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At least 595 records · Page 33

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NASA NTRS1993

Brain wave correlates of attentional states: Event related potentials and quantitative EEG analysis during performance of cognitive and perceptual tasks

The increased use of automation in the cockpits of commercial planes has dramatically decreased the workload requirements of pilots, enabling them to function more efficiently and with a higher degree of safety. Unfortunately, advances in technology have led to an unexpected problem: the decreased demands on pilots have increased the probability of inducing 'hazardous states of awareness.' A hazardous state of awareness is defined as a decreased level of alertness or arousal which makes an individual less capable of reacting to unique or emergency types of situations. These states tend to be induced when an individual is not actively processing information. Under such conditions a person is likely to let his/her mind wander, either to internal states or to irrelevant external conditions. As a result, they are less capable of reacting quickly to emergency situations. Since emergencies are relatively rare, and since the high automated cockpit requires progressively decreasing levels of engagement, the probability of being seduced into a lowered state of awareness is increasing. This further decreases the readiness of the pilot to react to unique circumstances such as system failures. The HEM Lab at NASA-Langley Research Center has been studying how these states of awareness are induced and what the physiological correlates of these different states are. Specifically, they have been interested in studying electroencephalographic (EEG) measures of different states of alertness to determine if such states can be identified and, hopefully, avoided. The project worked on this summer involved analyzing the EEG and the event related potentials (ERP) data collected while subjects performed under two conditions. Each condition required subjects to perform a relatively boring vigilance task. The purpose of using these tasks was to induce a decreased state of awareness while still requiring the subject to process information. Each task involved identifying an infrequently presented target stimulus. In addition to the task requirements, irrelevant tones were presented in the background. Research has shown that even though these stimuli are not attended, ERP's to them can still be elicited. The amplitude of the ERP waves has been shown to change as a function of a person's level of alertness. ERP's were also collected and analyzed for the target stimuli for each task. Brain maps were produced based on the ERP voltages for the different stimuli. In addition to the ERP's, a quantitative EEG (QEEG) was performed on the data using a fast Fourier technique to produce a power spectral analysis of the EEG. This analysis was conducted on the continuous EEG while the subjects were performing the tasks. Finally, a QEEG was performed on periods during the task when subjects indicated that they were in an altered state of awareness. During the tasks, subjects were asked to indicate by pressing a button when they realized their level of task awareness had changed. EEG epochs were collected for times just before and just after subjects made this reponse. The purpose of this final analysis was to determine whether or not subjective indices of level of awareness could be correlated with different patterns of EEG.

Freeman, Frederick G.↗

NASA NTRS2003

In-Space Propulsion: Where We Stand and What's Next

The focus of this paper will be on the three stages of in-space transportation propulsion systems, now commonly referred to as in-space propulsion (ISP); i.e., the transfer of payloads from low-Earth orbits into higher orbits or into trajectories for planetary encounters, including planetary landers and sample return launchers, if required. Functions required at the operational location where ISP must provide thrust for orbit include maintenance, position control, stationkeeping, and spacecraft altitude control; i.e., proper pointing and dynamic stability in inertial space; and the third function set to enable operations at various planetary locations, such as atmospheric entry and capture, descent to the surface and ascent, back to rendezvous orbit. The discussion will concentrate on where ISP stands today and some observations of what might be next in line for new ISP technologies and systems for near-term and future flight applications. The architectural choices that are applicable for ISP will also be described and discussed in detail.

