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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 973 records · Page 54
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Synthesis and Purification of Homogeneous Lipid-Based Peptide Nanocarriers by Overcoming Phospholipid Ester Hydrolysis

Despite the therapeutic promise of phospholipid-based nanocarriers, a major obstacle to their widespread clinical translation is a susceptibility to fatty acid ester hydrolysis, leading to lack of quality control and inconsistencies in self-assembly formulations. Using electrospray ionization mass spectrometry fragmentation in combination with matrix-assisted laser desorption/ionization time-of-flight mass spectrometry, we have demonstrated a method to detect hydrolysis of one or both of the fatty acid esters in a PEGylated phospholipid, DSPE-PEG, in conditions commonly applied during nanocarrier production. Because such carriers are increasingly being used to deliver peptide-based therapeutics, we further investigated the hydrolysis of phospholipid esters in conditions used for solid-phase peptide synthesis and high-performance liquid chromatography of peptides. We ultimately detail a synthetic strategy to reliably produce pure phospholipid–peptide bioconjugates (peptide amphiphiles), while avoiding unintended or unnoticed hydrolyzed byproducts that could lead to polymorphic nanotherapeutics with dampened therapeutic efficacy. We believe that such an approach could help standardize phospholipid–peptide-based therapeutic development, testing, and clinical translation.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2014

Homogeneous Hydrogenation of CO₂ to Methyl Formate Utilizing Switchable Ionic Liquids

Capture of CO₂ and subsequent hydrogenation allows for base/alcohol-catalyzed conversion of CO₂ to methylformate in one pot. The conversion of CO₂ proceeds via alkylcarbonates, to formate salts and then formate esters, which can be catalyzed by base and alcohol with the only byproduct being water. The system operates at mild conditions (300 psi H₂, 140 °C). Reactivity is strongly influenced by temperature and choice of solvent. In the presence of excess of base (DBU) formate is predominant product while in excess of methanol methyl formate is major product. 110 °C yields formate salts, 140 °C promotes methylformate. The authors acknowledge internal Laboratory Directed Re-search and Development (LDRD) funding from Pacific Northwest National Laboratory (PNNL). PNNL is operated by Battelle for the U.S. Department of Energy.

catalysis↗
DOE OSTI2023

Optimizing the Synthetic Potential of O 2 : Implications of Overpotential in Homogeneous Aerobic Oxidation Catalysis

Molecular oxygen is the quintessential oxidant for organic chemical synthesis, but many challenges continue to limit its utility and breadth of applications. Extensive historical research has focused on overcoming kinetic challenges presented by the ground-state-triplet electronic structure of O 2 and the various reactivity and selectivity challenges associated with reactive oxygen species derived from O 2 reduction. This Perspective will analyze thermodynamic principles underlying catalytic aerobic oxidation reactions, borrowing concepts from the study of the oxygen reduction reaction (ORR) in fuel cells. This analysis is especially important for "oxidase"-type liquid-phase catalytic aerobic oxidation reactions, which proceed by a mechanism that couples two sequential redox half-reactions: (1) substrate oxidation, and (2) oxygen reduction, typically affording H 2 O 2 or H 2 O. The catalysts for these reactions feature redox potentials that lie between the potentials associated with the substrate oxidation and oxygen reduction reactions, and changes in the catalyst potential lead to variations in effective overpotentials for the two half reactions. Catalysts that operate at low ORR overpotential retain more thermodynamic driving force for the substrate oxidation step, enabling O 2 to be used in more challenging oxidations. While catalysts that operate at high ORR overpotential have less driving force available for substrate oxidation, they often exhibit different or improved chemoselectivity relative to the high-potential catalysts. The concepts are elaborated in a series of case studies to highlight their implications for chemical synthesis. Examples include comparisons of (a) NO x /oxoammonium and Cu/nitroxyl catalysts, (b) high-potential quinones and amine oxidase biomimetic quinones, and (c) Pd aerobic oxidation catalysts, with or without NO x cocatalysts. In addition, we show how reductive activation of O 2 provides a means to access potentials not accessible with conventional oxidase-type mechanisms. Altogether, this analysis highlights the central role of catalyst overpotential in guiding the development of aerobic oxidation reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

A Library of Selenourea Precursors to PbSe Nanocrystals with Size Distributions near the Homogeneous Limit

