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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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All sourcesNASA NTRSDOE OSTI
NASA NTRS1992

Equations of motion of slung-load systems, including multilift systems

General simulation equations are derived for the rigid body motion of slung-load systems. This work is motivated by an interest in trajectory control for slung loads carried by two or more helicopters. An approximation of these systems consists of several rigid bodies connected by straight-line cables or links. The suspension can be assumed elastic or inelastic. Equations for the general system are obtained from the Newton-Euler rigid-body equations with the introduction of generalized velocity coordinates. Three forms are obtained: two generalize previous case-specific results for single-helicopter systems with elastic and inelastic suspensions, respectively; and the third is a new formulation for inelastic suspensions. The latter is derived from the elastic suspension equations by choosing the generalized coordinates so that motion induced by cable stretching is separated from motion with invariant cable lengths, and by then nulling the stretching coordinates to get a relation for the suspension forces. The result is computationally more efficient than the conventional formulation, is readily integrated with the elastic suspension formulation, and is easily applied to the complex dual-lift and multilift systems. Results are given for two-helicopter systems; three configurations are included and these can be integrated in a single simulation. Equations are also given for some single-helicopter systems, for comparison with the previous literature, and for a multilift system. Equations for degenerate-body approximations (point masses, rigid rods) are also formulated and results are given for dual-lift and multilift systems. Finally, linearlized equations of motion are given for general slung-load systems are presented along with results for the two-helicopter system with a spreader bar.

Cicolani, Luigi S.↗
NASA NTRS1991

Tiltrotor Acoustic Flight Test: Terminal Area Operations

This paper provides a comprehensive description of an acoustic flight test of the XV- 15 Tiltrotor Aircraft with Advanced Technology Blades (ATB) conducted in August and September 1991 at Crows Landing, California. The purpose of this cooperative research effort of the NASA Langley and Ames Research Centers was to obtain a preliminary, high quality database of far-field acoustics for terminal area operations of the XV-15 at a takeoff gross weight of approximately 14,000 lbs for various glide slopes, airspeeds, rotor tip speeds, and nacelle tilt angles. The test also was used to assess the suitability of the Crows Landing complex for full scale far-field acoustic testing. This was the first acoustic flight test of the XV-15 aircraft equipped with ATB involving approach and level flyover operations. The test involved coordination of numerous personnel, facilities and equipment. Considerable effort was made to minimize potential extraneous noise sources unique to the region during the test. Acoustic data from the level flyovers were analyzed, then compared with data from a previous test of the XV-15 equipped with Standard Metal Blades

SantaMaria, O. L.↗
NASA NTRS2020

UAS Service Supplier Network Performance

This report summarizes the performance of Unmanned Aircraft System (UAS) Service Suppliers (USS) in the Technical Capability Level 4 (TCL4) flight test performed by NASA and its partners in support of the UAS Traffic Management (UTM) concept. TCL4 is the final in a series of TCL demonstrations of a traffic management system for small UAS (sUAS). All demonstrations have been executed in collaboration with industry partners. The [FAA 2018] UTM Concept of Operations document describes UTM as:...the manner in which the FAA will support operations for predominantly sUAS operating in low altitude airspace. UTM utilizes industry’s ability to supply services under FAA’s regulatory authority where these services do not currently exist. It is a community-based traffic management system, where the Operators are responsible for the coordination, execution, and management of operations, with rules of the road established by FAA. UTM is designed to support the demand and expectations for a broad spectrum of operations with ever-increasing complexity and risk. UTM should be considered a collection of services rather than a monolithic application. The following section describes the architecture at a high level. For further insight, the FAA’s concept document [FAA 2018] or NASA’s earlier concept publication [NASA 2016] should be consulted.

