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At least 415 records · Page 23
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Lifetime risk of suicide among survivors of the atomic bombings of Japan

Abstract Aims The long-term physical health effects of the atomic bombings of Hiroshima and Nagasaki are well characterised, but the psychological effects remain unclear. Therefore, we sought to determine whether measures of exposure severity, as indirect measures of psychological trauma arising from exposure to the atomic bombings, are associated with suicide mortality among atomic bomb survivors. Methods The Life Span Study is a prospective cohort study of 93 741 Japanese atomic bomb survivors who were located within 10 km of the hypocentre in Hiroshima or Nagasaki at the time of the bombings in 1945, and 26 579 residents of Hiroshima and Nagasaki who were not in either city at the time of the bombings, matched to survivors on city, sex and age. Measures of exposure severity included: proximity to the hypocentre, type of shielding between the survivor and the blast and self-reported occurrence of acute radiation and thermal injuries. Date of death was obtained from the Japanese National Family Registry system. Cause of death was obtained from death certificates. Adjusted hazard ratios (HRs) were estimated from Cox regression models overall and stratified by sex and age. Results During the 60-year follow-up period (1950–2009), 1150 suicide deaths were recorded among 120 231 participants (23.6 per 100 000 person-years): 510 among 70 092 women (17.2 per 100 000 person-years) and 640 among 50 139 men (33.6 per 100 000 person-years). Overall, there was no association of proximity, type of shielding or the occurrence of acute injuries with suicide mortality. Among those <25 years of age at the time of the bombings, increased suicide risk was observed for survivors outside v . shielded inside any structure (HR: 1.24; 95% confidence interval (CI): 1.03, 1.48; interaction p = 0.054) and for those who reported flash burns (HR: 1.32; 95% CI: 1.00, 1.73; interaction p = 0.025). Sex-stratified analyses indicated that these associations were limited to men. Among women, closer proximity to the hypocentre was associated with a non-significant increase in suicide risk, with a positive association between proximity and suicide risk observed among women <15 years of age (HR: 1.09 per km; 95% CI: 1.00, 1.18; interaction p = 0.067). Conclusions Proximity to the hypocentre, shielding and acute injury presence do not generally appear to influence suicide mortality among atomic bomb survivors. However, heterogeneity may exist by age and sex, with younger survivors potentially more sensitive to psychological trauma. Coupled with other studies, our results suggest the importance of long-term monitoring of mental health among young populations exposed to catastrophic events or mass trauma.

Psychiatry↗
DOE OSTI2022

Temperature Dependence of FDR Response for Thermally Aged Low-Voltage Cables

Frequency Domain Reflectometry (FDR) has attracted significant attention for use in nuclear power plants (NPPs) for non-destructive cable health monitoring. However, cable aging detection using FDR faces challenges due to its high sensitivity to environmental factors such as temperature, vibrations, proximity to other cables, and so on. This work aims to evaluate the influence of measurement temperature on the FDR reflected signal in a low voltage cable undergoing accelerated thermal aging. A 100 ft long multi-core low-voltage unshielded power cable insulated with flame retardant ethylene propylene rubber (FR-EPR) and covered by a chloro-polyethylene (CPE) jacket was selected for this study. The cable was energized during aging by a 480 VAC 3-phase motor, and a 30 ft mid-section of this cable was routed through an air circulating oven held at 140 °C for up to an effective aging time of 62 days. FDR measurements were taken periodically with the oven on (at 140 °C) and with the oven off (at 22 °C). A comparative analysis of data collected at both temperatures showed that the FDR response was strongly dependent on measurement temperature. FDR measurements at ambient temperature showed large peaks corresponding to impedance changes in the aged section of the cable after 3 days of aging. These peaks continued to rise steadily with increasing aging time. However, for measurements taken at 140 °C, slowly rising peaks in the oven region (aged section) were observed only after a lead time of 23 days of aging. This work highlights the importance of measurement temperature on the performance of FDR as a condition monitoring tool for aging cables.

