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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 1,459 records · Page 81
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Spontaneous Hall effect enhanced by local Ir moments in epitaxial Pr 2 Ir 2 O 7 thin films

Rare-earth pyrochlore iridates ( RE 2 Ir 2 O 7 ) consist of two interpenetrating cation sublattices, the RE with highly frustrated magnetic moments, and the iridium with extended conduction orbitals significantly mixed by spin-orbit interactions. The coexistence and coupling of these two sublattices create a landscape for discovery and manipulation of quantum phenomena such as the topological Hall effect, massless conduction bands, and quantum criticality. Thin films allow extended control of the material system via symmetry-lowering effects such as strain. While bulk Pr 2 Ir 2 O 7 shows a spontaneous hysteretic Hall effect below 1.5 K, we observe the effect at elevated temperatures up to 15 K in epitaxial thin films on (111) yttria-stabilized zirconia (YSZ) substrates synthesized via solid-phase epitaxy. Similar to the bulk, the lack of observable long-range magnetic order in the thin films points to a topological origin. We use synchrotron-based element-specific x-ray diffraction and x-ray magnetic circular dichroism to compare powders and thin films to attribute the spontaneous Hall effect in the films to localization of the Ir moments. Further, we link the thin-film Ir local moments to lattice distortions absent in the bulklike powders. We conclude that the elevated-temperature spontaneous Hall effect is caused by the topological effect originating either from the Ir or Pr sublattice, with interaction strength enhanced by the Ir local moments. This spontaneous Hall effect with weak net moment highlights the effect of vanishingly small lattice distortions as a means to discover topological phenomena in metallic frustrated magnetic materials.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Milestone M4FT-13LL0807071: International Collaboration - Radionuclide Interactions and Transport in Geologic Repository Environments - Pu Interaction with Bentonite

The focus of this project is to investigate radionuclide interactions with natural and engineered materials, specifically the mineral bentonite that will be used in EU repositories and possibly in US high-level waste repository designs. These experiments are designed to develop a mechanistic understanding of Pu interactions with representative mineral substrates under granitic chemical conditions. The sorption/desorption experiments cover a large range of Pu concentrations and will be compared to sorption/desorption experiment with montmorillonite. The experiments are being coordinated with the Colloid Formation and Migration (CFM) international project led by Karlsruhe Institute of Technology and located at the Grimsel Test Site underground research laboratory in Switzerland. Experiments will be completed by 8/15/2014. Milestone M4FT-13LL0807071 is a progress report on this effort. The research is addressing the following FEPs/needs identified in the R&D Roadmap: 2.2.09.05 - radionuclide speciation and solubility in host rock; 2.2.09.55 - sorption of dissolved radionuclides in host rock; 2.2.09.59 - colloidal transport in host rock.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2017

The Role of Electronic Excitations on Chemical Reaction Dynamics at Metal, Semiconductor and Nanoparticle Surfaces

Chemical reactions are often facilitated and steered when carried out on solid surfaces, essential for applications such as heterogeneous catalysis, solar energy conversion, corrosion, materials processing, and many others. A critical factor that can determine the rates and pathways of chemical reactions at surfaces is the efficiency and specificity of energy transfer; how fast does energy move around and where does it go? For reactions on insulator surfaces energy transfer generally moves in and out of vibrations of the adsorbed molecule and the underlying substrate. By contrast, on metal surfaces, metallic nanoparticles and semiconductors, another pathway for energy flow opens up, excitation and de-excitation of electrons. This so-called “nonadiabatic” mechanism often dominates the transfer of energy and can directly impact the course of a chemical reaction. Conventional computational methods such as molecular dynamics simulation do not account for this nonadiabatic behavior. The current DOE-BES funded project has focused on developing the underlying theoretical foundation and the computational methodology for the prediction of nonadiabatic chemical reaction dynamics at surfaces. The research has successfully opened up new methodology and new applications for molecular simulation. In particular, over the last three years, the “Electronic Friction” theory, pioneered by the PI, has now been developed into a stable and accurate computational method that is sufficiently practical to allow first principles “on-the-fly” simulation of chemical reaction dynamics at metal surfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Optical Polarization Based Genomic Sensor