Rios, Joseph L.↗
NASA NTRSDate not supplied

LIS-Hydro: Authoritative Source for OCONUS Hydro-Intelligence

U.S. military forces are often tasked to participate in a variety of transboundary water-related decision-making activities, including humanitarian assistance operations through Department of State tasking, support of in-country infrastructure development activities that help develop or improve diplomatic relationships, and support of transboundary water treaty negotiations or disputes to reduce risk of conflict caused by water security issues. The U.S. intelligence communities have identified the coordination over shared water resources as an area of significant concern to U.S. national security (U.S. National Defense Strategy, 2018). Such transboundary water issues are projected to intensify in the future under increasingly complex population dynamics, political tensions due to parallel issues, and a changing climate. A 2017 joint NASA, USACE/RDC, and U.S. Air Force co-sponsored workshop revealed a lack of sufficient decision support tools and access to timely technical and contextual information needed to assess and respond to potential water-related threats around the world. The need for an integrated operational service, with the capacity to combine and synthesize hydrological modeling, assimilation, forecasting, and visualization capabilities across the U.S. Government, was highlighted as a key recommendation. In direct response, a subset of the U.S. Department of Defense, National Intelligence Community, and Oak Ridge National Laboratory are collaborating on the development of a fully integrated hydro-modeling and streamflow prediction system (i.e., LIS-Hydro). Completion of the project and sustainment of the operational capability by Air Force Weather will establish a national asset to assist federal agencies implement government-wide strategies around water resources (U.S. Global Water Strategy, 2017). The hydrological products and services will, for the very first time, establish a routinely available authoritative source of global water intelligence information supporting war-fighters, planners, and decision makers at all echelons and services of the U.S. military, Federal government, and intelligence community. A summary of the interagency scientific collaboration in addressing some of the key gaps and needs identified during the 2017 workshop will be presented.

Land Information System↗
DOE OSTI2025

Hierarchical Resilience Planning for Networked Microgrids: A Case Study of Puerto Rico

Microgrids can be designed to enhance the energy resilience of communities and critical infrastructures, such as hospitals, data centers, and communication networks, which are vulnerable to frequent weather-related disruption. Coordinating multiple microgrids in a network can leverage the geographical diversity of load and generation resources while enabling resilient and cost-effective planning of the distribution system. Designing a networked microgrid is complex, involving intricate technical assessment, cost-benefit analysis, site-specific requirements, and the evaluation of existing resources. Therefore, this paper proposes a hierarchical resilience planning framework and performs an extensive techno-economic analysis for the design of a networked microgrid. Hierarchical resilience planning involves technology sizing at an individual community level to meet the critical load and satisfy resilience criteria, and resource optimization at networked microgrid level to provide a higher level of resilience and energy adequacy. A real-world case of Puerto Rico's cooperative microgrid “Microrred de la Montaña” is investigated considering localized electricity tariffs, site-specific demand profiles, solar generation, and existing hydro resources. Multiple optimization scenarios are developed based on the resiliency requirement to estimate the capacity of solar photovoltaic and battery energy storage (BES) to be installed at each substation. The results provide the optimal sizing for individual community and networked microgrid to withstand 1day and 3-day outages along with the criteria for critical load.

13 - HYDRO ENERGY↗
DOE OSTI2022

Basin-Wide Approaches to Hydropower Licensing

This presentation summarizes findings from a 2020 NREL technical report including the FERC relicensing process for non-federal hydropower projects, analyzes FERC-licensed projects with license expiration dates from 2018-2037, discusses FERC's authority to coordinate license terms of hydropower projects within a shared river basin and provides basin-wide case studies and considerations to hydropower relicensing. In the United States there are 1,043 active FERC-licensed hydroelectric projects with a total capacity of 56,097 MW. Of those, 647 with a total capacity of 21,870 MW have license expiration dates from 2018-2037. The expected workload in conjunction with the time, cost, and complexity associated with issuing a single new license has led to initiatives that aim to increase the efficiency of the relicensing process. Federal and state regulators and licensees in California, Maine, New York, and Wisconsin have begun to develop approaches to look at hydropower relicensing as part of a larger system - a river basin. These basin-wide approaches seek to coordinate different stages of the relicensing process for multiple projects at the same time. The goal of these basin-wide approaches is to increase the efficiency of the relicensing process and allow for a more comprehensive analysis of the cumulative impacts of the projects within the basin. These innovative approaches to relicensing could also reduce the workload for regulators and costs associated with relicensing. This presentation discusses some of the findings from the Basin-wide Approaches to Hydropower Relicensing: Case Studies and Considerations including a summary of the key considerations for the FERC relicensing process for non-federal hydropower projects, key findings from the analysis of FERC-licensed projects with license expiration dates from 2018-2037, discusses FERC's authority to coordinate license terms of hydropower projects within a shared river basin and provides basin-wide case studies and considerations to hydropower relicensing.

basin-wide↗
DOE OSTI2018

Surface Morphology and Electrical Properties of Cu 3 BTC 2 Thin Films Before and After Reaction with TCNQ