Sriraman, Aishwarya↗
DOE OSTI2022

PWR loading pattern optimization with reinforcement learning

The core loading pattern optimization problem belongs to the class of combinatorial optimization problem and has been studied since the dawn of commercial nuclear energy industry. It is characterized by multiple objectives and constraints, with a very high number of candidate patterns, which makes it impossible to solve explicitly. Stochastic optimization methodologies including Genetic Algorithms and Simulated Annealing are used by different nuclear utilities and vendors to perform fuel cycle reload design. Nevertheless, hand-designed solutions continue to be the prevalent method in the industry. To improve the state-of-the-art core reload patterns, we aim to create a method as scalable as possible, that agrees with the designer's goal of performance and safety. To help in this task Deep Reinforcement Learning (DRL), in particular Proximal Policy Optimization is leveraged. DRL has recently experienced a strong impetus from its successes applied to games, sometimes even reaching 'super-human' performances. This paper lays out the foundation of this method and proposes to study the behavior of several hyper-parameters that influence the DRL algorithm. The algorithm is highly dependent on multiple factors such as an exploration/exploitation trade-off that manifests through different parameters such as the number of loading patterns seen and the number of samples collected before a policy update, but also the shape of the objective function derived for the core design. Experimental results also demonstrate the effectiveness of the method in finding high-quality solutions from scratch within a reasonable amount of time. (authors)

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
DOE OSTI2023

Extended Bandwidth Spread Spectrum Time Domain Reflectometry Cable Test for Thermal Aging, Low Resistance Fault, and Water Detection

In 2022, researchers at Pacific Northwest National Laboratory (PNNL) used the Accelerated and Real-Time Environmental Nodal Assessment (ARENA) cable and motor test bed to characterize spread spectrum time domain reflectometry (SSTDR) and compare the responses of an SSTDR instrument to those of a frequency domain reflectometry (FDR) instrument. Results showed both techniques could detect and locate cable anomalies such as phase-to-phase low resistance and shorts, thermal insulation damage, mechanical insulation damage, and the presence or absence of water in some conditions. The SSTDR tests used a commercial instrument provided by LiveWire Innovations Inc. This commercial instrument performed tests at 6, 12, 24, and 48 MHz bandwidth. The results of these tests were compared to FDR tests where bandwidths could be extended up to 1.3 GHz, although the best responses for cable tests were from 100 to 500 MHz. Lower bandwidth signals can propagate better along the cable while higher bandwidths have higher resolution for impedance change reflections allowing more precise indication of location and separation of anomalies. The 2022 research found that FDR responses were clearer than SSTDR and speculated that a higher bandwidth SSTDR could more successfully detect and locate cable anomalies. One advantage of the SSTDR system investigated was that it was designed for energized online use up to 1,000 volts, which may be a significant advantage for nuclear power plant use. The LiveWire SSTDR instrument is an established product in the rail and aircraft industry and updating the SSTDR hardware parameters is difficult to justify without more conclusive testing. Therefore, a software adjustable laboratory SSTDR instrument was developed by PNNL and was used to test extended bandwidth SSTDR cable tests. Within the ARENA test bed, 42 cable conditions were tested with the PNNL SSTDR, FDR, and the LiveWire SSTDR—each operating at four different bandwidths. Observations and conclusions regarding the relative performance of the three instruments over different bandwidths are note below. Responses of the PNNL SSTDR (at 50 MHz) and the LiveWire SSTDR (at 48 MHz) were similar. The PNNL SSTDR higher frequency bandwidths behaved as expected showing sharper peaks and higher noise. This validated the PNNL SSTDR as a reasonable implementation of the SSTDR technology. Lower bandwidth SSTDR responses (particularly 6 and 12 MHz) may have increased value for use within longer cables but were not particularly effective at identifying anomalous cable behavior in the 100 ft cables tested here. The higher bandwidths of the PNNL SSTDR (50, 100, 200, and 400 MHz) did not provide substantially clearer cable reflectometry responses, but having the higher frequency responses available did add to the cable test evaluation. Strong responses to shorts and low impedance faults between phases were particularly evident in the higher bandwidth PNNL SSTDR and the FDR data. Measurements were repeatable, with similar responses obtained from a thermally aged cable for tests taken a month apart. Signal noise was affected in the unshielded cable by the local in-tray cable arrangement including proximity to metal edges and rungs of the cable tray. Foam isolation of the cable from the tray metal reduced in both FDR and SSTDR responses. Cable condition monitoring in nuclear power plants will likely benefit from both more informative off-line testing methods and from the development of on-line methods for continuous monitoring of cables in use. The LWRS-funded ARENA test bed was a valuable resource for this development and direct comparison of nuclear electrical cable condition monitoring technologies. Test results are targeted to guide industry advancement of testing and monitoring tools for cable aging management.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
DOE OSTI2023