Optical fluorescence-based DNA assays are commonly used for pathogen detection and consist of an optical substrate containing DNA capture molecules, binding of target RNA or DNA sequences, followed by detection of the hybridization event with a fluorescent probe. Though fluorescence detection can offer exquisite signal-to-background ratios, with high specificity, vast opportunities exist to improve current optical-based genomic sensing approaches. For these reasons, there is a clear need to explore alternative optical sensing paradigms to alleviate these restrictions. Bio-templated nanomaterial synthesis has become a powerful concept for developing new platforms for bio-sensing, as the biomolecule of interest can act as part of the sensing transducer mechanism. We explored the use of DNA origami structures to immobilize gold nanoparticles in very precise localized arrangements producing unique optical absorption properties with implications in novel DNA sensing schemes. We also explored the use of in-situ TEM as a novel characterization method for DNA-nanoparticle assemblies.

47 OTHER INSTRUMENTATION↗
DOE OSTI2024

Emergence of catalytic function in prebiotic information-coding polymers

Life as we know it relies on the interplay between catalytic activity and information processing carried out by biological polymers. Here we present a plausible pathway by which a pool of prebiotic information-coding oligomers could acquire an early catalytic function, namely sequence-specific cleavage activity. Starting with a system capable of non-enzymatic templated replication, we demonstrate that even non-catalyzed spontaneous cleavage would promote proliferation by generating short fragments that act as primers. Furthermore, we show that catalytic cleavage function can naturally emerge and proliferate in this system. Specifically, a cooperative catalytic network with four subpopulations of oligomers is selected by the evolution in competition with chains lacking catalytic activity. The cooperative system emerges through the functional differentiation of oligomers into catalysts and their substrates. The model is inspired by the structure of the hammerhead RNA enzyme as well as other DNA- and RNA-based enzymes with cleavage activity that readily emerge through natural or artificial selection. We identify the conditions necessary for the emergence of the cooperative catalytic network. In particular, we show that it requires the catalytic rate enhancement over the spontaneous cleavage rate to be at least 10 2 –10 3 , a factor consistent with the existing experiments. The evolutionary pressure leads to a further increase in catalytic efficiency. The presented mechanism provides an escape route from a relatively simple pairwise replication of oligomers toward a more complex behavior involving catalytic function. This provides a bridge between the information-first origin of life scenarios and the paradigm of autocatalytic sets and hypercycles, albeit based on cleavage rather than synthesis of reactants.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

Emergence of catalytic function in prebiotic information-coding polymers

Life as we know it relies on the interplay between catalytic activity and information processing carried out by biological polymers. Here we present a plausible pathway by which a pool of prebiotic information-coding oligomers could acquire an early catalytic function, namely sequence-specific cleavage activity. Starting with a system capable of non-enzymatic templated replication, we demonstrate that even non-catalyzed spontaneous cleavage would promote proliferation by generating short fragments that act as primers. Furthermore, we show that catalytic cleavage function can naturally emerge and proliferate in this system. Specifically, a cooperative catalytic network with four subpopulations of oligomers is selected by the evolution in competition with chains lacking catalytic activity. The cooperative system emerges through the functional differentiation of oligomers into catalysts and their substrates. The model is inspired by the structure of the hammerhead RNA enzyme as well as other DNA- and RNA-based enzymes with cleavage activity that readily emerge through natural or artificial selection. We identify the conditions necessary for the emergence of the cooperative catalytic network. In particular, we show that it requires the catalytic rate enhancement over the spontaneous cleavage rate to be at least 10 2 –10 3 , a factor consistent with the existing experiments. The evolutionary pressure leads to a further increase in catalytic efficiency. The presented mechanism provides an escape route from a relatively simple pairwise replication of oligomers toward a more complex behavior involving catalytic function. This provides a bridge between the information-first origin of life scenarios and the paradigm of autocatalytic sets and hypercycles, albeit based on cleavage rather than synthesis of reactants.

