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS1982

Method of neutralizing the corrosive surface of amine-cured epoxy resins

The corrosive alkaline surface layer of an epoxy resin product formed by the curing of the epoxy with an aliphatic amine is eliminated by first applying a non-solvent to remove most or all of the free unreacted amine and then applying a layer of a chemical reagent to neutralize the unused amine or amine functional groups by forming a substituted urea. The surface then may be rinsed with acetone and then with alcohol. The non-solvent may be an alcohol. The neutralizing chemical reagent is a mono-isocyanate or a mono-isothiocyanate. Preferred is an aromatic mono-isocyanate such as phenyl isocyanate, nitrophenyl isocyanate and naplthyl isocyanate.

Lee, S. Y.↗
NASA NTRS1995

Polybenzimidazoles via aromatic nucleophilic displacement

Novel molecular weight controlled and endcapped polybenzimidazoles (PBI) are prepared by the aromatic nucleophilic displacement reaction of di(hydroxyphenyl benzimidazole) monomers with activated aromatic dihalides or activated aromatic dinitro compounds. The PBI are endcapped with mono(hydroxyphenyl) benzimidazoles. The polymerizations are carried out in polar aprotic solvents such as N-methyl-2-pyrrolidinone or N,N-dimethylacetamide using alkali metal bases such as potassium carbonate at elevated temperatures under nitrogen. Mono(hydroxyphenyl) benzimidazoles are synthesizedby reacting phenyl-4-hydroxybenzoate with aromatic (o-diamine)s in diphenylsulfone. Molecular weight controlled and endcapped PBI of new chemical structures are prepared that exhibit a favorable combination of physical and mechanical properties.

Connell, John W.↗
NASA NTRS1997

Polybenzimidazoles Via Aromatic Nucleophilic Displacement

Novel molecular weight controlled and endcapped polybenzimidazoles (PBI) are prepared by the aromatic nucleophilic displacement reaction of di(hydroxyphenylbenzimidazole) monomers with activated aromatic dihalides or activated aromatic dinitro compounds. The PBI are endcapped with mono(hydroxyphenyl)benzimidazoles. The polymerizations are carried out in polar aprotic solvents such as N-methyl-2-pyrrolidinone or N,N-dimethylacetamide using alkali metal bases such as potassium carbonate at elevated temperatures under nitrogen. Mono(hydroxyphenyl)benzimidazoles are synthesized by reacting phenyl-4-hydroxybenzoate with aromatic (o-diamine)s in diphenylsulfone. Molecular weight controlled and endcapped PBI of new chemical structures are prepared that exhibit a favorable combination of physical and mechanical properties.

Connell, John W.↗
NASA NTRS1995

Hydroxycinnamic acid-derived polymers constitute the polyaromatic domain of suberin

Suberin is an abundant, complex, intractable, plant cell wall polymeric network that forms both protective and wound-healing layers. Its function is, therefore, critical to the survival of all vascular plants. Its chemical structure and biosynthesis are poorly defined, although it is known to consist of both aromatic and aliphatic domains. While the composition of the aliphatic component has been fairly well characterized, that of the phenolic component has not. Using a combination of specific carbon-13 labeling techniques, and in situ solid state 13C NMR spectroscopic analysis, we now provide the first direct evidence for the nature of the phenolic domain of suberin and report here that it is almost exclusively comprised of a covalently linked, hydroxycinnamic acid-derived polymeric matrix.

NASA Discipline Plant Biology↗
NASA NTRS2005

The UV to Near-IR Optical Properties of PAHs: A Semi-Empirical Model

Interstellar Polycyclic Aromatic Hydrocarbon (PAH) infrared emission features represent an important and unique diagnostic tool of the chemical and physical conditions throughout the universe. However, one challenge facing the widely accepted PAH emission model has been the detection of infrared features in regions of low UV flux. Utilizing recently published laboratory Near Infrared VIR) PAH ion absorption data measured in our laboratory, we build upon previous models for PAH ion absorption in the UV-Vis to extrapolate a new model which incorporates PAH ion absorption in the NIR. This model provides a basis for comparing the relative energy absorption of PAH ions in the UV-Vis and NIR regions for a wide variety of stellar types. This model demonstrates that the radiation from late-type stars can pump the mid-IR PAH features.