Using iterative random forest to find geospatial environmental and Sociodemographic predictors of suicide attempts

Despite a recent global decrease in suicide rates, death by suicide has increased in the United States. It is therefore imperative to identify the risk factors associated with suicide attempts to combat this growing epidemic. In this study, we aim to identify potential risk factors of suicide attempt using geospatial features in an Artificial intelligence framework. We use iterative Random Forest, an explainable artificial intelligence method, to predict suicide attempts using data from the Million Veteran Program. This cohort incorporated 405,540 patients with 391,409 controls and 14,131 attempts. Our predictive model incorporates multiple climatic features at ZIP-code-level geospatial resolution. We additionally consider demographic features from the American Community Survey as well as the number of firearms and alcohol vendors per 10,000 people to assess the contributions of proximal environment, access to means, and restraint decrease to suicide attempts. In total 1,784 features were included in the predictive model. Our results show that geographic areas with higher concentrations of married males living with spouses are predictive of lower rates of suicide attempts, whereas geographic areas where males are more likely to live alone and to rent housing are predictive of higher rates of suicide attempts. We also identified climatic features that were associated with suicide attempt risk by age group. Additionally, we observed that firearms and alcohol vendors were associated with increased risk for suicide attempts irrespective of the age group examined, but that their effects were small in comparison to the top features. Taken together, our findings highlight the importance of social determinants and environmental factors in understanding suicide risk among veterans.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2022

Fundamental Investigations into the Properties and Performance of Advanced Materials

Intelligent engineering designs require an accurate understanding of material behavior, since any uncertainties or gaps in knowledge must be counterbalanced with heightened factors of safety, leading to overdesign. Therefore, building better structures and pushing the performance of new components requires an improved understanding of the thermomechanical response of advanced materials under service conditions. This dissertation provides fundamental investigations of several advanced materials: thermoset polymers, a common matrix material for fiber-reinforced composites and nanocomposites; aluminum alloy 7075-T6 (AA7075-T6), a high-performance aerospace material; and ceramic matrix composites (CMCs), an advanced composite for extreme-temperature applications. To understand matrix interactions with various interfaces and nanoinclusions at their fundamental scale, the properties of thermoset polymers are studied at the atomistic scale. An improved proximity-based molecular dynamics (MD) technique for modeling the crosslinking of thermoset polymers is carefully established, enabling realistic curing simulations through its ability to dynamically and probabilistically perform complex topology transformations. The proximity-based MD curing methodology is then used to explore damage initiation and the local anisotropic evolution of mechanical properties in thermoset polymers under uniaxial tension with an emphasis on changes in stiffness through a series of tensile loading, unloading, and reloading experiments. Aluminum alloys in aerospace applications often require a fatigue life of over 109 cycles, which is well over ii the number of cycles that can be practically tested using conventional fatigue testing equipment. In order to study these high-life regimes, a detailed ultrasonic cycle fatigue study is presented for AA7075-T6 under fully reversed tension-compression loading. The geometric sensitivity, frequency effects, size effects, surface roughness effects, and the corresponding failure mechanisms for ultrasonic fatigue across different fatigue regimes are investigated. Finally, because CMCs are utilized in extreme environments, oxidation plays an important role in their degradation. A multiphysics modeling methodology is thus developed to address the complex coupling between oxidation, mechanical stress, and oxygen diffusion in heterogeneous carbon fiber-reinforced CMC microstructures.

