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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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93 records · Page 6
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Development of (NO)Fe(N 2 S 2 ) as a Metallodithiolate Spin Probe Ligand: A Case Study Approach

The ubiquity of sulfur–metal connections in nature inspires the design of bi- and multimetallic systems in synthetic inorganic chemistry. Common motifs for biocatalysts developed in evolutionary biology include the placement of metals in close proximity with flexible sulfur bridges as well as the presence of π-acidic/delocalizing ligands. This Account will delve into the development of a (NO)Fe(N 2 S 2 ) metallodithiolate ligand that harnesses these principles. The Fe(NO) unit is the centroid of a N 2 S 2 donor field, which as a whole is capable of serving as a redox-active, bidentate S-donor ligand. Its paramagnetism as well as the ν(NO) vibrational monitor can be exploited in the development of new classes of heterobimetallic complexes. We offer four examples in which the unpaired electron on the {Fe(NO)} 7 unit is spin-paired with adjacent paramagnets in proximal and distal positions. First, the exceptional stability of the (NO)Fe(N 2 S 2 )-Fe(NO) 2 platform, which permits its isolation and structural characterization at three distinct redox levels, is linked to the charge delocalization occurring on both the Fe(NO) and the Fe(NO) 2 supports. This accommodates the formation of a rare nonheme {Fe(NO)} 8 triplet state, with a linear configuration. A subsequent FeNi complex, featuring redox-active ligands on both metals (NO on iron and dithiolene on nickel), displayed unexpected physical properties. Our research showed good reversibility in two redox processes, allowing isolation in reduced and oxidized forms. Various spectroscopic and crystallographic analyses confirmed these states, and Mössbauer data supported the redox change at the iron site upon reduction. Oxidation of the complex produced a dimeric dication, revealing an intriguing magnetic behavior. The monomer appears as a spin-coupled diradical between {Fe(NO)} 7 and the nickel dithiolene monoradical, while dimerization couples the latter radical units via a Ni 2 S 2 rhomb. Magnetic data (SQUID) on the dimer dication found a singlet ground state with a thermally accessible triplet state that is responsible for magnetism. A theoretical model built on an H 4 chain explains this unexpected ferromagnetic low-energy triplet state arising from the antiferromagnetic coupling of a four-radical molecular conglomerate. For comparison, two (NO)Fe(N 2 S 2 ) were connected through diamagnetic group 10 cations producing diradical trimetallic complexes. Antiferromagnetic coupling is observed between {Fe(NO)} 7 units, with exchange coupling constants (J) of -3, -23, and -124 cm –1 for Ni II , Pd II , and Pt II , respectively. This trend is explained by the enhanced covalency and polarizability of sulfur-dense metallodithiolate ligands. A central paramagnetic trans-Cr(NO)(MeCN) receiver unit core results in a cissoid structural topology, influenced by the stereoactivity of the lone pair(s) on the sulfur donors. This {Cr(NO)} 5 radical bridge, unlike all previous cases, finds the coupling between the distal Fe(NO) radicals to be ferromagnetic (J = 24 cm –1 ). The stability and predictability of this S = 1/2 moiety and the steric/electronic properties of the bridging thiolate sulfurs suggest it to be a likely candidate for the development of novel molecular (magnetic) compounds and possibly materials. The role of synthetic inorganic chemistry in designing synthons that permit connections of the (NO)Fe(N 2 S 2 ) metalloligand is highlighted as well as the properties of the heterobi- and polymetallic complexes derived therefrom.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1995

Asymmetric structure of five and six membered DNA hairpin loops

The tertiary structure of nucleic acid hairpins was elucidated by means of the accessibility of the single-strand-specific nuclease from mung bean. This molecular probe has proven especially useful in determining details of the structural arrangement of the nucleotides within a loop. In this study 3'-labeling is introduced to complement previously used 5'-labeling in order to assess and to exclude possible artifacts of the method. Both labeling procedures result in mutually consistent cleavage patterns. Therefore, methodological artifacts can be excluded and the potential of the nuclease as structural probe is increased. DNA hairpins with five and six membered loops reveal an asymmetric loop structure with a sharp bend of the phosphate-ribose backbone between the second and third nucleotide on the 3'-side of a loop. These hairpin structures differ from smaller loops with 3 or 4 members, which reveal this type of bend between the first and second 3' nucleotide, and resemble with respect to the asymmetry anticodon loops of tRNA.

NASA Discipline Exobiology↗
NASA NTRS1995

Curation of Federally Owned Archeological Collections at NASA Langley Research Center

As a Federal agency, NASA has a moral and legal obligation to the public to manage the archeological heritage resources under its control. Archeological sites are unique, nonrenewable resources that must be preserved so that future generations may experience and interpret the material remains of the past. These sites are protected by a wide array of federal regulations. These regulations are intended to ensure that our nation's cultural heritage is preserved for the study and enjoyment of future generations. Once a site has been excavated, all that remains of it are the artifacts and associated records which, taken together, allow researchers to reconstruct the past. With the contextual information provided by associated records such as field notes, maps and photographs, archeological collections can provide important information about life in the past. An integral component of the federal archeology program is the curation of these databases so that qualified scholars will have access to them in years to come. Standards for the maintenance of archeological collections have been codified by various professional organizations and by the federal government. These guidelines focus on providing secure, climate-controlled archival storage conditions for the collections and an adequate study area in which researchers can examine the artifacts and documents. In the 1970's and early 1980's, a group of NASA employees formed the LRC Historical and Archeological Society (LRCHAS) in order to pursue studies of the colonial plantations that ha been displaced by Langley Research Center (LaRC). They collected data on family histories and land ownership as well as conducting archeological surveys and excavations at two important 17th-20th century plantation sites in LaRC, Cloverdale and Chesterville. The excavations produced a wealth of information in the form of artifacts, photographs, maps and other documents. Unfortunately, interest on the part of the LRCHAS membership waned before a report was written, and since 1982 the artifacts have moldered in a flimsy trailer with no climate controls, which had once served as a field laboratory but which threatened to become a tomb for the collection. A recent analysis of Langley's cultural resources by Gray & Pape, Inc. recommended that the collection be organized, cataloged, and placed in a proper curation facility in accordance with Federal regulations. The project for the LARSS program was to research curation standards, organize the collection, catalog it, and prepare it for transfer to a facility which could provide adequate long-term curation conditions for the artifacts and documents. The first phase was to organize the artifacts, which were lying about the lab in various stages of cleaning, analysis, and conservation. Once all of the artifacts from the various excavation units and levels had been regrouped, they were cleaned and/or repackaged in archivally-stable materials. A basic catalog was prepared which will provide interested parties with a rough idea of what we have and where it can be found. Another aspect of the project was to organize the records left by the LRCHAS. Bundles of papers, photographs, and field data found in every corner and drawer of the laboratory trailer were put into order and, where appropriate, copies were made on acid-free Permabond paper for long term storage. Finally, the entire collection and most of the lab equipment was transferred into a secure, climate controlled room which will serve as an archive and study space for qualified scholars interested in exploring LaRC's rich historical heritage.

Eastman, John Arnold↗