Tkachenko, Alexei V. (ORCID:000000031291243X)↗
NASA NTRS1999

Transmission Measurement of the Third-Order Susceptibility of Gold

Gold nanoparticle composites are known to display large optical nonlinearities. In order to assess the validity of generalized effective medium theories (EMT's) for describing the linear and nonlinear optical properties of metal nanoparticle composites, knowledge of the linear and nonlinear susceptibilities of the constituent materials is a prerequisite. In this study the inherent nonlinearity of the metal is measured directly (rather than deduced from a suitable EMT) using a very thin gold film. Specifically, we have used the z-scan technique at a wavelength near the transmission window of bulk gold to measure the third-order susceptibility of a continuous thin gold film deposited on a quartz substrate surface-modified with a self-assembled monolayer to promote adhesion and uniformity without affecting the optical properties. We compare our results with predictions which ascribe the nonlinear response to a Fermi-smearing mechanism. Further, we note that the sign of the nonlinear susceptibility is reversed from that of gold nanoparticle composites.

Smith, David D.↗
NASA NTRS2003

Crystal structures of pinoresinol-lariciresinol and phenylcoumaran benzylic ether reductases and their relationship to isoflavone reductases

Despite the importance of plant lignans and isoflavonoids in human health protection (e.g. for both treatment and prevention of onset of various cancers) as well as in plant biology (e.g. in defense functions and in heartwood development), systematic studies on the enzymes involved in their biosynthesis have only recently begun. In this investigation, three NADPH-dependent aromatic alcohol reductases were comprehensively studied, namely pinoresinol-lariciresinol reductase (PLR), phenylcoumaran benzylic ether reductase (PCBER), and isoflavone reductase (IFR), which are involved in central steps to the various important bioactive lignans and isoflavonoids. Of particular interest was in determining how differing regio- and enantiospecificities are achieved with the different enzymes, despite each apparently going through similar enone intermediates. Initially, the three-dimensional x-ray crystal structures of both PLR_Tp1 and PCBER_Pt1 were solved and refined to 2.5 and 2.2 A resolutions, respectively. Not only do they share high gene sequence similarity, but their structures are similar, having a continuous alpha/beta NADPH-binding domain and a smaller substrate-binding domain. IFR (whose crystal structure is not yet obtained) was also compared (modeled) with PLR and PCBER and was deduced to have the same overall basic structure. The basis for the distinct enantio-specific and regio-specific reactions of PCBER, PLR, and IFR, as well as the reaction mechanism and participating residues involved (as identified by site-directed mutagenesis), are discussed.

NASA Discipline Plant Biology↗
NASA NTRS1992

Nonenzymatic template-directed synthesis on hairpin oligonucleotides. 2. Templates containing cytidine and guanosine residues

We have prepared hairpin oligonucleotides in which a 5'-terminal single-stranded segment contains cytidylate (C) and guanylate (G) residues. When these hairpin substrates are incubated with a mixture of cytidine 5'-phosphoro(2-methly)imidazolide (2-MeImpC) and guanosine 5'-phosphoro(2-methyl)imidazolide (2-MeImpG), the 5'-terminal segment acts as a template to facilitate sequence-specific addition of G and C residues to the 3'-terminus of the hairpin. If an isolated G residue is present at the 3'-end of the template strand, it is copied regiospecifically in the presence of 2-MeImpC and 2-MeImpG to give a product containing an isolated C residue linked to its G neighbors by 3'-5'-internucleotide bonds. However, if only 2-MeImpC is present in the reaction mixture, very little reaction occurs. Thus, the presence of 2-MeImpG catalyzes the incorporation of C. If the template strand contains a short sequence of G residues, it is copied in the presence of a mixture of 2-MeImpC and 2-MeImpG. If only 2-MeImpC is present in the reaction mixture, efficient synthesis occurs to give a final product containing one fewer C residue than the number of G residues in the template.