Schichtel, Jacob J.↗
DOE OSTI2023

Unitary limit and its far-reaching impact on neutron matter

This paper explores low-density neutron matter and its behavior in proximity to the unitary limit. To that end, unitary nucleon-nucleon potentials, with infinite 1 S 0 neutron-neutron scattering lengths, are constructed and the Berstch parameter is discussed in relation to results from ultra-cold atomic gases. A focal point is unitarity as a constraint for neutron matter and the symmetry energy, a topic that has been discussed in the literature. I revisit some of those arguments and emphasize the relevance of keeping a fi rm link with low-energy nuclear physics for robust predictions of neutron-rich systems. Here, the predictions are obtained from realistic few-nucleon forces based on chiral effective fi eld theory at N 3 LO.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2022

Expanding the Solar Workforce through the Illinois Community College System

The Illinois Green Economy Network (IGEN) is a consortium of all 39 Illinois community college districts working to grow the green economy in the state. The network aims to build capacity in sustainability and transform education by connecting business/industry and educators to resources, curating information and tools, cultivating partnerships, and advocating for change. Led by IGEN, the goal of the “Expanding the Solar Workforce through the Illinois Community College System” project was to create and sustain a comprehensive, statewide strategy that equips education and training providers, workers, businesses, and communities with resources and tools to prepare a solar workforce. A cohort of five Illinois community colleges participated in the program based on their capacity and interest, as well as their potential for and proximity to industry growth in the state: City Colleges of Chicago, John A. Logan College, Kankakee Community College, Lewis and Clark Community College, and Lincoln Land Community College. The project had three Objectives, 1) Address an unmet need by increasing the pool of skilled solar workers, 2) Keep pace with evolving needs of the solar workforce by improving programs to be more accessible and industry-driven, 3) Strengthen IGEN’s capacity as a statewide resource for solar education, training, and workforce initiatives. Overall, over 400 students were trained in solar installation practices, with over 40 businesses engaged. Additionally. the project spurred a number of innovations and the development of effective practices related to establishing and maintaining a solar installation program at a community college. This project sought to identify effective and scalable practices for developing a solar installation program which included the following components: enrolling students into aligned programs; developing curriculum and courses which meet industry needs; placing students in solar installation or related employment; and sustaining programming past grant funding. Through this project- IGEN was able to identify critical components of a solar installation program. Detailed further in this report these components describe 1) Necessary conditions for establishing a solar installation program, 2) Program structures use cases for different contexts, 3) Effective practices related to student pipeline development and program throughout. As a result of this project- all five participating community colleges have expressed support for continuing to offer solar installation training to their students. Additionally, three nonparticipating colleges in IGEN have expressed interest in adopting practice, courses, or curriculum developed through this program. IGEN has also committed to making the curriculum, course structure and other materials available on their website for accelerated adoption of effective practices both state and nationwide.

