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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 883 records · Page 49
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Application of the Recharge Estimation Tool (RET) to Prepare Spatially and Temporally Variable Recharge Boundary Conditions for Hanford Site Composite Analysis Vadose Zone Models

This environmental calculation file (ECF) describes the development of a tool for translating recharge estimates into readable input for STOMP© (Subsurface Transport Over Multiple Phases) vadose zone models primarily supporting the vadose zone (VZ) facets of the updated Hanford Site Composite Analysis (CA) and the Hanford Site Cumulative Impact Evaluation (CIE). The recharge estimates are spatiotemporally variable and are produced by the Recharge Evolution Tool (RET) described in Hanford Site-wide Natural Recharge Boundary Condition for Groundwater Models (ECF-HANFORD-15-0019). Outputs from the RET are given in Esri’s™ feature class format with yearly estimates and associated metadata encapsulated in file geodatabase objects. For STOMP models, the translated output is a text file in the format of an input boundary condition card, consistent with STOMP software requirements. The text file contains assimilated spatiotemporal recharge estimates produced by the RET. The tool discussed in this document will be referred to as the “RET2STOMP” tool.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2020

Dendrite Growth Morphology Modeling in Liquid and Solid Electrolytes

The main goal of this project is to develop a multi-scale modeling approach that connects micron-scale phase-field models and atomic-scale density functional theory (DFT)-based simulations via parameter- and relationship-passing in order to predict Li-metal dendrite morphology evolution, in both liquid and solid electrolytes. The key hypothesis of the DFT-informed phase-field multiscale modeling approach is that it can capture the electrochemical-mechanical driving forces and incorporate the roles of nano-meter-thin solid electrolyte interphase (SEI) in liquid electrolytes as well as of the microstructures of micro-meter-thick solid electrolytes (SEs) for all-solid-state batteries. In this project, we have formulated and implemented phase-field models to incorporate the electrochemical driving forces in liquid electrolytes and then incorporate mechanical driving forces to simulate dendrite growth in solid electrolytes with resolved microstructures. We have implemented two treatments for the SEI: an explicit model to include the microstructure of the SE or SEI in the phase field model and an implicit model to simulate the impact of nano-meter thick SEI in liquid electrolytes by varying the electrode/electrolyte interfacial properties. The key interfacial properties, including the electronic and ionic transport properties, the charge transfer reaction kinetics, and mechanical properties, were computed by DFT-based calculations. At the DFT-based model, one key advancement is to directly predict the charge transfer reaction kinetics at a complex Li/SEI/electrolyte interface by linking DFT with density functional tight binding (DFTB) calculations. As the main accomplishments, we have demonstrated two successful predictions in both solid electrolyte and liquid electrolyte based on this multiscale approach. The predicted intergranular Li dendrite growth in LLZO revealed the importance of trapped electrons at internal interfaces in the microstructure of LLZO. The predicted electroplating morphology of mossy Li and faceted Mg agreed well with experiments. The insights provided by the multiscale model and the model enabled electrolyte and SEI design will accelerate the development of Li-metal electrode for high energy density batteries, that meet DOE’s target on cell density (>350 Wh/kg) and cost below $100/kWhuse for EV applications.

25 ENERGY STORAGE↗
DOE OSTI2020

Sandia's Research in Support of COVID-19 Pandemic Response: Computing and Information Sciences

This report summarizes the goals and findings of eight research projects conducted under the Computing and Information Sciences (CIS) Research Foundation and related to the COVID- 19 pandemic. The projects were all formulated in response to Sandia's call for proposals for rapid-response research with the potential to have a positive impact on the global health emergency. Six of the projects in the CIS portfolio focused on modeling various facets of disease spread, resource requirements, testing programs, and economic impact. The two remaining projects examined the use of web-crawlers and text analytics to allow rapid identification of articles relevant to specific technical questions, and categorization of the reliability of content. The portfolio has collectively produced methods and findings that are being applied by a range of state, regional, and national entities to support enhanced understanding and prediction of the pandemic's spread and its impacts.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Status Report on Development of a Cask to Enable Pulsed Neutron Characterization of Irradiated Fuel