HKUST-1 or Cu 3 BTC 2 (BTC = 1,3,5-benzenetricarboxylate) is a prototypical metal–organic framework (MOF) that holds a privileged position among MOFs for device applications, as it can be deposited as thin films on various substrates and surfaces. Recently, new potential applications in electronics have emerged for this material when HKUST-1 was demonstrated to become electrically conductive upon infiltration with 7,7,8,8-tetracyanoquinodimethane (TCNQ). However, the factors that control the morphology and reactivity of the thin films are unknown. Here, we present a study of the thin-film growth process on indium tin oxide and amorphous Si prior to infiltration. From the unusual bimodal, non-log-normal distribution of crystal domain sizes, we conclude that the nucleation of new layers of Cu 3 BTC 2 is greatly enhanced by surface defects and thus difficult to control. We then show that these films can react with methanolic TCNQ solutions to form dense films of the coordination polymer Cu(TCNQ). This chemical conversion is accompanied by dramatic changes in surface morphology, from a surface dominated by truncated octahedra to randomly oriented thin platelets. The change in morphology suggests that the chemical reaction occurs in the liquid phase and is independent of the starting surface morphology. The chemical transformation is accompanied by 10 orders of magnitude change in electrical conductivity, from <10 –11 S/cm for the parent Cu 3 BTC 2 material to 10 –1 S/cm for the resulting Cu(TCNQ) film. In conclusion, the conversion of Cu 3 BTC 2 films, which can be grown and patterned on a variety of (nonplanar) substrates, to Cu(TCNQ) opens the door for the facile fabrication of more complex electronic devices.

2D nucleation↗
DOE OSTI2022

The emergence of valency in colloidal crystals through electron equivalents

Colloidal crystal engineering of complex, low-symmetry architectures is challenging when isotropic building blocks are assembled. In this study we describe an approach to generating such structures based upon programmable atom equivalents (nanoparticles functionalized with many DNA strands) and mobile electron equivalents (small particles functionalized with a low number of DNA strands complementary to the programmable atom equivalents). Under appropriate conditions, the spatial distribution of the electron equivalents breaks the symmetry of isotropic programmable atom equivalents, akin to the anisotropic distribution of valence electrons or coordination sites around a metal atom, leading to a set of well-defined coordination geometries and access to three new low-symmetry crystalline phases. All three phases represent the first examples of colloidal crystals, with two of them having elemental analogues (body-centred tetragonal and high-pressure gallium), while the third (triple double-gyroid structure) has no known natural equivalent. This approach enables the creation of complex, low-symmetry colloidal crystals that might find use in various technologies.

36 MATERIALS SCIENCE↗
DOE OSTI2025

From Electronic Structure to Ion Transport: Photoelectron Spectroscopy and Molecular Dynamics Simulations Reveal the Role of Anions in Lithium Battery Electrolytes

Electrolyte anions are pivotal for lithium battery performance, yet their fundamental electronic structural properties are not well understood. In this work, we employ a combination of negative-ion photoelectron spectroscopy (NIPES), ab initio calculations, and molecular dynamics (MD) simulations to investigate the electronic structures of three representative electrolyte anions. This multiscale approach enables us to elucidate how their intrinsic electronic properties govern anion–solvent interactions in gas-phase clusters, as well as lithium-ion (Li + ) solvation structures and ion transport behavior in the condensed phase. NIPES reveals that difluoro(oxalato)borate (DFOB – ), bis(fluorosulfonyl)imide (FSI – ), and bis(oxalato)borate (BOB – ) all exhibit high electron binding energies, with vertical/adiabatic detachment energies increasing from DFOB – (6.09/5.70 eV) to FSI – (6.80/6.10 eV) to BOB – (6.82/6.40 eV), correlating with enhanced oxidation stability. Ab initio calculations reveal that DFOB – /FSI – –solvent complexes bind Li + ∼ 10 kcal/mol stronger than BOB – series, aligning with the strength of a Li + –anion model. DFOB – exhibits pronounced charge localization on both oxygen and fluorine atoms, enabling their involvement in Li + coordination. In contrast, fluorine atoms in FSI – are largely electron-depleted and remain excluded from direct Li + binding. MD simulations further demonstrate that LiDFOB and LiFSI systems exhibit Li + diffusion coefficients three and five times higher than those of LiBOB across four common solvents. Notably, LiFSI salt in acetonitrile (AN) exhibits the fastest Li + diffusion among 12 electrolyte systems, highlighting the synergistic effect of FSI – and AN in promoting ion mobility. In conclusion, these findings provide a molecular-level understanding of the critical roles of anion and its microsolvation in optimizing Li + diffusion dynamics, once again emphasizing the positioning of FSI – and DFOB – as prime candidates for next-generation electrolytes.