14 SOLAR ENERGY↗
DOE OSTI2024

Achieving Unprecedented CO 2 Utilization InCO 2 Concrete™: System Design, Product Development and Process Demonstration

Anthropogenic sources of carbon dioxide are generated from a number of sources, but the key among these are ordinary Portland cement (OPC) production and combustion of fossil fuels. Cement production is the largest global CO 2 source from the mineral decomposition of carbonates. This is due to the clinkering process whereby limestone (mainly consisting of CaCO 3 ) is decomposed into CaO and CO 2 , and combined with silica rich clays at high temperatures to form clinkers (i.e. the four key minerals that comprise cement). The high temperature range of 1400 – 1550°C required for this process accounts for up to 60% of the generated CO 2 from cement production. Combination of the limestone decomposition and thermal requirements of the clinkering process causes cement production to contribute 8-9% of annual global CO 2 emissions. Combustion of fossil fuels (coal, oil and gas) was shown to contribute a much larger portion of global CO 2 emissions. As of 2018, combustion of fossil fuels accounted for 65% of global CO 2 , where 41% was derived from stationary sources for electricity and heat generation and the other 24% was related to transport. To reduce these contributions, key steps forward in CO 2 utilization technologies are required. Therefore, a CO 2 mineralization technology (CO 2 mineralization concrete) to reduce the OPC content in concrete, while utilizing flue gas emissions from fossil fuel combustion has been developed to address both areas simultaneously. This Reversa™ technology utilizes low-carbon cementation agents produced by in situ CO 2 mineralization (“mineral carbonation reactions”) to offer a promising alternative to OPC. CO 2 mineralization relies upon the reaction of dissolved CO 2 with inorganic alkaline reactants to precipitate mineral carbonates (e.g., CaCO 3 ), which bind proximate particles and achieve cementation. Herein, a concrete green body, which is composed of a mixture of binder, water, and mineral aggregates, is exposed to CO 2 borne in industrial flue gas streams. This manner of CO 2 mineralization allows the production of construction components that feature equivalent engineering attributes as their OPC-based counterparts while featuring a much smaller embodied carbon intensity (eCI). The purpose of this project is to demonstrate the feasibility of the Reversa process evolving from a TRL-3 technology at the bench-scale up to TRL-6 technology at the pilot-scale. The reliability of the Reversa technology was tested to prove the effective production of three standard industrial concrete products selected during the course of the project. The results detailed herein will demonstrate the evolution of this technology to the industrial scale. The culmination of this work resulted in 9 production runs completed at the National Carbon Capture Center (NCCC), Wilsonville, AL, using natural gas (NG) flue gas as the CO 2 source. Over the course of the production runs at NCCC, the CO 2 utilization as a function of time, 24-h CO 2 uptake, electricity usage, and 28-d net area compressive strength recorded for each run. Collection of this data will be used to determine the success of the demonstration goals: (1) achieving in excess of 0.2gCO 2 /g reactant , (2) achieving greater than 50% reduction in global warming potential compared to standard produced units, and (3) ensuring compliance of carbonated concrete with industry standard specifications.

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

Sampling off-axis neutrino fluxes with the short-baseline near detector

The short-baseline near detector (SBND), the near detector in the short-baseline neutrino program at Fermi National Accelerator Laboratory, is located just 110 m from the booster neutrino beam target. Thanks to this close proximity, relative to its 4 m × 4 m front face, neutrinos enter SBND over a range of angles from 0° to approximately 1.6°, enabling the detector to sample variations in the neutrino flux as a function of the angle—a technique known as precision reaction-independent spectrum measurement (PRISM), referred to here as SBND-PRISM. In this paper, we show how muon- and electron-neutrino fluxes vary as a function of the neutrino beam axis angle and how this can be exploited to expand the physics potential of SBND. We make use of a model that predicts an angle-dependent electron-neutrino excess signal to illustrate this effect, such as 𝜈 𝜇 → 𝜈 𝑒 oscillations. We present how SBND-PRISM provides a method to add robustness against uncertainties in cross-section modeling and, more generally, uncertainties that do not depend on the spatial position of neutrino interaction inside the detector. The fluxes, along with their associated covariance matrices, are made publicly available with this publication.