We present the design of a shielding cask that allows pulsed neutron characterization of irradiated fuel rodlets prior to their destructive examination in hot cells. The goal is to provide complementary and informative measurements that will inform subsequent hot cell PIE examinations by identifying typical and atypical regions with respect to microstructure, tomographic data, or isotope densities. Time-of-flight neutron diffraction has the potential to offer efficient, non-destructive and non-contact microstructural characterization of irradiated fuel pins with spatial resolution of 1 mm3 to 1 cm3 while for energy-resolved neutron imaging (and by extension tomography) a resolution of 100 μm was demonstrated. The potential results include crystallinity vs. amorphous volumes and microstructural information such as phase compositions and textures from the diffraction data as well as distances (e.g. pellet to cladding), cracks, and isotopic distributions of minor actinides, fission products as well as fission gas partial pressures e.g. in the plenum from energy resolved neutron imaging. The capability will identify regions of atypical behavior and provide cost effective bulk characterization of entire samples prior to destructive evaluation in hot cells. This effort is a collaboration between LANL, INL, ORNL, and UC Berkeley. A key facet of the initiative is the ability to cost effectively ship irradiated fuels from INL to the pulsed spallation neutron source at LANSCE. The irradiated fuel would be loaded in the custom designed cask (designated RaMHaM) at INL hot cells which then could be shipped in a BRR Type B shipment container between INL and LANL. No hot cell is required after the loading of the sample at INL in the pathway laid out in this report, greatly simplifying handling at LANL.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2020

Hanford Site-wide Natural Recharge Boundary Condition for Groundwater Models

The purpose of this environmental calculation file (ECF) is to document the development of a tool that generates temporally and spatially variable representations of natural recharge for the Hanford Site. A key feature of the recharge evolution tool (RET) is that it applies sanctioned natural recharge rates varying as a function of the condition/cover of the ground surface and soil type at different points in time. No hydrologic calculations are performed by the RET, this script works as a lookup database between spatial and temporal datasets to assign research-based recharge rates to corresponding regions throughout the Hanford Site. This work will support vadose zone and groundwater models for the Hanford Site. Although efforts will focus on generating recharge estimates for the entirety of the Hanford Site, the focus scope of this work will be the Central Plateau Area to support the Composite Analysis Vadose Zone facet. In other words, the reliability of this calculation will be greatest within the Central Plateau Area and decrease with departures from that geographic region.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2020

2019 Site Environmental Report (Volume 1)

Brookhaven National Laboratory (BNL) is managed on behalf of the Department of Energy (DOE) by Brookhaven Science Associates (BSA), a partnership between the Research Foundation for the State University of New York on behalf of Stony Brook University and Battelle. For over 70 years, the Laboratory has played a lead role in the DOE Science and Technology mission and continues to contribute to the DOE’s missions in energy resources, environmental quality, and national security. BNL manages its world-class scientific research with particular sensitivity to environmental issues and community concerns. The Laboratory’s Environmental, Safety, Security, and Health (ESSH) Policy reflects the commitment of BNL’s management to fully integrate environmental stewardship into all facets of its mission and operations. BNL prepares an annual Site Environmental Report (SER) in accordance with DOE Order 231.1B, Environment, Safety, and Health Reporting. The report is written to inform the public, regulators, employees, and other stakeholders of the Laboratory’s environmental performance during the calendar year in review. Volume I of the SER summarizes environmental data; environmental management performance; compliance with applicable DOE, federal, state, and local regulations; and performance in restoration and surveillance monitoring programs. BNL has prepared annual SERs since 1971 and has documented nearly all its environmental history since the Laboratory’s inception in 1947. Volume II of the SER, the Groundwater Status Report, is also prepared annually to report on the status of groundwater protection and restoration efforts. Volume II includes detailed technical summaries of groundwater data and treatment system operations and is intended for regulators and other technically oriented stakeholders. A summary of the information contained in Volume II is included in Chapter 7, Groundwater Protection, of this volume.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Metalorganic chemical vapor deposition of ZnGeN 2 films on GaN: effects of cation stoichiometry on surface morphology and crystallinity