25 ENERGY STORAGE↗
DOE OSTI2025

Supramolecular Assembly of Lanthanide-Binding Tag Peptides for Aqueous Separation of Rare Earth Elements

Selective and eco-friendly separation and purification methods for rare earth elements (REEs) are necessary to meet the increasing demand for these valuable metals, which are extensively used in modern electronics and clean energy technologies. Mining feedstocks consist of REE mixtures as stable trivalent cations (Ln 3+ ) that are difficult to separate due to their identical charge and similar size. Lanthanide-binding tags (LBTs), peptide chelates that coordinate Ln 3+ in binding pockets, show promise as selective, high-affinity extractants. We demonstrate that the LBT variant LBTLLA 5– , designed for high selectivity for Tb 3+ , is an effective extractant, forming complexes with REEs in solution that subsequently organize into self-assembling structures rich in Ln 3+ . These structures condense into aggregates that can be separated, enabling an efficient, all-aqueous, eco-friendly separation process. The self-assembled structures are studied using dynamic light scattering, ζ-potential measurements, transmission electron microscopy, anomalous small-angle X-ray scattering, inductively coupled plasma optical emission spectroscopy, and ultraviolet–visible absorption spectroscopy, which confirm LBTLLA 5– peptide-REE ion binding and the further assembly of micron-scale structures rich in REEs. Molecular dynamics simulations reveal the interactions promoting aggregation as well as the integrity of the binding pocket upon self-assembly. We find that LBTLLA 5– :Ln 3+ complexes recruit excess cations within the macrostructures, and we demonstrate that aggregation and selective separation can be controlled by manipulating the metal-peptide ratio in solution. Furthermore, we demonstrate separation from equimolar mixtures of REE pairs Tb 3+ -Lu 3+ and Tb 3+ -La 3+ , supporting the application of LBT peptides as a platform for the selective separation of REEs.

LBT peptides↗
DOE OSTI2025

Chlorocobaltate-Enabled Selective Separation of CoCl 2 from Mixed Chloride and Nitrate Salts of Mn, Co, and Ni

Described here is the effect of anionic metalates─chlorocobaltate and nitratocobaltate─on the heat-driven separation of the critical element cobalt from potentially competing transition metal salts. Resins bearing the hexadentate glycolamide receptor L (PS-L) exhibit sorption capacities, Q = 1.33 mmol/g for CoCl 2 and Q = 0.66 mmol/g for Co(NO 3 ) 2 , as inferred from sorption isotherm studies. This trend runs counter to the typical Hofmeister series for anion selectivity. Ion chromatographic analysis of a mixed CoCl 2 /Co(NO 3 ) 2 solution revealed an increase in chloride content from 55 mol % to 90 mol % after a single thermally driven catch-and-release cycle. This chloride-selective behavior was recapitulated in a mixed-metal cation, mixed-anion system containing the chloride and nitrate salts of Mn(II), Co(II), and Ni(II) at near-equimolar concentrations. PS-L also displayed enhanced selectivity for Co using this mixed stock solution as observed by ICP-OES. In contrast, for a nitrate-only solution containing Mn(II), Co(II), and Ni(II), PS-L showed increased affinity for Mn, with its proportion rising from 36.6 mol % to 58.1% after a single catch-and-release cycle. Density functional theory calculations support the suggestion that the enhanced uptake of Co(II) in chloride-rich media arises from the high thermodynamic stability of [CoCl 4 ] 2– , which facilitates its outer-sphere coordination to cationic resin-bound cobalt species. Single crystal X-ray crystallographic analyzes of L•MCl 2 (M = Mn, Co, Ni) and L•M(NO 3 ) 2 (M = Mn, Co) confirmed metal complexation by L in the solid state and the concomitant formation of metalate counteranions. Here, the present study highlights a relatively simple approach for separating cobalt from its transition metal congeners.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Structural basis of the promiscuity of the unusual Fe(II) and 2-oxoglutarate dependent human aspartate/asparagine-β-hydroxylase

