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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 OSTI2022

Enzymatic Nitrogen Insertion into Unactivated C–H Bonds

Selective functionalization of aliphatic C–H bonds, ubiquitous in molecular structures, could allow ready access to diverse chemical products. While enzymatic oxygenation of C–H bonds is well established, the analogous enzymatic nitrogen functionalization is still unknown; nature is reliant on pre-oxidized compounds for nitrogen incorporation. Likewise, synthetic methods for selective nitrogen derivatization of unbiased C–H bonds remain elusive. In this work, new-to-nature heme-containing nitrene transferases were used as starting points for the directed evolution of enzymes to selectively aminate and amidate unactivated C(sp3)–H sites. The desymmetrization of methyl- and ethylcyclohexane with divergent site selectivity is offered as demonstration. The evolved enzymes in these lineages are highly promiscuous and show activity towards a wide array of substrates, providing a foundation for further evolution of nitrene transferase function. Computational studies and kinetic isotope effects (KIEs) are consistent with a stepwise radical pathway involving an irreversible, enantiodetermining hydrogen atom transfer (HAT), followed by a lower-barrier diastereoselectivity determining radical rebound step. In-enzyme molecular dynamics (MD) simulations reveal a predominantly hydrophobic pocket with favorable dispersion interactions with the substrate. Here, by offering a direct path from saturated precursors, these enzymes present a new biochemical logic for accessing nitrogen-containing compounds.

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

Biocatalytic Synthesis of α-Amino Esters via Nitrene C–H Insertion

α-Amino esters are precursors to noncanonical amino acids used in developing small-molecule therapeutics, biologics, and tools in chemical biology. α-C–H amination of abundant and inexpensive carboxylic acid esters through nitrene transfer presents a direct approach to α-amino esters. Methods for nitrene-mediated amination of the protic α-C–H bonds in carboxylic acid esters, however, are underdeveloped. This gap arises because hydrogen atom abstraction (HAA) of protic C–H bonds by electrophilic metal-nitrenoids is slow: metal-nitrenoids preferentially react with polarity-matched, hydridic C–H bonds, even when weaker protic C–H bonds are present. This study describes the discovery and evolution of highly stable protoglobin nitrene transferases that catalyze the enantioselective intermolecular amination of the α-C–H bonds in carboxylic acid esters. We developed a high-throughput assay to evaluate the activity and enantioselectivity of mutant enzymes together with their sequences using the Every Variant Sequencing (evSeq) method. Furthermore, the assay enabled the identification of enantiodivergent enzymes that function at ambient conditions in Escherichia coli whole cells and whose activities can be enhanced by directed evolution for the amination of a range of substrates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Highly Reversible Mg Insertion in Nanostructured Bi for Mg Ion Batteries

Rechargeable magnesium batteries have attracted wide attention for energy storage. Currently, most studies focus on Mg metal as the anode, but this approach is still limited by the properties of the electrolyte and poor control of the Mg plating/stripping processes.1,2 Here we report the synthesis and application of Bi nanotubes as a high performance anode material for rechargeable Mg ion batteries. The nanostructured Bi anode delivers a high reversible specific capacity (350 mAh/gBi, or 3430 mAh/cm3 Bi), excellent stability, and high columbic efficiency (95 % initial and very close to 100% afterwards). The good performance is attributed to the unique properties of in-situ formed, interconnected nanoporous bismuth. Such nanostructures can effectively accommodate the large volume change without losing electric contact and significantly reduce diffusion length for Mg2+. Significantly, the nanostructured Bi anode can be used with conventional electrolytes which will open new opportunities to study Mg ion battery chemistry and further improve the properties. The performance and the stability of a full cell Mg ion battery have been demonstrated with conventional electrolytes. This work suggests that other high energy density alloy compounds may also be considered for Mg-ion chemistry for high capacity electrode materials.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2015

Realizing the Full Potential of Insertion Anodes for Mg-ion Batteries Through the Nano-Structuring of Sn

For next-generation rechargeable batteries, magnesium is of great interest as an alternative to Lithium due to its relative abundance, low toxicity, and bivalent charge (3833 mAh/cm3 and 2205 mAh/g). However, Mg-ion batteries face unique challenges related to the formation of anode passivation layers, anode-electrolyte-cathode incompatibilities, slow solid-state Mg2+ diffusion, and ion trapping. Using analytical (scanning) transmission electron microscopy ((S)TEM) and ab initio modeling, we have investigated Mg2+ intercalation and extraction mechanisms in β-SnSb alloy nanoparticles (NPs). During the first several charge-discharge cycles, the SnSb particles irreversibly break down into a network of pure-Sn and Sb-rich sub-particles, as Mg-ions replace Sn ions in the SnSb lattice. Once the morphology has stabilized, the small Sn NPs (< 20 nm) are responsible for the majority of reversible storage capacity, while the Sb-rich particles trap substitutional-Mg atoms in the lattice and are significantly less active. This result strongly indicates that pure-Sn nanoparticles on a graphene support can act as a high capacity anode for Mg-ion batteries.

Environmental Molecular Sciences Laboratory↗