Novel optoelectronic device designs based on the heterostructures of III-N and II-IV-N 2 are promising to advance device performance significantly. For example, by utilizing InGaN-ZnGeN 2 quantum well (QW) structures instead of pure InGaN, the band structure engineering in the QW active region can lead to improved electron-hole wavefunction overlap, and thus enhance the radiative efficiency for photon generation. These novel heterostructures have great potential to address the current challenge of low quantum efficiency in InGaN QW based light emitting diodes emitting in green and beyond. The materials development of ZnGeN 2 is still at an early stage as compared to the much matured GaN material system. In an ideal octet rule preserving ordered structure of ZnGeN 2 , every N atom is coordinated by exactly two Zn and two Ge atoms. However, local violation of octet rule can be caused by non-ideal coordination of N by the cations. The disordered structure is thermodynamically less favorable but can still be achieved, for example, in kinetics-limited growth regime. The ordered ZnGeN 2 has a bandgap very close to that of GaN (~3.4 eV) and a lattice mismatch of <0.1% with GaN. Interestingly, the valence band of ZnGeN 2 has been predicted to be ~1 eV above that of GaN, which has inspired novel designs for high efficiency light emitters. In this work, we investigated the metalorganic chemical vapor deposition (MOCVD) of ZnGeN 2 films on GaN/c-sapphire templates. Diethylzinc (DEZn), germane (GeH4) and ammonia were used as the precursors for Zn, Ge and N, respectively. A systematic study was conducted to investigate the cation stoichiometry as a function of growth temperature (TG), total reactor pressure (P) and DEZn/GeH 4 molar flow rate ratio (RII/IV). Under the investigated growth window, the Zn/(Zn+Ge) composition in the films, determined from energy dispersive X-ray spectroscopy, decreased monotonically with increase in TG but increased with increase in P and RII/IV. Atom probe tomography data did not indicate the presence of any secondary phases such as Zn 3 N 2 or Ge 3 N 4 . The surface morphology and crystallinity of the grown films had strong correlation with the Zn/(Zn+Ge) composition. The scanning electron microscopy images showed that the near-stoichiometric films have planar surfaces whereas Zn-rich films had crystallites on their surface and the Zn-poor films had faceted surface. Scanning transmission electron microscopy (STEM) imaging revealed that the Zn-rich and Zn-poor films have columnar and filament-like morphology, respectively, whereas the near-stoichiometric films have continuous film-like cross-sectional morphology. TEM nano-diffraction patterns as well as X-ray diffraction 2θ-ω scan profiles indicate that the near stoichiometric films are single crystalline. Nano-diffraction pattern of the stoichiometric films resembled that of a disordered ZnGeN 2 structure. Room temperature Raman spectra of near-stoichiometric films showed only the phonon density of states like features of a cation disordered ZnGeN 2 . Cathodoluminescence and photoluminescence spectra measured at different temperatures had similar features with peak emission wavelength at ~ 2 eV. In conclusion, the stoichiometry of ZnGeN 2 films can be widely tuned by tuning the MOCVD growth parameters. The surface morphology and the crystallinity of the films were found to have strong correlation with the Zn/(Zn+Ge) composition. The stoichiometric ZnGeN 2 films grown on GaN were demonstrated with uniform surface morphology and high crystalline quality. The results from this work will provide pathway to implement ZnGeN 2 in device structures.

Karim, Md Rezaul↗
DOE OSTI2020

How to Actively Not be a Barrier to Diversity Efforts in Physics

Systemic racism permeates all facets of our society and the recent horrific killings of George Floyd, Breonna Taylor and many others are just one of the many reminders of this. The serious lack of underrepresented minorities (URMs) in physics is proof that our field is no exception to discrimination and racism. In light of the recent events, it is important to confront ourselves about how our own complicity and inaction have perpetuated racism and a culture that allows racist actions to thrive.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2020

Pre-Commercial Scale-Up of a Gas-Fired Absorption Heat Pump

The project sought to advance the maturity of SMTI’s 80 kBTU/hr residential space and water heating GAHP from the engineering prototype stage (TRL-7) to pre-production readiness by addressing manufacturing, balance of system design and installation, cost, reliability, and field application questions. As part of this project, the project team has: (1) Matured the design package for a commercially ready product (2) Demonstrated compliance with relevant ANSI standards (3) Completed manufacturing and assembly process specifications (4) Completed total production cost estimates and capital equipment requirements (5) Initiated component and system level reliability assessments (6) Completed a small field demonstration including measured performance, installation requirements and expected costs, and customer/key stakeholder feedback. (7) Completed a Techno-economic analysis for representative applications and climate zones, including justification for utility incentive programs. (8) Completed a market intelligence report. Scope of Work: A multi-faceted project was completed that included: (a) design for manufacturing tasks for both the sealed system and balance of system, (b) development and trial of key manufacturing processes and techniques, (c) evaluation of component and system level reliability, (d) exploration of make/buy decisions including impact on cost and required capital. Additionally, (e) installation and monitoring of a small number of field test units was completed to demonstrate energy savings and collect customer/installer feedback, and (f) a focused market research task was completed to explore potential barriers and improve market introduction plans. These tasks addressed many of the remaining technical risks regarding long-term reliability, verification of manufacturing cost estimates and identification of cost concerns, identify installation and balance of system design criteria necessary to achieve energy savings and installed cost goals, and identify market barriers and strategies prior to product market introduction.