Protein-hydroxylation catalysed by Fe(II) and 2-oxoglutarate (2OG) dependent oxygenases is an important regulatory mechanism in human biology. Such oxygenases typically coordinate their Fe(II) cofactor via a conserved triad of an aspartate- or glutamate- and two histidine-residues. By contrast, aspartate/asparagine β-hydroxylase (AspH), which catalyses asparagine/aspartate-residue oxidation in epidermal growth factor-like domains (EGFDs), has only two histidine-residues (H679, H725), with a water occupying the site normally occupied by an aspartate- or glutamate-residue. We describe mechanistic studies with catalytically active AspH crystals. Turnover studies with single crystals under cryogenic conditions give (3 R)-hydroxylated EGFDs with the product alcohol coordinating Fe(II) trans to H725. Time-resolved serial crystallography of microcrystals using an acoustic droplet ejection system, coupled to X-ray emission analyses, demonstrate turnover within 1.5 s, giving a product complex in which Fe(II) is regenerated. Solution and crystallographic studies with the O 2 surrogate nitric oxide imply O 2 binds to Fe(II) trans to H725. The additional Fe-chelating water is maintained throughout AspH catalysis and is not directly involved in substrate hydroxylation, because O 2 is the sole oxygen source in alcohol products, as shown by 18 O labelling studies. The results reveal how AspH accommodates both aspartate- and asparagine-substrates and will assist in efforts targeting AspH for cancer treatment.

de Munnik, Mariska↗
DOE OSTI2024

Resolving local ordering and structure in Mn x Ge 1- x Te alloys through thermodynamic ensembles of pair distribution functions

Characterizing local bonding environments in complex materials is essential for understanding and optimizing their properties. Equally as important is the ability to predict local motifs as a function of synthesis conditions, enhancing chemists’ ability to design properties into materials. In this study, we present an approach to leverage statistical mechanics to generate temperature- and energy-informed ensemble averaged pair distribution functions (PDFs). This method, which we have named Thermodynamic Ensemble Averages of PDFs for Ordering and Transformations (TEAPOT), utilizes density functional theory (DFT) to relax supercells while incorporating energetic penalties for local order, enabling accurate and computationally efficient analysis of local structure. We apply this method to the neutron PDF measurements of the pseudobinary MnTe–GeTe (MGT) alloy, demonstrating its capability to resolve complex local distortions and chemical ordering. Our results reveal detailed insights into phase transformations and local distortions driven by Mn substitution. For compositions that globally present as rock salt, our analysis reveals that Ge coordination geometry is heavily impacted by synthesis temperature. We propose that high temperature synthesis conditions promote a lowered Ge polyhedra distortion, promoting high charge carrier mobility due to the alignment of local and global structure. Incorporating statistical mechanics and computation into experimental analysis thus guides synthesis of tailored local structure.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Protein engineering of a ubiquitin-variant inhibitor of APC/C identifies a cryptic K48 ubiquitin chain binding site

Ubiquitin (Ub)-mediated proteolysis is a fundamental mechanism used by eukaryotic cells to maintain homeostasis and protein quality, and to control timing in biological processes. Two essential aspects of Ub regulation are conjugation through E1-E2-E3 enzymatic cascades and recognition by Ub-binding domains. An emerging theme in the Ub field is that these 2 properties are often amalgamated in conjugation enzymes. In addition to covalent thioester linkage to Ub’s C terminus for Ub transfer reactions, conjugation enzymes often bind noncovalently and weakly to Ub at “exosites.” However, identification of such sites is typically empirical and particularly challenging in large molecular machines. In this work, studying the 1.2-MDa E3 ligase anaphase-promoting complex/cyclosome (APC/C), which controls cell division and many aspects of neurobiology, we discover a method for identifying unexpected Ub-binding sites. Using a panel of Ub variants (UbVs), we identify a protein-based inhibitor that blocks Ub ligation to APC/C substrates in vitro and ex vivo. Biochemistry, NMR, and cryo-electron microscopy (cryo-EM) structurally define the UbV interaction, explain its inhibitory activity through binding the surface on the APC2 subunit that recruits the E2 enzyme UBE2C, and ultimately reveal that this APC2 surface is also a Ub-binding exosite with preference for K48-linked chains. The results provide a tool for probing APC/C activity, have implications for the coordination of K48-linked Ub chain binding by APC/C with the multistep process of substrate polyubiquitylation, and demonstrate the power of UbV technology for identifying cryptic Ub-binding sites within large multiprotein complexes.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2019