Mattioda, A. L.↗
NASA NTRS1994

The Origins of Polycyclic Aromatic Hydrocarbons: Are They Everywhere?

During the past 15 years considerable progress in observational techniques has been achieved in the middle-infrared region (5000-500 per centimeter, 2-20 micron), the region where most diagnostic molecular vibrations occur. Spectra of many different astronomical infrared sources, some deeply embedded in dark molecular clouds and others at their edges, are now available. These spectra provide a powerful probe, not only for the identification of interstellar molecules in both the gas and solid phases, but also of the physical and chemical conditions which prevail in these two very different domains. The two lectures will focus on the evidence that polycyclic aromatic hydrocarbons (PAHs) are an important, ubiquitous and abundant interstellar species. PAHs are. extremely stable species which can range in size from a few angstroms across to several hundred angstroms (PAHs are also the building blocks of amorphous carbon particles). This identification rests on the suggestive agreement between the laboratory spectra of PAHs with a set of IR emission bands which emanate from many different sources where ultraviolet starlight impinges on a "dusty" region. The picture is that individual PAHs are first pumped into highly vibrationally excited states and relax by fluorescence at their fundamental vibrational frequencies. That PAHs are a ubiquitous interstellar component has serious ramifications in other spectral regions as well, including the strong extinction in the ultraviolet, and the classic visible diffuse interstellar bands discovered more than 50 years ago (but unexplained to this day) The first part of the course will focus on the interpretation of astronomical spectra. The second lecture will start by showing how recent laboratory data on PAHs taken under realistic interstellar conditions has con borated the PAH hypothesis and led to great insight into the conditions in the PAH containing regions. This lecture will end by reviewing the ever-increasing evidence for interstellar PAHs in meteorites and interplanetary dust particles. This in conjunction with the recent suggestion that PAHs are abundant in Jupiter's atmosphere will make the point that "PAHs are Everywhere".

Allamandola, L. J.↗
NASA NTRS1995

Plasma processing of interstellar PAHs into solar system kerogen

Processes resulting in the formation of hydrocarbons of carbonaceous chondrites and the identity of the interstellar molecular precursors involved are an objective of investigations into the origin of the solar system and perhaps even life on earth. We have combined the resources and experience of an astronomer and physicists doing laboratory simulations with those of a chemical expert in the analysis of meteoritic hydrocarbons, in a project that investigated the conversion of polycyclic aromatic hydrocarbons (PAHs) formed in stellar atmospheres into alkanes found in meteorites. Plasma hydrogenation has been found in the University of Alabama at Birmingham Astrophysics Laboratory to produce from the precursor PAH naphthalene, a new material having an IR absorption spectrum (Lee, W. and Wdowiak, T.J., Astrophys. J. 417, L49-L51, 1993) remarkably similar to that obtained at Arizona State University of the benzene-methanol extract of the Murchison meteorite (Cronin, J.R. and Pizzarello, S., Geochim. Cosmochim. Acta 54, 2859-2868, 1990). There are astrophysical and meteoritic arguments for PAH species from extra-solar sources being incorporated into the solar nebula, where plasma hydrogenation is highly plausible. Conversion of PAHs into alkanes could also have occurred in the interstellar medium. The synthesis of laboratory analogs of meteoritic hydrocarbons through plasma hydrogenation of PAH species is underway, as is chemical analysis of those analogs. The objective is to clarify this heretofore uninvestigated process and to understand its role during the origin of the solar system as a mechanism of production of hydrocarbon species now found in meteorites. Results have been obtained in the form of time-of-flight spectroscopy and chemical analysis of the lab analog prepared from naphthalene.

