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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 379 records · Page 21
All sourcesNASA NTRSDOE OSTI
NASA NTRS2008

Molecules for Fluorescence Detection of Specific Chemicals

A family of fluorescent dye molecules has been developed for use in on-off fluorescence detection of specific chemicals. By themselves, these molecules do not fluoresce. However, when exposed to certain chemical analytes in liquid or vapor forms, they do fluoresce (see figure). These compounds are amenable to fixation on or in a variety of substrates for use in fluorescence-based detection devices: they can be chemically modified to anchor them to porous or non-porous solid supports or can be incorporated into polymer films. Potential applications for these compounds include detection of chemical warfare agents, sensing of acidity or alkalinity, and fluorescent tagging of proteins in pharmaceutical research and development. These molecules could also be exploited for use as two-photon materials for photodynamic therapy in the treatment of certain cancers and other diseases. A molecule in this family consists of a fluorescent core (such as an anthracene or pyrene) attached to two end groups that, when the dye is excited by absorption of light, transfer an electron to the core, thereby quenching the fluorescence. The end groups can be engineered so that they react chemically with certain analytes. Upon reaction, electrons on the end groups are no longer available for transfer to the core and, consequently, the fluorescence from the core is no longer quenched. The chemoselectivity of these molecules can be changed by changing the end groups. For example, aniline end groups afford a capability for sensing acids or acid halides (including those contained in chemical warfare agents). Pyridine or bipyridyl end groups would enable sensing of metal ions. Other chemicals that can be selectively detected through suitable choice of end groups include glucose and proteins. Moreover, the fluorescent cores can be changed to alter light-absorption and -emission characteristics: anthracene cores fluoresce at wavelengths around 500 nm, whereas perylene cores absorb and emit at wavelengths of about 600 nm.

Fedor, Steve↗
NASA NTRS2009

Detecting Airborne Mercury by Use of Polymer/Carbon Films

Films made of certain polymer/carbon composites have been found to be potentially useful as sensing films for detecting airborne elemental mercury at concentrations on the order of tens of parts per billion or more. That is to say, when the polymer/carbon composite films are exposed to air containing mercury vapor, their electrical resistances decrease by measurable amounts. Because airborne mercury is a health hazard, it is desirable to detect it with great sensitivity, especially in enclosed environments in which there is a risk of a mercury leak from lamps or other equipment. The present effort to develop polymerbased mercury-vapor sensors complements the work reported in NASA Tech Briefs Detecting Airborne Mercury by Use of Palladium Chloride (NPO- 44955), Vol. 33, No. 7 (July 2009), page 48 and De tecting Airborne Mer cury by Use of Gold Nanowires (NPO-44787), Vol. 33, No. 7 (July 2009), page 49. Like those previously reported efforts, the present effort is motivated partly by a need to enable operation and/or regeneration of sensors under relatively mild conditions more specifically, at temperatures closer to room temperature than to the elevated temperatures (greater than 100 C ) needed for regeneration of sensors based on noble-metal films. The present polymer/carbon films are made from two polymers, denoted EYN1 and EYN2 (see Figure 1), both of which are derivatives of poly-4-vinyl pyridine with amine functional groups. Composites of these polymers with 10 to 15 weight percent of carbon were prepared and solution-deposited onto the JPL ElectronicNose sensor substrates for testing. Preliminary test results showed that the resulting sensor films gave measurable indications of airborne mercury at concentrations on the order of tens of parts per billion (ppb) or more. The operating temperature range for the sensing films was 28 to 40 C and that the sensor films regenerated spontaneously, without heating above operating temperature (see Figure 2).