NASA Program Exobiology↗
NASA NTRS2010

Advanced Flip Chips in Extreme Temperature Environments

The use of underfill materials is necessary with flip-chip interconnect technology to redistribute stresses due to mismatching coefficients of thermal expansion (CTEs) between dissimilar materials in the overall assembly. Underfills are formulated using organic polymers and possibly inorganic filler materials. There are a few ways to apply the underfills with flip-chip technology. Traditional capillary-flow underfill materials now possess high flow speed and reduced time to cure, but they still require additional processing steps beyond the typical surface-mount technology (SMT) assembly process. Studies were conducted using underfills in a temperature range of -190 to 85 C, which resulted in an increase of reliability by one to two orders of magnitude. Thermal shock of the flip-chip test articles was designed to induce failures at the interconnect sites (-40 to 100 C). The study on the reliability of flip chips using underfills in the extreme temperature region is of significant value for space applications. This technology is considered as an enabling technology for future space missions. Flip-chip interconnect technology is an advanced electrical interconnection approach where the silicon die or chip is electrically connected, face down, to the substrate by reflowing solder bumps on area-array metallized terminals on the die to matching footprints of solder-wettable pads on the chosen substrate. This advanced flip-chip interconnect technology will significantly improve the performance of high-speed systems, productivity enhancement over manual wire bonding, self-alignment during die joining, low lead inductances, and reduced need for attachment of precious metals. The use of commercially developed no-flow fluxing underfills provides a means of reducing the processing steps employed in the traditional capillary flow methods to enhance SMT compatibility. Reliability of flip chips may be significantly increased by matching/tailoring the CTEs of the substrate material and the silicon die or chip, and also the underfill materials. Advanced packaging interconnects technology such as flip-chip interconnect test boards have been subjected to various extreme temperature ranges that cover military specifications and extreme Mars and asteroid environments. The eventual goal of each process step and the entire process is to produce components with 100 percent interconnect and satisfy the reliability requirements. Underfill materials, in general, may possibly meet demanding end use requirements such as low warpage, low stress, fine pitch, high reliability, and high adhesion.

Ramesham, Rajeshuni↗
DOE OSTI2014

The structure of Plasmodium falciparum serine hydroxymethyltransferase reveals a novel redox switch that regulates its activities

The crystal structure of P. falciparum SHMT revealed snapshots of an intriguing disulfide/sulfhydryl switch controlling the functional activity. Plasmodium falciparum serine hydroxymethyltransferase (PfSHMT), an enzyme in the dTMP synthesis cycle, is an antimalarial target because inhibition of its expression or function has been shown to be lethal to the parasite. As the wild-type enzyme could not be crystallized, protein engineering of residues on the surface was carried out. The surface-engineered mutant PfSHMT-F292E was successfully crystallized and its structure was determined at 3 Å resolution. The PfSHMT-F292E structure is a good representation of PfSHMT as this variant revealed biochemical properties similar to those of the wild type. Although the overall structure of PfSHMT is similar to those of other SHMTs, unique features including the presence of two loops and a distinctive cysteine pair formed by Cys125 and Cys364 in the tetrahydrofolate (THF) substrate binding pocket were identified. These structural characteristics have never been reported in other SHMTs. Biochemical characterization and mutation analysis of these two residues confirm that they act as a disulfide/sulfhydryl switch to regulate the THF-dependent catalytic function of the enzyme. This redox switch is not present in the human enzyme, in which the cysteine pair is absent. The data reported here can be further exploited as a new strategy to specifically disrupt the activity of the parasite enzyme without interfering with the function of the human enzyme.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2016

Direct measurement of catalase activity in living cells and tissue biopsies

Spatiotemporal regulation of enzyme-substrate interactions governs the decision-making steps in biological systems. Enzymes, being functional units of every living cell, contribute to the macromolecular stability of cell survival, proliferation and hence are vital windows to unraveling the biological complexity. Experimental measurements capturing this dynamics of enzyme-substrate interactions in real time add value to this understanding. Furthermore these measurements, upon validation in realistic biological specimens such as clinical biopsies – can further improve our capability in disease diagnostics and treatment monitoring. Towards this direction, we describe here a novel, high-sensitive measurement system for measuring diffusion-limited enzyme-substrate kinetics in real time. Using catalase (enzyme) and hydrogen peroxide (substrate) as the example pair, we demonstrate that this system is capable of direct measurement of catalase activity in vitro and the measured kinetics follows the classical Michaelis-Menten reaction kinetics. We further demonstrate the system performance by measuring catalase activity in living cells and in very small amounts of liver biopsies (down to 1 μg total protein). Catalase-specific enzyme activity is demonstrated by genetic and pharmacological tools. Finally we show the clinically-relevant diagnostic capability of our system by comparing the catalase activities in liver biopsies from young and old mouse (liver and serum) samples. We discuss the potential applicability of this system in clinical diagnostics as well as in intraoperative surgical settings. - Highlights: • A novel, direct measurement of Catalase enzyme activity via, oxygen sensing method. • Steady-stateprofiles of Catalase activity follow the Michaelis-Menten Kinetics. • Catalase-specific activity demonstrated using genetic and pharmacological tools. • Overcomes limitations of spectroscopic methods and indirect calorimetric approaches. • Clear demonstration of the applicability in cancer cells and aging animal tissues.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2014