Sackheim, Robert L.↗

NASA NTRS2007

Video Guidance Sensor and Time-of-Flight Rangefinder

A proposed video guidance sensor (VGS) would be based mostly on the hardware and software of a prior Advanced VGS (AVGS), with some additions to enable it to function as a time-of-flight rangefinder (in contradistinction to a triangulation or image-processing rangefinder). It would typically be used at distances of the order of 2 or 3 kilometers, where a typical target would appear in a video image as a single blob, making it possible to extract the direction to the target (but not the orientation of the target or the distance to the target) from a video image of light reflected from the target. As described in several previous NASA Tech Briefs articles, an AVGS system is an optoelectronic system that provides guidance for automated docking of two vehicles. In the original application, the two vehicles are spacecraft, but the basic principles of design and operation of the system are applicable to aircraft, robots, objects maneuvered by cranes, or other objects that may be required to be aligned and brought together automatically or under remote control. In a prior AVGS system of the type upon which the now-proposed VGS is largely based, the tracked vehicle is equipped with one or more passive targets that reflect light from one or more continuous-wave laser diode(s) on the tracking vehicle, a video camera on the tracking vehicle acquires images of the targets in the reflected laser light, the video images are digitized, and the image data are processed to obtain the direction to the target. The design concept of the proposed VGS does not call for any memory or processor hardware beyond that already present in the prior AVGS, but does call for some additional hardware and some additional software. It also calls for assignment of some additional tasks to two subsystems that are parts of the prior VGS: a field-programmable gate array (FPGA) that generates timing and control signals, and a digital signal processor (DSP) that processes the digitized video images. The additional timing and control signals generated by the FPGA would cause the VGS to alternate between an imaging (direction-finding) mode and a time-of-flight (range-finding mode) and would govern operation in the range-finding mode.

Bryan, Thomas↗

NASA NTRS2015

Hyperspectral Microwave Atmospheric Sounder (HyMAS) - New Capability in the CoSMIR-CoSSIR Scanhead

Lincoln Laboratory and NASA's Goddard Space Flight Center have teamed to re-use an existing instrument platform, the CoSMIR/CoSSIR system for atmospheric sounding, to develop a new capability in hyperspectral filtering, data collection, and display. The volume of the scanhead accomodated an intermediate frequency processor(IFP), that provides the filtering and digitization of the raw data and the interoperable remote component (IRC) adapted to CoSMIR, CoSSIR, and HyMAS that stores and archives the data with time tagged calibration and navigation data. The first element of the work is the demonstration of a hyperspectral microwave receiver subsystem that was recently shown using a comprehensive simulation study to yield performance that substantially exceeds current state-of-the-art. Hyperspectral microwave sounders with approximately 100 channels offer temperature and humidity sounding improvements similar to those obtained when infrared sensors became hyperspectral, but with the relative insensitivity to clouds that characterizes microwave sensors. Hyperspectral microwave operation is achieved using independent RF antenna/receiver arrays that sample the same area/volume of the Earth's surface/atmosphere at slightly different frequencies and therefore synthesize a set of dense, finely spaced vertical weighting functions. The second, enabling element of the proposal is the development of a compact 52-channel Intermediate Frequency processor module. A principal challenge in the development of a hyperspectral microwave system is the size of the IF filter bank required for channelization. Large bandwidths are simultaneously processed, thus complicating the use of digital back-ends with associated high complexities, costs, and power requirements. Our approach involves passive filters implemented using low-temperature co-fired ceramic (LTCC) technology to achieve an ultra-compact module that can be easily integrated with existing radio frequency front-end technology. This IF processor is universally applicable to other microwave sensing missions requiring compact IF spectrometry. The data include 52 operational channels with low IF module volume (less than 100 cubic centimeters) and mass (less than 300 grams) and linearity better than 0.3 percent over a 330,000 dynamic range.

multispectral↗

NASA NTRS2015

Hyperspectral Microwave Atmospheric Sounder (HyMas) - New Capability in the CoSMIR-CoSSIR Scanhead

Lincoln Laboratory and NASA's Goddard Space Flight Center have teamed to re-use an existing instrument platform, the CoSMIRCoSSIR system for atmospheric sounding, to develop a new capability in hyperspectral filtering, data collection, and display. The volume of the scanhead accomodated an intermediate frequency processor(IFP), that provides the filtering and digitization of the raw data and the interoperable remote component (IRC) adapted to CoSMIR, CoSSIR, and HyMAS that stores and archives the data with time tagged calibration and navigation data.The first element of the work is the demonstration of a hyperspectral microwave receiver subsystem that was recently shown using a comprehensive simulation study to yield performance that substantially exceeds current state-of-the-art. Hyperspectral microwave sounders with 100 channels offer temperature and humidity sounding improvements similar to those obtained when infrared sensors became hyperspectral, but with the relative insensitivity to clouds that characterizes microwave sensors. Hyperspectral microwave operation is achieved using independent RF antennareceiver arrays that sample the same areavolume of the Earths surfaceatmosphere at slightly different frequencies and therefore synthesize a set of dense, finely spaced vertical weighting functions. The second, enabling element of the proposal is the development of a compact 52-channel Intermediate Frequency processor module. A principal challenge in the development of a hyperspectral microwave system is the size of the IF filter bank required for channelization. Large bandwidths are simultaneously processed, thus complicating the use of digital back-ends with associated high complexities, costs, and power requirements. Our approach involves passive filters implemented using low-temperature co-fired ceramic (LTCC) technology to achieve an ultra-compact module that can be easily integrated with existing RF front-end technology. This IF processor is universally applicable to other microwave sensing missions requiring compact IF spectrometry.The data include 52 operational channels with low IF module volume (100cm3) and mass (300g) and linearity better than 0.3 over a 330K dynamic range.