03 NATURAL GAS↗
DOE OSTI2021

Recommendations for Distributed Energy Resource Access Control

Cybersecurity for internet - connected Distributed Energy Resources (DER) is essential for the safe and reliable operation of the US power system. Many facets of DER cybersecurity are currently being investigated within different standards development organizations, research communities, and industry committees to address this critical need. This report covers DER access control guidance compiled by the Access Controls Subgroup of the SunSpec/Sandia DER Cybersecurity Workgroup. The goal of the group was to create a consensus - based technical framework to minimize the risk of unauthorized access to DER systems. The subgroup set out to define a strict control environment where users are authorized to access DER monitoring and control features through three steps: (a) user is identified using a proof-of-identity, (b) the user is authenticated by a managed database, (c) and the user is authorized for a specific level of access. DER access control also provides accountability and nonrepudiation within the power system control environment that can be used for forensic analysis and attribution in the event of a cyber-attack. This paper covers foundational requirements for a DER access control environment as well as offering a collection of possible policy, model, and mechanism implementation approaches for IEEE 1547-mandated communication protocols.

45 MILITARY TECHNOLOGY, WEAPONRY, AND NATIONAL DEF↗
DOE OSTI2021

Elucidating Hydrogen Reaction-Induced Water Desorption from Oxide-Passivated Metal Surfaces for Plasma Applications

Elucidating the mechanisms responsible for sub-microsecond desorption of water and other impurities from electrode surfaces at high heating rates is crucial for understanding pulsed power behavior. Ionization of desorbed impurities in the vacuum regions causes power or current loss; devising methods to limit such desorption during the short time scale of pulsed power is needed to improve corresponding applications. Previous molecular modeling studies have strongly suggested that, under high vacuum conditions, the amount of water impurity desorbing from oxide surfaces on metal electrodes is at a sub-monolayer level at room temperature, which appears insufficient to explain observed pulsed power energy losses at high current densities. In this work, we apply Density Functional Theory (DFT) techniques to show that hydrogen trapped inside iron metal can diffuse into hematite (α-Fe 2 O 3 ) on the metal surface, ultimately reacting with the oxide to form Fe(II) and H 2 O. The latter desorbs at elevated temperature and may explain the anomalous amount of desorbed impurity inferred from pulsed-power experiments. We also apply a suite of characterization techniques to demonstrate that when iron metal is heated to 650 °C, the dominant surface oxide component becomes α-Fe 2 O 3 . The oxide facets exposed are found to be a mixture of (0001), (10-10), and others, in agreement with the DFT models used.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2021

Concurrent Optimization of Capital Cost and Expected O&M

Concentrating solar power (CSP) technologies can utilize heat from concentrated sunlight from a field of tracking mirrors to generate electricity, reform fuel, provide process heat, or augment fossil plant heat sources. Electricity-generating power tower systems focus light from thousands of independent heliostats onto a thermal receiver, which uses the focused light to warm a heat transfer fluid (HTF), typically, a molten nitrate salt. The HTF is then sent to a power generation cycle or diverted into thermal energy storage (TES) for later use. Thermal storage is – in principle – a straightforward proposition. However, optimal utilization of a TES resource is complex and multi-faceted: thermal energy may be dispatched to produce electricity immediately upon first availability, or thermal energy may be reserved for next-day peak periods at risk of filling storage and dumping energy, or a portion of the thermal energy can be reserved to maintain equipment temperatures, reducing power cycle startup time, etc. Many possible dispatch permutations variously emphasize producing peak power, operating through transients, expediting daily startup, etc. The best operation strategy can change day-to-day throughout the year, depending on the weather and market pricing forecasts. The project we describe in this report develops a software package that allows users to explore design optimization, operations decisions, and performance characterization of concentrating solar power tower plants. Users interface with the tool through a scripting language, and results are reported in time series tables, plots, runtime logs, and design outputs. Users choose from a list of variables such as tower height, solar multiple, design-point irradiance, thermal storage size, etc., and specify information about the system using a list of parameters. The software can then optimize the specified variables to reduce the cost of energy produced by the system while meeting certain production requirements, accounting for uncertain weather and electricity price forecasts, and correcting for equipment failures or repair time. The software we develop is the first comprehensive design tool of its kind to incorporate all of these aspects while being deployed as open source.