Controllable synthesis of mesoporous Co{sub 3}O{sub 4} nanoflake array and its application for supercapacitor

Graphical abstract: Electrodeposited mesoporous Co{sub 3}O{sub 4} nanoflake arrays exhibit porous structure composed of mesoporous nanoflakes and high supercapacitor performance. - Highlights: • Mesoporous Co{sub 3}O{sub 4} nanoflake arrays are prepared via electrodeposition method. • Mesoporous nanowall arrays are favorable for fast ion/electron transfer. • Mesoporous Co{sub 3}O{sub 4} nanoflake arrays show excellent supercapacitor performance. - Abstract: A mesoporous Co{sub 3}O{sub 4} nanoflake array grown on carbon cloth is prepared by a facile electrodeposition method with a following annealing process. The as-prepared Co{sub 3}O{sub 4} nanoflake possesses a continuous mesopores ranging from 2 to 5 nm and grows tightly on the substrate forming a porous net-like structure with macropores of 20–200 nm. The electrochemical performance of the mesoporous Co{sub 3}O{sub 4} nanoflake arrays as pseudocapcitor electrode are investigated by cyclic voltammograms and galvanostatic charge/discharge tests in 2 M KOH. The as-prepared Co{sub 3}O{sub 4} array exhibits a high discharge capacitance and excellent rate capability with 450 F g{sup −1}, 436 F g{sup −1}, 408 F g{sup −1}, 380 F g{sup −1}and 363 F g{sup −1} at 1, 2, 4, 10, and 20 A g{sup −1}, respectively. The specific capacitance of 81% is maintained from 1 A g{sup −1} to 20 A g{sup −1}. The electrode also shows rather good cycling stability and exhibits a specific capacitance of 414 F g{sup −1} after 5000 cycles.

36 MATERIALS SCIENCE↗
DOE OSTI2026

High Temperature High Vacuum Mechanical Property Assessment of Zirconium Nuclear Fuel Cladding

This report presents the mechanical characterization of a specific Zry-4 cladding batch serving as the foundation for a diverse range of fuel performance research at Oak Ridge National Laboratory (ORNL). This effort supports research needs for the U.S. Department of Energy (DOE), particularly regarding evaluating accident tolerant fuel (ATF) cladding coating concepts, expanding understanding of cladding response to loss-of-coolant accidents (LOCA) transients, refining post-critical heat flux (CHF) limits (t@T), and upcoming irradiation campaigns. The central objective was to define the baseline performance of the substrate Zircaloy-4 (Zry-4) material leveraged across ORNL Advanced Fuel Campaign (AFC) efforts through controlled high-temperature vacuum tensile testing. This work begins to address gaps in existing models where implementation based on nominal heat-treatment labels, such as stress relief annealed (SRA), often fail to capture the interplay of recovery, recrystallization, and grain growth. To quantify this, data was benchmarked against the Pacific Northwest National Laboratory (PNNL) stress strain model to determine where this material falls in comparison to assumed values for materials in the same heat treatment regime. Analysis of the tensile data revealed that this specific SRA batch exhibits a transitional microstructural state best described by an effective cold-work (CW) parameter of 0.09, diverging from the previous estimation of 0.5 for SRA materials. Additionally, comparative testing of Cr coated specimens demonstrated no distinct difference in axial strength relative to the bare substrate. This suggests that the strengthening benefits of Cr coatings observed in burst scenarios are driven by residual stress mechanisms acting solely in the hoop direction.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2016

Second spatial derivative analysis of cortical surface potentials recorded in cat primary auditory cortex using thin film surface arrays: Comparisons with multi-unit data

Current source density analysis of recordings from penetrating electrode arrays has traditionally been used to examine the layer- specific cortical activation and plastic changes associated with changed afferent input. Here, we report on a related analysis, the second spatial derivative (SSD) of surface local field potentials (LFPs) recorded using custom designed thin-film polyimide substrate arrays.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2019