sounding↗

NASA NTRS2018

Safe2Ditch Autonomous Crash Management System for Small Unmanned Aerial Systems: Concept Definition and Flight Test Results

Small unmanned aerial systems (sUAS) have the potential for a large array of highly-beneficial applications. These applications are too numerous to comprehensively list, but include search and rescue, fire spotting, precision agriculture, etc. to name a few. Typically sUAS vehicles weigh less than 55 lbs and will be performing flight operations in the National Air Space (NAS). Certain sUAS applications, such as package delivery, will include operations in the close proximity of the general public. The full benefit from sUAS is contingent upon the resolution of several technological areas in order to provide an acceptable level of risk for widespread sUAS operations. Operations of sUAS vehicles pose risks to people and property on the ground as well as manned aviation. Several of the more significant sUAS technological areas include, but are not limited to: autonomous sense and avoid and deconfliction of sUAS from other sUAS and manned aircraft, communications and interfaces between the vehicle and human operators, and the overall reliability of the sUAS and constituent subsystems. While all of the technological areas listed contribute significantly to the safe execution of the sUAS flight operations, contingency or emergency systems can greatly contribute to sUAS risk mitigations to manage situations where the vehicle is in distress. The Safe2Ditch (S2D) system is an autonomous crash management system for sUAS. Its function is to enable sUAS to execute emergency landings and avoid injuring people on the ground, damaging property, and lastly preserving the sUAS and payload. A sUAS flight test effort was performed to test the integration of sub-elements of the S2D system with a representative sUAS multi-rotor.

Glaab, Louis J.↗

NASA NTRSDate not supplied

Spacesuit and Mobility Performance Changes

The complex interactions between the human body and spacesuit lead to changes inmovement patterns and mobility performancesof the wearer. In general, factors including the geometric properties, such as shape and size, mechanical properties of the suit, and pressurization of the suit are known to be associated with altered movement patterns as compared to an unsuited human.However, their relative contributions have not been explicitly quantified from the mobility performance perspectives. The goal of this study wasthus to assessthe effects fromthe different types of mobility constraintconditions, namely by wearing either a 3D printed hard upper torso (HUT) assembly orfully pressurized spacesuit. The outcome was also compared against the unsuited motions. For this study, an xEMU (exploration Extravehicular Mobility Unit) suitwas considered, which is the next generation spacesuit developed by NASA. In each test condition, the subject was asked to move the arm and hand as prescribedfor different task types, and the corresponding body segment locations were recordedusing a 3D motion capture system. The following three tasks were performedand analyzed: 1) Outward one-handed reaches:the subject in a standing pose made sweeping motions with the extended right arm from the extreme end-to-end positions, including side-to-side at different elevations and top-to-bottom at different azimuths. 2) Outward two-handed reaches:similarto the previous task, howeverthe subject kept the hands together during the motions in order to assessthe areas that can be reached by both hands. 3) Inward one-handed reaches:the subject made right-hand reach motions to the surface of the HUT.The hand traces collected from each task were modeled by a template shape parametrically deformed with a radial basis function. This process enabled foran abstraction of the hand traces into a smooth surface envelope representing the maximally reachable area of the test subject, of which the shapes and sizes were compared across the different test conditions. The preliminary analysis has shown that theoverall size of reachenvelopes decreases in a pressurized suit compared to 3D printed mockup HUT and unsuited conditions. The specific shape of the envelopes, which were determined by the reachable and unreachable zones, alsovary with the testconditions, and the differences werepronounced with the inward reaches to the HUT surface. The latter observation ispotentially relatedto the increased demandfor shoulder and elbow flexions.Overcomingthe resistance from the pressurizedsoft goods and mechanical constraints of the shoulder assemblywas seen to be associated with the difference in motion patterns between the suited and unsuited conditions. Overall, the information quantified from this study is expected to provide structured metrics for spacesuit mobility, which can improve design optimization and human-system integration.