Shevade, Abhijit↗
NASA NTRS2016

Environmental Temperature Effect on the Far-Infrared Absorption Features of Aromatic-Based Titan's Aerosol Analogs

Benzene detection has been reported in Titans atmosphere both in the stratosphere at ppb levels by remote sensing and in the thermosphere at ppm levels by the Cassini's Ion and Neutral Mass Spectrometer. This detection supports the idea that aromatic and heteroaromatic reaction pathways may play an important role in Titans atmospheric chemistry, especially in the formation of aerosols. Indeed, aromatic molecules are easily dissociated by ultraviolet radiation and can therefore contribute significantly to aerosol formation. It has been shown recently that aerosol analogs produced from a gas mixture containing a low concentration of aromatic and/or heteroaromatic molecules (benzene, naphthalene, pyridine, quinoline and isoquinoline) have spectral signatures below 500/cm, a first step towards reproducing the aerosol spectral features observed by Cassini's Composite InfraRed Spectrometer (CIRS) in the far infrared. In this work we investigate the influence of environmental temperature on the absorption spectra of such aerosol samples, simulating the temperature range to which aerosols, once formed, are exposed during their transport through Titans stratosphere. Our results show that environmental temperature does not have any major effect on the spectral shape of these aerosol analogs in the far-infrared, which is consistent with the CIRS observations.

Gautier, Thomas↗
NASA NTRS2014

Titan Aerosol Analog Absorption Features Produced from Aromatics in the Far Infrared

We present results on the formation of Titan aerosol analogs produced via far-UV irradiation of five aromatic precursors: benzene, naphthalene, pyridine, quinoline and isoquinoline. This is the first reported evidence of far-IR emission features observed below 200 per cm in laboratory-created Titan aerosols. These laboratory studies were motivated by recent analyses of Cassini Composite Infrared Spectrometer (CIRS) spectra that show a broad aerosol emission feature in the far-IR spectral region centered near 140 per cm, which is unique to Titan's photochemically-produced aerosol. We find that all three of the aerosol analogs formed from nitrogen-containing aromatics have similar broad emission features near that of the observed CIRS far-IR aerosol spectral feature. In addition, the inclusion of 1.5% methane to that of trace amounts of benzene also gives rise to an aerosol with a weak far-IR emission feature located below 200 per cm.

atmosphere↗
NASA NTRS2026

Molecular Inventory and Comparative Organic Profiling of A Homogenized Aggregate Sample From Asteroid (101955) Bennu

Evaluating the distribution and diversity of solvent-soluble organic molecules in extraterrestrial materials provide information about the physicochemical environments where prebiotic chemistry occurred and is essential for assessing the inventory of prebiotic compounds available to the early Earth. In this work, we conducted a comprehensive molecular characterization of solvent-soluble organic compounds in a homogenized aggregate sample (ID: OREX-800107-128) of unsorted regolith from asteroid (101955) Bennu returned by NASA’s OSIRIS-REx mission. Using two-dimensional gas chromatography coupled with high-resolution time-of-flight mass spectrometry (GC×GC-HRMS), we identified 87 organic compounds across several molecular classes, including alkanes, polycyclic aromatic hydrocarbons, and nitrogen-, oxygen-, and sulfur-bearing species. Comparison with the organic inventory of CI (Orgueil), C2-ungrouped (Tagish Lake and Tarda), and CM2 (Murchison) carbonaceous chondrites revealed that Bennu sample OREX-800107-128 is most similar to Tagish Lake and Tarda yet compositionally distinct from all of these meteorites. This Bennu sample exhibits a relatively high abundance of low-molecular-weight aromatics (e.g., toluene), pyridine derivatives, and sulfur species such as dimethyl sulfite, consistent with episodic low-temperature aqueous alteration. The presence of these organic compounds suggests that this material experienced chemically diverse processes in the parent body conducive to complex organic synthesis, including aldol condensation reactions responsible for N- and O-bearing compounds. We also compared the molecular distributions of this Bennu sample and previously analyzed samples from (162173) Ryugu to assess potential common origins between these two carbonaceous asteroids. Bennu shows more chemically diverse and nitrogen-rich organic materials than Ryugu. While both asteroids share broadly similar primitive compositions, the observed chemical differences indicate distinct evolutionary histories within a likely common formation environment though whether Bennu and Ryugu derive from a single compositionally heterogeneous parent body or from multiple closely related progenitors remains unresolved. Further detailed comparative analyses of material from Bennu, Ryugu, and specific carbonaceous meteorites (e.g., Tagish Lake and Tarda) will provide new insights into how the N-rich molecular profile observed in Bennu samples was formed and evolved in the outer Solar System.