Chemical Imaging of Atmospheric Particles

Airborne particles are very dynamic and highly reactive components of the Earth’s atmosphere. Their high surface area and water content provide a unique reaction environment for multiphase chemistry that continually modifies particle composition and properties that consequently impact air quality as well as concentrations of gas-phase species. By absorbing and scattering solar and terrestrial radiation, particles directly influence the planet’s radiative balance. Their indirect effects include modifying the nucleation, lifetime, and physical properties of clouds. Due to the sensitivity of the atmospheric environment to all these variables, fundamental studies of chemical transformations of atmospheric particles, their sources, continuously evolving composition, and physical properties are of highest research priority. Accurate descriptions of particles and their effects in the atmosphere require comprehensive information not only on the particle-type populations and their size distributions and concentrations, but also on the diversity and the spatial heterogeneity of chemical components within individual particles. Developments and applications of modern chemical imaging approaches for off-line characterization of atmospheric particles have been at the forefront of modern experimental studies and have resulted in a transformative impact in atmospheric chemistry and physics. This Account presents a synopsis of recent advances in chemical imaging of atmospheric particles collected on substrates during field and laboratory experiments. The unique advantage of chemical imaging methods is that they simultaneously provide two analytical measurements: imaging of particles to assess variability in their individual sizes and morphology, as well as particle specific speciation of their composition and spatial heterogeneity of different chemical components within individual particles. We also highlight analytical chemistry approaches that enable chemical imaging of particles with different levels of elemental and molecular specificity, including applications of multimodal methodologies where the same or similar groups of particles are probed by two or more complementary techniques. These approaches provide unique experimental insights on the nature and sources of particles, understanding their physical properties, atmospheric reactivity, and transformations. Chemical imaging data provide unique experimental input for atmospheric models that simulate aging and changes in particle-type populations, internal composition, and their associated optical and cloud forming properties. Here, we highlight applications of chemical imaging in selected recent studies, discuss their existing limitations, and forecast future research directions for this area.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2017

Heavy Metal-Free Tannin from Bark for Sustainable Energy Storage

A novel renewable cathode made from earth abundant, low-cost materials can contribute to the intermittent storage needs of renewable energy-based society. In this work, we report for the first-time tannin from Nature as a cathode material. Our approach exploits the charge storage mechanism of the redox active quinone moiety. Tannins extracted from tree bark using environmental friendly aqueous solvents have the highest phenol content (5.56 mol g -1 ) among all the natural phenolic biopolymers, 5000 times higher than lignin. Tannins coupled with a conductive polymer polypyrrole acquire high specific capacitance values of 370 F g -1 at 0.5 A g -1 as well as excellent rate performance of 196 F g -1 at 25 A g -1 . Additionally, we employed carbonized wood as an electrode substrate to produce a sustainable electrochemical device with dramatically improved performance compared to conventional devices. The high surface area provided by the well-aligned, cellular porosity of wood-derived substrate combined with the high mobility of ions and electrons in the carbonized cell walls and deposited tannin can achieve an areal capacitance of 4.6 F cm -2 at 1 mA cm -2 , which is 1.5 times higher than activated wood carbon.

09 BIOMASS FUELS↗
DOE OSTI2023

Prospects and challenges for nitrogen-atom transfer catalysis

Incorporation of nitrogen-based functional groups can profoundly impact the chemical and physical properties of organic small molecules. One-step conversion of C–H bonds to C–N bonds via C–H amination promises to streamline the synthesis of nitrogen-containing compounds. In pursuit of this promise, nitrogen-group transfer (NGT) from metal nitrenes (i.e., ligand supported M–NR complexes) has been the focus of intense research and development. In contrast, potentially complementary nitrogen-atom transfer (NAT) chemistry, in which a terminal metal nitride (i.e., ligand-supported M–N complex) engages with a C–H bond, is undeveloped. While the earliest examples of stoichiometric NAT chemistry were reported 25 years ago, catalytic protocols are only now beginning to emerge. Furthermore, we summarize the current state-of-the-art in NAT chemistry and discuss opportunities and challenges for the development of NAT catalysis as a platform for incorporation of nitrogen into organic small molecules. Specifically, we 1) highlight the synthetic complementarity of NGT and NAT chemistry, 2) discuss critical aspects of nitride electronic structure that dictate the philicity of supported metal atom, 3) examine the characteristic reactivity of metal nitrides towards substrate functionalization reactions, and 4) present emerging strategies and remaining obstacles to harnessing NAT for selective, catalytic nitrogenation of unfunctionalized organic small molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