K Han Kim↗

NASA NTRSDate not supplied

APIS: Honeybee Foraging Task Assignment for Use in Uncertain and Unreliable Environments

Multiagent Cyber-Physical-Human (CPH) systems in realistic environments operate under uncertain conditions. Communication among agents, aimed at reducing the uncertainty, is itself subject to uncertainty. We propose to manage uncertainties in autonomous, long-duration operations of multiagent systems via a modified Honeybee Foraging (HBF) behavioral scheme. The resulting system, Autonomous Persistent Intelligent Swarm (APIS),incorporates two new behaviors to ameliorate informational uncertainty. When “scouting”, agents are tasked based on informational quality and reliability rather than solely on priorities. When “dancing”, agents are tasked to rendezvous with other dancing agents to exchange information at close range, where successful communication is guaranteed. When coupled with uncertainty-aware modeling across agents, these behaviors improve situational awareness and resilience of the system, enabling it to function under more uncertain conditions arising during long-duration missions.

Autonomous systems↗

NASA NTRSDate not supplied

APIS: Honeybee Foraging Task Assignment for Use in Uncertain and Unreliable Environments

Autonomous systems↗

NASA NTRSDate not supplied

Towards an Optimal Estimation Retrieval of Cirrus Cloud Optical and Microphysical Properties Using Hyperspectral Shortwave Instruments and A Fast Radiative Transfer Algorithm

Cirrus cloud retrieval products (here, cloud optical depth, effective particle size, and cloud top height) are important inputs into numerical weather and climate models. Uncertainties in such retrieval products, as a matter of course, propagate downstream, impacting model calculations. Improvements in high-quality global cirrus cloud optical and microphysical data products from satellite observations are needed to understand and reduce retrieval uncertainties. Hyperspectral instruments produce high-resolution and information-dense radiance spectra, thus offering the opportunity to reduce uncertainties in retrieval products. An optimal estimation-based cirrus cloud optical and microphysical product retrieval is under development for the NASA Airborne Visible/Infrared Imaging Spectrometer (AVIRIS) and the Earth Surface Mineral Dust Source Investigation (EMIT) instruments, and the forthcoming Climate Absolute Radiance and Refractivity Observatory Pathfinder (CLARREO-Pathfinder). The spectral coverage of all three instruments includes the ultraviolet, visible, and near-infrared. In this study a very fast radiative transfer model, the Principal Component-based Radiative Transfer Model in the solar spectral region (PCRTM-Solar), is used for forward modeling computations. This will reduce the computational burden in the forward radiance and Jacobian calculations as the cost function is minimized, enabling the entire AVIRIS, EMIT, and CLARREO-Pathfinder spectral range to be used in the optimal estimation framework. Using the entire spectrum will maximize the information content, resulting in a more robust and more accurate retrieval. As a first step, the retrieval is being designed for single layer ice clouds over open ocean water. Preliminary results will be shown.

Jeffrey Mast↗

DOE OSTI2012

THE CALCULATION OF BURNABLE POISON CORRECTION FACTORS FOR PWR FRESH FUEL ACTIVE COLLAR MEASUREMENTS

Verification of commercial low enriched uranium light water reactor fuel takes place at the fuel fabrication facility as part of the overall international nuclear safeguards solution to the civilian use of nuclear technology. The fissile mass per unit length is determined nondestructively by active neutron coincidence counting using a neutron collar. A collar comprises four slabs of high density polyethylene that surround the assembly. Three of the slabs contain {sup 3}He filled proportional counters to detect time correlated fission neutrons induced by an AmLi source placed in the fourth slab. Historically, the response of a particular collar design to a particular fuel assembly type has been established by careful cross-calibration to experimental absolute calibrations. Traceability exists to sources and materials held at Los Alamos National Laboratory for over 35 years. This simple yet powerful approach has ensured consistency of application. Since the 1980's there has been a steady improvement in fuel performance. The trend has been to higher burn up. This requires the use of both higher initial enrichment and greater concentrations of burnable poisons. The original analytical relationships to correct for varying fuel composition are consequently being challenged because the experimental basis for them made use of fuels of lower enrichment and lower poison content than is in use today and is envisioned for use in the near term. Thus a reassessment of the correction factors is needed. Experimental reassessment is expensive and time consuming given the great variation between fuel assemblies in circulation. Fortunately current modeling methods enable relative response functions to be calculated with high accuracy. Hence modeling provides a more convenient and cost effective means to derive correction factors which are fit for purpose with confidence. In this work we use the Monte Carlo code MCNPX with neutron coincidence tallies to calculate the influence of Gd{sub 2}O{sub 3} burnable poison on the measurement of fresh pressurized water reactor fuel. To empirically determine the response function over the range of historical and future use we have considered enrichments up to 5 wt% {sup 235}U/{sup tot}U and Gd weight fractions of up to 10 % Gd/UO{sub 2}. Parameterized correction factors are presented.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2015