sample return↗
DOE OSTI2020

Heteroatom-doped porous carbons for clean energy applications and methods for their synthesis

Methods for a facile, template free and one-step synthesis of nanoporous carbons by using a heterocyclic aromatic organic compound as a single source precursor of both carbon and nitrogen are described. The heterocyclic aromatic organic compound contains nitrogen in pyrrolic and/or pyridinic positions and is chemically activated with NaOH, KOH or ZnCl2 at high temperatures in a solid state mixture as a synthesis protocol to promote fine micropores during carbonization. Nanoporous carbons synthesized by these methods that have superior gas sorption/storage and energy storage properties are also described. The nanoporous carbons are useful as carbon sequestration agents and supercapacitors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Ion-imbibed membranes based on proton conducting aromatic polyether type copolymers and their application in redox flow batteries

The present invention relates to a class of polymer ion imbibed membranes for electrolyte flow batteries. The membranes are a conducting aromatic polyether type copolymer bearing nitrogen heterocycles groups, especially pyridine type. While the membranes can be used in acid, basic, and neutral electrolytes, the nitrogen heterocycles in the membrane interact with acid in the electrolyte to form a proton transport network, so as to keep the proton transport performance of the membrane. The membrane has excellent mechanical stability and thermostability as well as tunable porosity.

Paloumbis, George↗
DOE OSTI2024

Products and methods for organ protection with noble nanoparticles

Products and methods for redirecting the pathological biochemical process of accumulation of reduced pyridine nucleotides under deleterious hypoxia conditions toward the reduction of the precursor salt and the biosynthesis of biologically compatible, antioxidant noble metal nanoparticles and the simultaneous restoring of the tissue redox state are provided. The products and methods have application in the treatment of hypoxia and hypoxia-related diseases and disorders. Such products and methods are also useful in organ transplantation and recovery, in screening of anti-hypoxia agents, and in detecting elevated levels of the reducing equivalents of the redox state, for example, NADH, NADPH, GSH, and TrxSH 2 , in cells, tissues, or organs.

Rozhkova, Elena A.↗
DOE OSTI2025

Exploring the influence of transition metals on f-element bonding

The United States aims to triple its nuclear energy production by 2050, which will result in increased uranium usage and spent nuclear fuel generation. This highlights the need for a comprehensive understanding of actinide coordination chemistry, which is crucial for the extraction, processing, purification, and fabrication of uranium-based fuels. Moreover, it is vital for the reprocessing or safe disposal of nuclear waste and effective remediation efforts. Achieving this successfully requires an in-depth understanding of f-electron behavior, as “the role of 5f electrons in bond formation remains a fundamental topic in actinide chemistry”. Introducing a second metal into the system can increase structural dimensionality and diversify structural architecture. Heterometallic systems can also alter material properties, such as magnetic and spectroscopic characteristics, luminescence, and actinide mobility. Additionally, secondary transition metals, even when present only in the second coordination sphere and not directly coordinated, can influence the electron density at the actinyl metal center. In this study, uranium heterometallic single crystals were synthesized by incorporating transition metals such as iron(III), iron(II), nickel(II), manganese(II), copper(I), and cobalt(II). The crystals were formed using 2,6-pyridine dicarboxylic acid and other structurally similar ligands with varying functional groups. The synthesized crystals were analyzed using an extensive array of analytical and computational characterization techniques, including single crystal X-ray diffraction, Raman and infrared spectroscopy, and density functional theory calculations.