NASA Discipline Exobiology↗
DOE OSTI2021

Redundancy in Aromatic O -Demethylation and Ring-Opening Reactions in Novosphingobium aromaticivorans and Their Impact in the Metabolism of Plant-Derived Phenolics

ABSTRACT Lignin is a plant heteropolymer composed of phenolic subunits. Because of its heterogeneity and recalcitrance, the development of efficient methods for its valorization still remains an open challenge. One approach to utilize lignin is its chemical deconstruction into mixtures of monomeric phenolic compounds, followed by biological funneling into a single product. Novosphingobium aromaticivorans DSM 12444 has been previously engineered to produce 2-pyrone-4,6-dicarboxylic acid (PDC) from depolymerized lignin by simultaneously metabolizing multiple aromatics through convergent routes involving the intermediates 3-methoxygallic acid (3-MGA) and protocatechuic acid (PCA). We investigated enzymes predicted to be responsible for O -demethylation and oxidative aromatic ring opening, two critical reactions involved in the metabolism of phenolic compounds by N. aromaticivorans . The results showed the involvement of DesA in O -demethylation of syringic and vanillic acids, LigM in O- demethylation of vanillic acid and 3-MGA, and a new O- demethylase, DmtS, in the conversion of 3-MGA into gallic acid (GA). In addition, we found that LigAB was the main aromatic ring-opening dioxygenase involved in 3-MGA, PCA, and GA metabolism and that a previously uncharacterized dioxygenase, LigAB2, had high activity with GA. Our results indicate a metabolic route not previously identified in N. aromaticivorans that involves O -demethylation of 3-MGA to GA. We predict that this pathway channels ∼15% of the carbon flow from syringic acid, with the rest following ring opening of 3-MGA. The new knowledge obtained in this study allowed for the creation of an improved engineered strain for the funneling of aromatic compounds that exhibits stoichiometric conversion of syringic acid into PDC. IMPORTANCE For lignocellulosic biorefineries to effectively contribute to reduction of fossil fuel use, they need to become efficient at producing chemicals from all major components of plant biomass. Making products from lignin will require engineering microorganisms to funnel multiple phenolic compounds to the chemicals of interest, and N. aromaticivorans is a promising chassis for this technology. The ability of N. aromaticivorans to efficiently and simultaneously degrade many phenolic compounds may be linked to having functionally redundant aromatic degradation pathways and enzymes with broad substrate specificity. A detailed knowledge of aromatic degradation pathways is thus essential to identify genetic engineering targets to maximize product yields. Furthermore, knowledge of enzyme substrate specificity is critical to redirect flow of carbon to desired pathways. This study described an uncharacterized pathway in N. aromaticivorans and the enzymes that participate in this pathway, allowing the engineering of an improved strain for production of PDC from lignin.

Biotechnology & Applied Microbiology↗
DOE OSTI2020

Investigation of structural effects of aromatic compounds on sooting tendency with mechanistic insight into ethylphenol isomers

Small aromatic molecules with oxygen-containing functional groups are a promising class of fuel additives, as they can be readily sourced from depolymerized lignin. These oxygenated aromatic compounds (OACs) show a lower sooting tendency than aromatic hydrocarbons, but OACs having alkyl groups such as ethylphenol show a higher sooting tendency than other OACs such as phenol and anisole, despite the oxygen moiety. In this study, we investigate the relationship between chemical structure and soot precursor formation to explain observed differences in the sooting tendency of OACs and to gain insight into how alkyl or oxygenated substituents on the aromatic ring affect soot precursor formation. The weakest bond for 15 aromatic compounds was identified and cleavage of these bonds was shown to generate either benzyl or phenoxy radicals. A linear relationship between standard enthalpy of formation (ΔH f o ) of these radicals and the yield sooting index (YSI) was found, and thus ΔH f ° can be applied as a metric to estimate YSIs of various aromatic compounds; higher ΔH f o of a radical indicates an increase in the radical reactivity and leads to more soot precursor formation. Flow reactor experiments were performed for 2-ethylphenol and 3-ethylphenol to elucidate how ortho and meta substitution effects the sooting tendency. Soot precursors were identified from the experiment and their formation pathways were investigated computationally. 2-ethylphenol produces more oxygenated products than 3-ethylphenol since the ortho position has increased resonance stabilization of radical intermediates, which leads to lower YSI. Overall, these results further inform the selection of potential biomass-derived fuel blendstocks that have favorable sooting tendencies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2023