Here, we report a tunable library of N,N,N' -trisubstituted selenourea precursors and their reaction with lead oleate at 60–150 °C to form carboxylate-terminated PbSe nanocrystals in quantitative yields. Single exponential conversion kinetics can be tailored over 4 orders of magnitude by adjusting the selenourea structure. The wide range of conversion reactivity allows the extent of nucleation ([nanocrystal] = 4.6–56.7 μM) and the size following complete precursor conversion (d = 1.7–6.6 nm) to be controlled. Narrow size distributions (σ = 0.5–2%) are obtained whose spectral line widths are dominated (73–83%) by the intrinsic single particle spectral broadening, as observed using spectral hole burning measurements. Here, the intrinsic broadening decreases with increasing size (fwhm = 320–65 meV, d = 1.6–4.4 nm) that derives from exciton fine structure and exciton–phonon coupling rather than broadening caused by the size distribution.

36 MATERIALS SCIENCE↗
DOE OSTI2012

Chemically homogeneous and thermally reversible oxidation of epitaxial graphene

With its exceptional charge mobility, graphene holds great promise for applications in next-generation electronics. In an effort to tailor its properties and interfacial characteristics, the chemical functionalization of graphene is being actively pursued. The oxidation of graphene via the Hummers method is most widely used in current studies, although the chemical inhomogeneity and irreversibility of the resulting graphene oxide compromises its use in high-performance devices. Here, we present an alternative approach for oxidizing epitaxial graphene using atomic oxygen in ultrahigh vacuum. Atomic-resolution characterization with scanning tunnelling microscopy is quantitatively compared to density functional theory, showing that ultrahigh-vacuum oxidization results in uniform epoxy functionalization. Furthermore, this oxidation is shown to be fully reversible at temperatures as low as 260 8C using scanning tunnelling microscopy and spectroscopic techniques. In this manner, ultrahigh-vacuum oxidation overcomes the limitations of Hummers-method graphene oxide, thus creating new opportunities for the study and application of chemically functionalized graphene.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

Probing oxygen vacancy concentration and homogeneity in solid-oxide fuel-cell cathode materials on the subunit-cell level

Oxygen vacancy distributions and dynamics directly control the operation of solid-oxide fuel cells and are intrinsically coupled with magnetic, electronic, and transport properties of oxides. For understanding the atomistic mechanisms involved during operation of the cell it is highly desirable to know the distribution of vacancies on the unit cell scale. Here, we develop an approach for direct mapping of oxygen vacancy concentrations based on local lattice parameter measurements by scanning transmission electron microscopy. The concept of chemical expansivity is demonstrated to be applicable on the sub-unit cell level: local stoichiometry variations produce local lattice expansion that can be quantified. The vacancy mapping reveals strong difference in magnetic properties of lanthanum strontium cobaltite model systems induced by different substrate symmetry, opening pathways for structural tuning of the vacancy concentrations and their gradients.

Oxygen Stoichimetry↗
DOE OSTI2022

High-efficiency, anode-free lithium–metal batteries with a close-packed homogeneous lithium morphology

Anode-free lithium–metal batteries (LMBs) are ideal candidates for high-capacity energy storage as they eliminate the need for a conventional graphite electrode or excess lithium–metal anode. Current anode-free LMBs suffer from low Coulombic efficiency (CE) due to poor lithium stripping efficiency. Advanced electrolyte development is a promising route to maximize lithium plating and stripping CE and minimize capacity fade. However, a poor understanding of the mechanisms by which advanced electrolytes improve performance hampers progress in the practical development of anode-free LMBs. Here, we use synchrotron techniques and other tools to analyze the influence of three commercially available electrolytes on the composition, heterogeneity, kinetics, morphology, and electrochemistry of anode-free LMBs. Advanced electrolytes improve the electrochemical performance of anode-free LMBs by forming much denser and better-packed Li morphologies on a Cu current collector than on the conventional electrolyte. Li plates uniformly over the electrode area with the advanced electrolytes rather than in a few active sites. Inactive crystalline Li with heterogeneous distribution dominates the capacity degradation of anode-free cells, especially with the conventional electrolyte, indicating that reducing the amount of “dead” crystalline Li will significantly improve the cycling stability of anode-free cells. Finally, the understanding of the Li plating and stripping process obtained from this work will accelerate the development of anode-free LMBs with high efficiency.

25 ENERGY STORAGE↗