14 SOLAR ENERGY↗
DOE OSTI2021

It begins - digitizing the Rocky Flats Collection

From 1952 to 1989, the Rocky Flats Plant near Golden, Colorado, manufactured plutonium cores - the nuclear weapon pits that still exist in the nation’s nuclear weapons stockpile. Not only did Rocky Flats personnel produce these plutonium cores, they also documented every facet of this highly technical process. Moreover, Rocky Flats was a premier center for actinide research and development, with these data as relevant today as they were yesterday

96 KNOWLEDGE MANAGEMENT AND PRESERVATION↗
DOE OSTI2021

Demonstration and Validation of Additively Manufactured Intensified Device for Enhanced Carbon Capture

In FY 2018 and 2019, ORNL personnel designed, prototyped, characterized, and tested the enhancement of amine-based carbon capture using additively manufactured intensified devices, i.e., devices combining multiple thermodynamic and kinetic processes into one unit operation. State of the art scrubbing technology often employs inter-stage cooling which requires multiple stages of single-purpose unit operations, leading to larger equipment size, higher capital cost, and sometimes less than optimal operating conditions for each piece of equipment. It was proposed that integrating multiple thermodynamic and kinetic operations into one unit could mitigate or negate these drawbacks. Heat and mass transfer studies demonstrated that an additively manufactured intensified device could significantly improve capture efficiency at bench scale. This project is a continuation of FEAA130 and aims at (1) demonstration and validation of enhanced CO 2 capture with 3D printed intensified devices (i.e., mass exchanger packing with internal cooling channels), for low-aqueous-solvent (LAS) based capture at the ORNL-constructed laboratory-scale (4.5-feet tall) column, namely Column A, with built-in cooling and (2) computational scoping on the conceptual design of a flexible and modular larger column, namely Column B, at ORNL for further demonstration of enhanced capture for aqueous solvent. To execute this multi-faceted project scope, an integrated project team from ORNL’s Manufacturing Science Division is tasked with applying capabilities in computational fluid dynamics (CFD), additive manufacturing, and absorber-scale demonstration/validation experiments.

42 ENGINEERING↗
DOE OSTI2021

Investigating User Experiences with Data Abstractions on High Performance Computing Systems

Scientific exploration generates expanding volumes of data that commonly require High Performance Computing (HPC) systems to facilitate research. HPC systems are complex ecosystems of hardware and software that frequently are not user friendly. The Usable Data Abstractions (UDA) project set out to build usable software for scientific workflows in HPC environments by undertaking multiple rounds of qualitative user research. Qualitative research investigates how individuals accomplish their work and our interview-based study surfaced a variety of insights about the experiences of working in and with HPC ecosystems. This report examines multiple facets to the experiences of scientists and developers using and supporting HPC systems. We discuss how stakeholders grasp the design and configuration of these systems, the impacts of abstraction layers on their ability to successfully do work, and the varied perceptions of time that shape this work. Examining the adoption of the Cori HPC at NERSC we explore the anticipations and lived experiences of users interacting with this system’s novel storage feature, the Burst Buffer. We present lessons learned from across these insights to illustrate just some of the challenges HPC facilities and their stakeholders need to account for when procuring and supporting these essential scientific resources to ensure their usability and utility to a variety of scientific practices.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2021

High-Efficiency, Low-Cost III-V Solar Cells by Dynamic Hydride Vapor Phase Epitaxy Coupled with Rapid, Polishing-Free Wafer Reuse through Orientation-Optimized (110) Spalling

We demonstrated (110) GaAs solar cells grown by D-HVPE with equivalent performance and material quality relative to (100) devices. Also, we developed a procedure for repeatable wafer-scale spalling of (110) GaAs. Spalled surfaces were free of the facets founds in (100) GaAs spalling, the large arrest lines found in (100) Ge spalling, and surface features greater than 3 µm in peak-to-valley height, which can otherwise degrade the efficiency of regrown III-V devices. A sub-µm step-terrace morphology was discovered on the post-spall wafer surface, resulting from the restricted cleavage system of GaAs, but we developed understanding of the factors that determine the resulting morphology, enabling ample opportunity for optimization of morphologies suitable for device growth and spall depth waste minimization on (110) GaAs. Lastly, we demonstrated a device grown on a previously spalled surface with only 8% relative efficiency difference to a cell grown on a new unspalled wafer. Significant optimization of the substrate regrowth conditions are required to enable higher efficiency, but these results highlight the promise of (110)-oriented devices coupled with substrate reuse by spalling as a pathway for low-cost III-V photovoltaics.