Heterogeneity and Chemical Reactivity of the Remote Troposphere Defined By Aircraft Measurements - Corrected

The NASA Atmospheric Tomography (ATom) mission built a photochemical climatology of air parcels based on in situ measurements with the NASA DC-8 aircraft along objectively planned profiling transects through the middle of the Pacific and Atlantic oceans. In this paper we present and analyze a data set of 10 s (2 km) merged and gap-filled observations of the key reactive species driving the chemical budgets of O3 and CH4 (O3, CH4, CO, H2O, HCHO, H2O2, CH3OOH, C2H6, higher alkanes, alkenes, aromatics, NOx, HNO3, HNO4, peroxyacetyl nitrate, and other organic nitrates), consisting of 146 494 distinct air parcels from ATom deployments 1 through 4. Six models calculated the O3 and CH4 photochemical tendencies from this modeling data stream for ATom 1. We find that 80 %–90 % of the total reactivity lies in the top 50 % of the parcels and 25 %–35 % in the top 10 %, supporting previous model-only studies that tropospheric chemistry is driven by a fraction of all the air. Surprisingly, the probability densities of species and reactivities averaged on a model scale (100 km) differ only slightly from the 2 km ATom 10 s data, indicating that much of the heterogeneity in tropospheric chemistry can be captured with current global chemistry models. Comparing the ATom reactivities over the tropical oceans with climatological statistics from six global chemistry models, we find generally good agreement with the reactivity rates for O3 and CH4. Models distinctly underestimate O3 production below 2 km relative to the mid-troposphere, and this can be traced to lower NOx levels than observed. Attaching photochemical reactivities to measurements of chemical species allows for a richer, yet more constrained-to-what-matters, set of metrics for model evaluation.

Tropospheric Chemistry↗
NASA NTRS1977

Sulfur compounds in coal

The literature on the chemical structure of the organic sulfur compounds (or functional groups) in coal is reviewed. Four methods were applied in the literature to study the sulfur compounds in coal: direct spectrometric and chemical analysis, depolymerization in drastic conditions, depolymerization in mild conditions, and studies on simulated coal. The data suggest that most of the organic sulfur in coal is in the form of thiophenic structures and aromatic and aliphatic sulfides. The relative abundance of the sulfur groups in bituminous coal is estimated as 50:30:20%, respectively. The ratio changes during processing and during the chemical analysis. The main effects are the transformation during processing of sulfides to the more stable thiophenic compounds and the elimination of hydrogen sulfide.

Attar, A.↗
NASA NTRS1979

Carbon fiber modification

The effect of several chemical treatments on the electrical and mechanical properties of carbon fibers was investigated with an optimum goal of increasing the electrical resistivity by a factor of 1000 without appreciably changing the mechanical properties. It was possible to effect resistivity increases from 10 to 50 percent without adversely affecting the tensile strength or Young's modulus for T-300 and C-6000 PAN fibers by treatments with either AlCl3 or nitric acid mixtures. Larger increases in the resistivity were produced with pitch fibers treated with nitric acid mixtures. This treatment also produced a partial decomposition of the pitch fiber and deterioration of the mechanical properties. The rationale behind the approch was to immobilize the conductivity producing pi electrons in the microscopic aromatic structure of the carbon fibers without destroying the strength producing sigma bonds. The investigations indicate that certain chemical treatments can produce such results, but the total reduction in the electrical conductivity which was achieved was not large enough to impact on problems which might arise from the high conductivities of the fibers.

Thompson, T. E.↗
DOE OSTI2025

Enhancing the Value of Wasted and Stranded Natural Gas Resources Through Conversion Into Aromatics Using Microwaves