37 - INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL C↗
DOE OSTI2024

CCDC 2391276: Experimental Crystal Structure Determination

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

(mu-2-[fluorobis(pyridin-2-yl)methyl]-7-[fluorobis↗
DOE OSTI2022

Microwave-assisted C–H oxidation of methylpyridylheteroarenes via a Kornblum-Type reaction

Expansion of the operational capacity of soft-Lewis basic complexant scaffolds towards improved physical properties for the chemoselective sequestration of minor actinides from the electronically similar lanthanides necessitates rapid access to synthons for efficient complexant construction for downstream employment in separations assays. Pursuant to the aforementioned, we were interested in exploring the potential utility of advanced, unsymmetric heteroarene constructs for separations which required access to pyridyl carbaldehydes. Limited commercial availability of synthetic precursors inspired our effort to define a chemoselective, microwave assisted, Kornblum-type reaction via C–H functionalization. This efficient reaction sequence uses I 2 as a mild oxidant without acidic or basic additives, in concert with DMSO as the solvent and putative oxygen source to afford a diverse array of heteroaryl products devoid of competitive remote methyl group oxidation, or degradation of the heteroaryl N atom. Finally, method development, substrate scope, and a preliminary mechanistic hypothesis supported by Density Functional Theory are presented herein.

1,2,4-triazine↗
DOE OSTI2022

Leveraging Nitrogen Linkages in the Formation of a Porous Thorium–Organic Nanotube Suitable for Iodine Capture

We report the synthesis, characterization, and iodine capture application of a novel thorium–organic nanotube, TSN-626, [Th 6 O 4 (OH) 4 (C 6 H 4 NO 2 ) 7 (CHO 2 ) 5 (H 2 O) 3 ]·3H 2 O. The classification as a metal–organic nanotube (MONT) distinguishes it as a rare and reduced dimensionality subset of metal–organic frameworks (MOFs); the structure is additionally hallmarked by low node connectivity. TSN-626 is composed of hexameric thorium secondary building units and mixed O/N-donor isonicotinate ligands that demonstrate selective ditopicity, yielding both terminating and bridging moieties. Because hard Lewis acid tetravalent metals have a propensity to bind with electron donors of rival hardness (e.g., carboxylate groups), such Th–N coordination in a MOF is uncommon. However, the formation of key structural Th–N bonds in TSN-626 cap some of the square antiprismatic metal centers, a position usually occupied by terminal water ligands. TSN-626 was characterized by using complementary analytical and computational techniques: X-ray diffraction, vibrational spectroscopy, N 2 physisorption isotherms, and density functional theory. TSN-626 satisfies design aspects for the chemisorption of iodine. The synergy between accessibility through pores, vacancies at the metal–oxo nodes, and pendent N-donor sites allowed a saturated iodine loading of 955 mg g –1 by vapor methods. Furthermore, the crystallization of TSN-626 diversifies actinide–MOF linker selection to include soft electron donors, and these Th–N linkages can be leveraged for the investigation of metal-to-ligand bonding and unconventional topological expressions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Systematic Study of Solid-State U(VI) Photoreactivity: Long-Lived Radicalization and Electron Transfer in Uranyl Tetrachloride

Reported are the syntheses, structural characterizations and luminescence properties of three novel [UO 2 Cl 4 ] 2- bearing compounds containing substituted 1,1’-dialkyl-4,4’-bipyridinum dications (i.e. viologens). These compounds undergo photoinduced luminescence quenching upon exposure to UV radiation. Further, this reactivity is concurrent with two phenomena: radicalization of the uranyl tetrachloride anion and photoelectron transfer to the viologen which constitutes the formal transfer of one electron from the [UO 2 Cl 4 ] 2- to the viologen species. This behavior is elucidated using electron paramagnetic resonance (EPR) spectroscopy and further probed through a series of characterization and computational techniques including Rehm-Weller analysis, time-dependent density functional theory (TD-DFT), and density of states (DOS). This work provides a systematic study of the photoreactivity of the uranyl unit in the solid state, an under-described aspect of fundamental uranyl chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Revealing the Influence of Binding Motifs on Electron Transfer and Recombination Kinetics for CdSe Quantum Dots Functionalized with a Modified Viologen