Abratenko, P. [Tufts University]↗
DOE OSTI2022

Genetic mapping of sorghum resistance to an Illinois isolate of Colletotrichum sublineola

Anthracnose leaf blight (ALB) is an economically important disease of sorghum [Sorghum bicolor (L.) Moench] caused by the fungal pathogen Colletotrichum sublineola Henn. ex Sacc. & Trotter. Although qualitative and quantitative resistance have been identified for ALB, the usefulness of resistance loci differs depending on the pathogen pathotype. Identifying resistance effective against unique pathogen pathotypes is critical to managing ALB, as the disease is managed primarily through the deployment of host resistance. We isolated C. sublineola from ALB-infected leaves collected in Illinois and found that the strain was a novel pathotype, as it produced a unique combination of virulence against a set of differential lines. Using this isolate, we inoculated 579 temperate-adapted sorghum conversion lines in 2019 and 2020. We then conducted a genome-wide association study (GWAS) and a metabolic pathway analysis using the Pathway Associated Study Tool (PAST). We identified 47 significant markers distributed across all chromosomes except chromosome 8. We identified 32 candidate genes based on physical proximity with significant markers, some of which have a known role in host defense. We identified 47 pathways associated with ALB resistance, indicating a role for secondary metabolism in defense to ALB. Our results are important to improve the understanding of the genetic basis of ALB resistance in sorghum and highlight the importance of developing durable resistance to ALB.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Analysis and prediction of intersection traffic violations using automated enforcement system data

We report that the automated enforcement system (AES) is an effective way of supplementing traditional traffic enforcement, and the traffic violation data from AES can also be effectively used for safety research. In this study, traffic violation data were used to analyze the influencing factors associated with traffic violations and to predict the probability of violations at intersections. The potential factors influencing violations include 24 independent factors related to time, space, traffic and weather. Results from a logistic model showed that the midday period, weekends, residential districts, collector roads, congested traffic conditions, high traffic flow, lower wind speed and low temperature would increase the probability of traffic violations. The probability of violations was predicted by the random forest algorithm, which was proven to be the best traffic violation prediction model among logistic regression, Gaussian naive Bayes, and support vector machine. Moreover, the proximity weighted synthetic oversampling technique (ProWSyn) method was applied to reduce the impact of the imbalance ratio (IR) and improve the model’s prediction performance. The receiver operating characteristics (ROC) curves and Precision-Recall (PR) curves illustrated that the random forest algorithm using oversampling data had the best classifier prediction performance than undersampling data. The area under curve (AUC) and out-of-bag (OOB) error with IR = 1 reached 0.914 and 0.0787, which showed the better performance of the random forest algorithm using ProWSyn in dealing with imbalanced traffic violation data.

42 ENGINEERING↗
DOE OSTI2024

AWAKEN Dual-Doppler Lidar (ADDLidar) Field Campaign Report

The AWAKEN Dual-Doppler Lidar (ADDLidar) experiment was conducted as part of the larger AWAKEN field campaign (https://www.nrel.gov/wind/awaken.html). The American Wake Experiment (AWAKEN) is an international, multi-institutional wind energy field campaign that was conducted from May 2022 to 2024, in the vicinity of the King Plains wind farm in north central Oklahoma. The goal of AWAKEN was to provide observations to better understand interactions between wind turbines in a wind farm and the interactions between the wind farm as a whole and the atmosphere. The focus of the ADDLidar campaign was to provide height-resolved measurements of wind speed and direction at key locations upwind of the wind farm to characterize the inflow and possible blockage effects upwind of the farm. Specifically, dual-Doppler scanning methods were employed to create a number of so-called virtual towers (Calhoun et al 2006, Debnath et al. 2017, Fernando et al. 2019, Hill et al. 2010, Newman et al. 2016, Newsom et al. 2008, 2015) upwind of the farm. The ADDLidar campaign involved the deployment of two U.S. Department of Energy Atmospheric Radiation Measurement (ARM) user facility scanning Doppler lidars (S/N 236 and 237) to AWAKEN sites A4 (36.361894°, -97.356352°) and A7 (36.347259°, -97.389968°). Both sites are located approximately 29 km south of the ARM Southern Great Plains (SGP) observatory C1 site, as shown in Figure 1. These sites were chosen for their close proximity to the most southerly row of turbines in the King Plains wind farm.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