Laser beam centering and pointing system

An optical instrument aligns an optical beam without the need for physical intervention of the instrument within the apparatus or platforms from which the trajectory of the beam to be ascertained. The alignment apparatus and method enable the desired function to be realized without the placement of physical apertures or sensors directly in the path of the beam through the system whose spatial position and slope is to be sought. An image plane provides the observer with a pair of well-defined images that are indicative of the beam centering and pointing alignment parameters. The optical alignment can be realized without the need for referencing to an external or fixed set of coordinates or fiducials. The instrument can therefore service situations where adverse environments would otherwise prohibit the use of such instruments, including regions of high radiation, high temperature, vacuum and/or cryogenic atmospheres.

42 ENGINEERING↗

DOE OSTI2012

KERENA safety concept in the context of the Fukushima accident

Within the last three years AREVA NP and E.On KK finalized the basic design of KERENA which is a medium sized innovative boiling water reactor, based on the operational experience of German BWR nuclear power plants (NPPs). It is a generation III reactor design with a net electrical output of about 1250 MW. It combines active safety equipment of service-proven designs with new passive safety components, both safety classified. The passive systems utilize basic laws of physics, such as gravity and natural convection, enabling them to function without electric power. Even actuation of these systems is performed thanks to basic physic laws. The degree of diversity in component and system design, achieved by combining active and passive equipment, results in a very low core damage frequency. The Fukushima accident enhanced the world wide discussion about the safety of operating nuclear power plants. World wide stress tests for operating nuclear power plants are being performed embracing both natural and man made hazards. Beside the assessment of existing power plants, also new designs are analyzed regarding the system response to beyond design base accidents. KERENA's optimal combination of diversified cooling systems (active and passive) allows passing efficiently such tests, with a high level of confidence. This paper describes the passive safety components and the KERENA reactor behavior after a Fukushima like accident. (authors)

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

DOE OSTI2016

Cleaning up Hanford: A Deep Borehole Disposal Concept for the Cs/Sr Capsules - 16249

The Hanford site in Washington State is possibly the most radioactive-contaminated site in the USA presenting a major environmental problem requiring urgent clean-up. Sealed capsules containing halides of strontium (Sr) and cesium (Cs) account for over a third of the total radioactivity. Interim storage for a period of 10-half-lives is an unappealing option since many of the capsules contain Cs-135, which has a half-life of 2.3 million years, and the dose received from the shorter-lived isotopes would remain dangerously high for several generations. Deep geological disposal of the capsules would be a safer solution. We discuss a new and revised conceptual model for disposal of the entire Hanford capsule inventory in a single deep geological borehole with a diameter that could be as little as 31 cm. The concept involves placing thirty capsules inside a steel-disposal container. Holes up to this size are regularly drilled to depths much greater than 5 km by the hydrocarbon industry and are well within current drilling capabilities. Numerical modeling work demonstrates the feasibility of the conceptual model. In particular we examine the thermal envelope generated as a function of time enabling decisions to be made on possible fillings for the borehole annulus. Variations on the disposal concept include disposing different combinations of capsules to control the heat output and thus the temperature rise. The results lend support to a comment attributed to Secretary Moniz that the Hanford capsules could be the world's first HLW to be disposed of in a deep borehole. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2025

Adapting Grid Criticality for Data Centers

This presentation explores the evolving definition of “critical load” in the electric grid, emphasizing the growing importance of digital infrastructure—particularly data centers—in grid resilience, restoration, and modernization. As utilities increasingly rely on AI-driven analytics and software-defined control systems, data centers have shifted from passive electricity consumers to essential computational hubs that enable National Critical Functions (NCFs) and support real-time grid operations. The deck examines the scale and impact of digital loads, the need for grid modernization to manage rapid load growth, and the diverse computing paradigms required for AI deployment. It introduces a tiered taxonomy for classifying critical loads, highlights operational dependencies between the grid and digital infrastructure, and discusses policy implications for integrating data centers into emergency planning and restoration protocols. Through case studies and practical frameworks, the presentation provides actionable insights for utilities, regulators, and planners navigating the digital transformation of the power sector.