The constrained architecture of mammalian Hox gene clusters

In many animal species with a bilateral symmetry, Hox genes are clustered either at one or at several genomic loci. This organization has a functional relevance, as the transcriptional control applied to each gene depends upon its relative position within the gene cluster. It was previously noted that vertebrate Hox clusters display a much higher level of genomic organization than their invertebrate counterparts. The former are always more compact than the latter, they are generally devoid of repeats and of interspersed genes, and all genes are transcribed by the same DNA strand, suggesting that particular factors constrained these clusters toward a tighter structure during the evolution of the vertebrate lineage. Here, we investigate the importance of uniform transcriptional orientation by engineering several alleles within the HoxD cluster, such as to invert one or several transcription units, with or without a neighboring CTCF site. We observe that the association between the tight structure of mammalian Hox clusters and their regulation makes inversions likely detrimental to the proper implementation of this complex genetic system. We propose that the consolidation of Hox clusters in vertebrates, including transcriptional polarity, evolved in conjunction with the emergence of global gene regulation via the flanking regulatory landscapes, to optimize a coordinated response of selected subsets of target genes in cis .

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Berkelium–carbon bonding in a tetravalent berkelocene

Interest in actinide–carbon bonds has persisted since actinide organometallics were first investigated for applications in isotope separation during the Manhattan Project. Transplutonium organometallics are rarely isolated and structurally characterized, likely owing to limited isotope inventories, a scarcity of suitable laboratory infrastructure, and intrinsic difficulties with the anaerobic conditions required. In this paper, we report the discovery of an organometallic “berkelocene” complex prepared from 0.3 milligrams of berkelium-249. Single-crystal x-ray diffraction shows a tetravalent berkelium ion between two substituted cyclooctatetraene ligands, resulting in the formation of berkelium–carbon bonds. The coordination in berkelocene resembles that of uranocene, and calculations show that the berkelium 5f orbitals engage in covalent overlap with the δ-symmetry orbitals of the cyclooctatetraenide ligand π system. Charge transfer from the ligands is diminished relative to uranocene and other actinocenes, which maximizes contributions from the stable, half-filled 5f 7 configuration of tetravalent berkelium.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

The Fluorescent Properties and Electronic Structure of Nd(111) Complexes with Carboxylic Acids

Mixed-ligand neodymium(III) complexes with carboxylic acids and nitrogen- and phosphorus-containing neutral ligands, which luminesce in the near-IR region, are studied by luminescence and X-ray photoelectron spectroscopies. It is found that coordination of neutral ligands through the nitrogen donor atom leads to an increase in the electron density at the neodymium(III) ion.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2025

Long-Range Allosteric Communication Modulated by Active Site Mn(II) Coordination Drives Catalysis in Xanthobacter autotrophicus Acetone Carboxylase

Acetone carboxylase (AC) from Xanthobacter autotrophicus is a 360 KDa α2β2γ2 heterohexamer that catalyzes the ATP-dependent formation of phosphorylated acetone and bicarbonate intermediates that react at Mn(II) metal active sites to form acetoacetate. Structural models of X. autotrophicus AC (XaAC) with and without nucleotides reveal that the binding and phosphorylation of the two substrates occurs ~40 Å from the Mn(II) active sites where acetoacetate is formed. Based on the crystal structures, a significant conformational change was proposed to open and close a tunnel that facilitates the passage of reaction intermediates between the sites for nucleotide binding and phosphorylation of substrates and Mn(II) sites of acetoacetate formation. We have employed electron paramagnetic resonance (EPR), kinetic assays, and hydrogen/deuterium exchange mass spectrometry (HDX-MS) of poised ligand-bound states and site-specific amino acid variants to complete an in-depth analysis of Mn(II) coordination and allosteric communication throughout the catalytic cycle. In contrast with the established paradigms for carboxylation, our analyses of XaAC suggested a carboxylate shift that couples both local and long-range structural transitions. Shifts in the coordination mode of a single carboxylic acid residue (αE89) mediate both catalysis proximal to a Mn(II) center and communication with an ATP active site in a separate subunit of a 180 kDa α2β2γ2 complex at a distance of 40 Å. This work demonstrates the power of combining structural models from X-ray crystallography with solution-phase spectroscopy and biophysical techniques to elucidate functional aspects of a multi-subunit enzyme.

Biochemistry & Molecular Biology↗