Natural gas flaring results in the waste of significant amounts of valuable domestic energy resources while also producing undesirable environmental impacts. Transforming natural gas into value-added chemicals via direct nonoxidative reactions presents a compelling alternative to flaring. However, traditional thermal reactor systems face challenges due to thermodynamic limitations and poor catalyst stability. Microwave-assisted reactions offer a sustainable, on-demand approach for chemical production from natural gas, suitable for compact, flexible reactor systems at the well-site that can be powered by renewable energy. This method offers a novel, non-traditional approach in catalyst activation and product selectivity compared to a conventional thermal method, potentially leading to faster rates, higher selectivities, and higher conversion efficiencies. Despite these advantages, challenges exist, such as the low microwave-sensitivity of the state-of-the-art zeolite catalyst that is highly active for the methane dehydroaromatization reaction. This presentation will discuss recent research from the National Energy Technology Laboratory concerning microwave-assisted natural gas conversion directly into aromatics. It will address the difficulties with microwave heating of traditional thermochemical catalysts, and the application of Multiphysics modeling to understand temperature and field strength in the reactor, to enhance chemical conversion. The presentation will also cover how heating aids can mitigate heating challenges and transform microwave catalysis into a quasi-thermal kinetic problem. Additionally, catalyst activation and deactivation under microwave conditions will be examined, along with the future outlook and needs for microwave enhanced catalysis applications.

catalysis↗
DOE OSTI2024

Gas–Phase Preparation of the 14π Hückel Polycyclic Aromatic Anthracene and Phenanthrene Isomers (C 14 H 10 ) via the Propargyl Addition–BenzAnnulation (PABA) Mechanism

Polycyclic aromatic hydrocarbons (PAHs) imply the missing link between resonantly stabilized free radicals and carbonaceous nanoparticles, commonly referred to as soot particles in combustion systems and interstellar grains in deep space. Whereas gas phase formation pathways to the simplest PAH – naphthalene (C 10 H 8 ) – are beginning to emerge, reaction pathways leading to the synthesis of the 14π Hückel aromatic PAHs anthracene and phenanthrene (C 14 H 10 ) are still incomplete. Here, by utilizing a chemical microreactor in conjunction with vacuum ultraviolet (VUV) photoionization (PI) of the products followed by detection of the ions in a reflectron time-of-flight mass spectrometer (ReTOF-MS), the reaction between the 1'- and 2'-methylnaphthyl radicals (C 11 H 9 •) with the propargyl radical (C 3 H 3 •) accesses anthracene (C 14 H 10 ) and phenanthrene (C 14 H 10 ) via the Propargyl Addition–BenzAnnulation (PABA) mechanism in conjunction with a hydrogen assisted isomerization. Furthermore, the preferential formation of the thermodynamically less stable anthracene isomer compared to phenanthrene suggests a kinetic, rather than a thermodynamics control of the reaction.

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

Effect of Solvent on the Interaction of Lignin with a Zeolite Nanosheet in the Condensed Phase

Lignin is the essential building block of lignocellulosic biomass, an excellent renewable source of different aromatic monomers for the polymer and biofuel industry. The depolymerization of lignin into value-added chemicals and fuels through the catalytic process poses a significant challenge due to the complex structure of lignin. Understanding lignin’s conformational diversity and dynamics in the liquid phase is crucial to designing an effective depolymerization process. Here, we conducted all-atom molecular dynamics simulations to understand the conformation and dynamics of softwood lignin on the all-silica zeolite nanosheet based on the MFI topology in a binary mixture of water–methanol at three different molar compositions (0%, 50%, and 100% methanol). We observed that the methanol–surface interaction is stronger than the water–surface interaction, and methanol readily diffused into the MFI core. Lignin surface contacts decrease with increasing methanol composition due to higher solubility and dynamics. Lignin dynamics on the surface in neat water is an order of magnitude smaller than methanol. Here, we also found that lignin adopts a slightly extended conformation when it stays on the surface than in the bulk solution phase for the pure water case, whereas for pure methanol and the binary solution structures are statistically similar.

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

Complete Genome Sequences of Four Natural Pseudomonas Isolates That Catabolize a Wide Range of Aromatic Compounds Relevant to Lignin Valorization

Many soil microorganisms have evolved catabolic strategies to utilize phenolic compounds arising from depolymerized lignin. We report the complete genome sequences of four Pseudomonas sp. isolates that demonstrated robust growth on a wide range of aromatic monomers and dimers that are relevant to the valorization of lignin into value-added chemicals.

59 BASIC BIOLOGICAL SCIENCES↗