29 - ENERGY PLANNING, POLICY AND ECONOMY↗

NASA NTRS2020

Shedding Light on Microbial Dark Matter with A Universal Language of Life

The majority of microbial genomes have yet to be cultured, and most proteins predicted from microbial genomes or sequenced from the environment cannot be functionally annotated. As a result, current computational approaches to describe microbial systems rely on incomplete reference databases that cannot adequately capture the full functional diversity of the microbial tree of life, limiting our ability to model high-level features of biological sequences. The scientific community needs a means to capture the functionally and evolutionarily relevant features underlying biology, independent of our incomplete reference databases. Such a model can form the basis for transfer learning tasks, enabling downstream applications in environmental microbiology, medicine, and bioengineering. Here we present LookingGlass, a deep learning model capturing a “universal language of life”. LookingGlass encodes contextually-aware, functionally and evolutionarily relevant representations of short DNA reads, distinguishing reads of disparate function, homology, and environmental origin. We demonstrate the ability of LookingGlass to be fine-tuned to perform a range of diverse tasks: to identify novel oxidoreductases, to predict enzyme optimal temperature, and to recognize the reading frames of DNA sequence fragments. LookingGlass is the first contextually-aware, general purpose pre-trained “biological language” representation model for short-read DNA sequences. LookingGlass enables functionally relevant representations of otherwise unknown and unannotated sequences, shedding light on the microbial dark matter that dominates life on Earth.

A Hoarfrost↗

DOE OSTI2018

A practical computational method for the anisotropic redshift-space three-point correlation function

Here, we present an algorithm enabling computation of the anisotropic redshift-space galaxy threepoint correlation function ( 3 PCF) scaling as N 2 , with N the number of galaxies. Our previous work showed how to compute the isotropic 3 PCF with this scaling by expanding the radially binned density field around each galaxy in the survey into spherical harmonics and combining these coefficients to form multipole moments. The N 2 scaling occurred because this approach never explicitly required the relative angle between a galaxy pair about the primary galaxy. Here, we generalize this work, demonstrating that in the presence of azimuthally symmetric anisotropy produced by redshift-space distortions (RSD), the 3 PCF can be described by two triangle side lengths, two independent total angular momenta, and a spin. This basis for the anisotropic 3 PCF allows its computation with negligible additional work over the isotropic 3 PCF. We also present the covariance matrix of the anisotropic 3 PCF measured in this basis. Our algorithm tracks the full 5 D redshift-space 3 PCF, uses an accurate line of sight to each triplet, is exact in angle, and easily handles edge correction. It will enable use of the anisotropic large-scale 3 PCF as a probe of RSD in current and upcoming large-scale redshift surveys.

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2025

Imine Reductase-Catalyzed, Radical-Mediated Asymmetric Cyano Group Migration

Functional group migration (FGM) reactions represent a fundamental class of transformations in organic chemistry, enabling the repositioning of functional moieties in nonobvious ways. However, catalytic asymmetric radical-mediated FGMs remain rare due to the inherent challenges of achieving catalyst-controlled enantioselectivity over free radical intermediates. Herein, we repurpose imine reductases (IREDs), a class of biotechnologically important enzymes known for their substrate promiscuity, to enable the first examples of catalytic asymmetric cyano group migration via a radical mechanism. An orthogonal set of radical enzymes, including PbaIREDCym and SmiIREDCym, was engineered, allowing both 1,4- and 1,5-cyano group migration reactions to occur in an enantiodivergent fashion. The use of the nonionic surfactant TPGS-1000 was found to improve both the yield and enantioselectivity of these cyano migration reactions. Furthermore, this biocatalytic process exhibited a broad substrate scope and is readily scalable, affording a rare example of chiral nonamine product assembly with imine reductases. More broadly, stereoselective radical biocatalysis with engineered IREDs and other versatile enzymes provides a potentially general solution to challenging asymmetric FGM reactions.

Biocatalysis↗