14 SOLAR ENERGY↗
DOE OSTI2021

Analytic Framework for Optimal Sizing of Hydrogen Fueling Stations for Heavy Duty Vehicles at Ports (CRADA 512)

This CRADA presents the strategy that PNNL and Sandia National Laboratories (SNL) will take to support Seattle City Light (SCL) in properly sizing a hydrogen station for class 8 drayage trucks at the Port of Seattle (Port), as part of a coordinated plan of mixed uses for hydrogen. The proper sizing for the fueling station is unique from past experiences because it will be part of a coordinated plan for a multi-use scheme for the hydrogen, and not a stand-alone fueling station. The multiple use-streams, and their relative values, will impact all facets of station sizing and design, including fueling rates, storage technology and size, equipment selection, and safety considerations. The future deployment of this fueling station, and its proper sizing, is seen as a critical first step in the larger vision of utilizing hydrogen to address a range of issues for SCL and the Port. These include, but are not limited to, large scale fueling of medium duty (MD) and heavy duty (HD) vehicles to reduce emissions, support of adjacent light duty (LD) vehicles, support of critical port operation during extreme events (e.g. resiliency), mitigation of capital intensive electrical distribution system upgrades to support evolving port operations, a market resource that can be used by SCL to generate revenue, and support of planned future maritime operations that currently require heavy use of shipboard hydrogen. While the broader use of hydrogen by SCL and the Port is not the focus of this CRADA, how its use impacts the design of the initial vehicle fueling station, and the modular approach, are the central work. As such, this project will develop the framework and process for developing a modular station design that considers the broader range of coordinate uses of hydrogen as an energy resource.

08 HYDROGEN↗
DOE OSTI2022

Allosteric control of electron transfer in nitrogenase and nitrogenase-like enzymes (Final Report)

More than a third of all known proteins to date are either oxidoreductases or metalloproteins. The diversity of metal cofactors and redox centers in these proteins make them attractive candidates for engineering protein-based biocatalysts, biosensors, and biofuel cells, among other necessary tools for the bioeconomy. Many of these enzymes function as large multi-subunit complexes arranged as symmetric or asymmetric assemblies, and the purpose of this architecture is unclear. The goal of the project was to address this fundamental question by investigating the mechanism of action of two oxidoreductases: Nitrogenase and DPOR (Dark-Operative Protochlorophyllide Oxidoreductase, a nitrogenase-like oxidoreductase). Nitrogenase and DPOR play key roles in nitrogen fixation and photosynthesis, processes essential to sustaining life. Both proteins are arranged as two symmetrical halves with each half capable of substrate reduction. For more than half a century, substrate reduction by nitrogenase has been presumed to occur independently within the two identical halves. Funded by this DOE grant we have now shown that both nitrogenase and DPOR function asymmetrically. Electron transfer in one half suppresses activity in the other. Thus, we have demonstrated that the two halves do not function in an independent manner; rather, catalytic events in one-half allosterically suppress activity and electron transfer (ET) in the other. This alternating-site mechanism has significant implications on our current understanding of substrate reduction by these enzymes and offers a new mechanistic paradigm for the reactions they catalyze. Our work now provides a mechanistic map of the how the two symmetric catalytic halves work together to establish and maintain the sequential-site mechanism through multiple ET cycles to achieve substrate reduction. There is substantive need for bio-inspired tools that enable reduction of nitrogen and other substrates, as well as photosynthesis, for energy and food production. Understanding the workings of enzymes like nitrogenase and DPOR that mediate multi-electron redox chemistry is vital for designing such synthetic tools. The timing of our research coincides with the biotechnological breakthrough of light-driven artificial N2 reduction by nitrogenase, achieved using the native enzyme with both halves arranged in a mirror-like architecture as catalyst. Together with such discoveries, our research now reveal unknown facets of the reaction mechanism and hold promise for designing more effective catalysts.

59 BASIC BIOLOGICAL SCIENCES↗