Anchoring of molecules to the surfaces of semiconductor nanocrystals (NCs) presents an opportunity to leverage the precise synthetic tunability of molecular function and the remarkable light harvesting properties of NCs to drive photochemical reactions. However, charge transfer between the two species depends not only on the energy level alignments but also on the details of their binding interactions, which are difficult to probe. Here, in this work, we characterize the binding between CdSe quantum dots (QDs) and a new phosphonated derivative of the electron acceptor methyl viologen, designed to attach to the QD surface via the phosphonate group. We use isothermal titration calorimetry to probe the thermodynamics of the QD–molecule interaction and use the parameters determined therein to analyze transient absorption spectroscopy measurements of forward and back electron transfer from QDs to the viologen. We find that the ligand-like phosphonate binding leads to an electron-transfer rate constant that is 3 orders of magnitude smaller than that for the face-on binding of the bipyridine ring of methyl viologen. Back electron transfer is also significantly slower in the derivative. Interestingly, a minor fraction of the phosphonated derivative also binds in the face-on configuration, with similar forward and back electron transfer kinetics as methyl viologen. Numerical simulations show that the ligand-like binding will lead to significantly improved quantum yields of photocatalysis over a wide range of reaction rates. By independently characterizing binding thermodynamics and charge transfer kinetics, this work reveals how the complexities underlying electron transfer at the NC–molecule interface determine photocatalytic outcomes. This work also represents a step toward controlling forward and back electron transfer kinetics via rational molecular design.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Exploring Fluoropyridine Electrolytes in Li–S Batteries: Balancing Performance and Stability across Temperatures

A novel high-donor 3-fluoropyridine (3FPy) electrolyte has been introduced for use in Li-S batteries, demonstrating an inhibition effect on the polysulfide shuttle, even without the addition of LiNO 3 . In this study, fluoropyridine electrolytes, including 2-fluoropyridine (2FPy) and 3FPy electrolytes, are studied using electrochemical analysis, mass spectrometry (MS), and high-performance liquid chromatography (HPLC) methods. Collision-induced dissociation spectra revealed that Li + preferentially solvates with different fluoropyridines, with 2FPy exhibiting a stronger interaction due to ortho-fluorine's influence, compared to 4FPy and 3FPy. However, MS and HPLC analyses showed that 2FPy is reactive with polysulfides, while 3FPy offers high solubility for polysulfides and sulfur without reacting with them at room temperature. Further, despite 3FPy performing well at room temperature, further electrochemistry studies at elevated (60 °C) and reduced (0 °C) temperatures reveal the challenges. At high temperatures, LiNO 3 is essential to suppress the polysulfide shuttle; and at low temperatures, the performance with the 3FPy electrolyte significantly lags behind that of the ether-based electrolyte.

25 ENERGY STORAGE↗
DOE OSTI2022

High-Temperature Pretreatment Effect on Co/SiO 2 Active Sites and Ethane Dehydrogenation

Here, we report the synthesis, optimization, and characterization of Co/SiO 2 for ethane nonoxidative dehydrogenation. Co/SiO 2 is synthesized via strong electrostatic adsorption using the widely available Co(NO 3 ) 2 as the precursor. We demonstrate that high-temperature pretreatment (900 °C) in an inert atmosphere can significantly enhance the initial activity of the Co/SiO 2 catalyst. X-ray absorption near-edge spectroscopy (XANES), temperature-programmed reduction (TPR), and high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) suggest that highly dispersed Co(II) clusters are more active than Co 0 or CoO x nanoparticles. Fourier transform infrared (FTIR) and isopropanol (IPA) temperature-programmed desorption and density functional theory (DFT) calculations suggest that high-temperature treatment significantly increases the density of active Lewis acid sites, possibly via surface dehydroxylation of the catalyst.

36 MATERIALS SCIENCE↗