AWAKEN Dual-Doppler Lidar (ADDLidar) Field Campaign Report

The AWAKEN Dual-Doppler Lidar (ADDLidar) experiment was conducted as part of the larger AWAKEN field campaign (https://www.nrel.gov/wind/awaken.html). The American Wake Experiment (AWAKEN) is an international, multi-institutional wind energy field campaign that was conducted from May 2022 to 2024, in the vicinity of the King Plains wind farm in north central Oklahoma. The goal of AWAKEN was to provide observations to better understand interactions between wind turbines in a wind farm and the interactions between the wind farm as a whole and the atmosphere. The focus of the ADDLidar campaign was to provide height-resolved measurements of wind speed and direction at key locations upwind of the wind farm to characterize the inflow and possible blockage effects upwind of the farm. Specifically, dual-Doppler scanning methods were employed to create a number of so-called virtual towers (Calhoun et al 2006, Debnath et al. 2017, Fernando et al. 2019, Hill et al. 2010, Newman et al. 2016, Newsom et al. 2008, 2015) upwind of the farm. The ADDLidar campaign involved the deployment of two U.S. Department of Energy Atmospheric Radiation Measurement (ARM) user facility scanning Doppler lidars (S/N 236 and 237) to AWAKEN sites A4 (36.361894°, -97.356352°) and A7 (36.347259°, -97.389968°). Both sites are located approximately 29 km south of the ARM Southern Great Plains (SGP) observatory C1 site, as shown in Figure 1. These sites were chosen for their close proximity to the most southerly row of turbines in the King Plains wind farm.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Complex pH-Dependent Interactions between Weak Polyelectrolyte Block Copolymer Micelles and Molecular Fluorophores

Amphiphilic block copolymers with weak polyelectrolyte blocks can assemble stimulus-responsive nanostructures and interfaces. Applications of these materials in drug delivery, biomimetics, and sensing largely rely on the well-understood swelling of polyelectrolyte chains upon deprotonation, often induced by changes in pH or ionic strength. This deprotonation can also tune interfacial interactions between the polyelectrolyte blocks and surrounding solution, an effect which is less studied than morphological swelling of polyelectrolytes but can be just as critical for intended function. Here, we investigate whether the pH-driven morphological response of polyelectrolyte-bearing nanostructures also affects the interactions of these nanostructures with molecules in solution, using micelles of a short-chain polybutadiene-block-poly(acrylic acid) (pBd–pAA) as a model system. Here we introduce a Förster resonance energy transfer (FRET) approach to probe interactions between micelles and fluorescent molecular solutes as a function of solution pH. As expected, the pAA corona of these pBd–pAA micelles increases in thickness monotonically as a function of pH. However, FRET efficiency, which provides a metric of the spatial proximity of fluorescently labeled micelles and freely diffusing fluorophores, exhibits complex nonmonotonic behavior as a function of pH, indicating that the average separation of micelles and acceptor fluorophores is not strictly correlated with micelle swelling. Dialysis experiments quantify the affinity of fluorophores for micelles as a function of pH, confirming that changes in FRET are driven almost entirely by the pH-dependent affinity of the pAA block for the investigated molecular fluorophores, not simply by a shape change of the pAA corona. This study provides key insights into the interfacial interactions between weak-polyelectrolyte-bearing nanostructures and molecular solutes, of importance for the development of their stimulus-responsive applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Mycobacterium tuberculosis CitA activity is modulated by cysteine oxidation and pyruvate binding

As an adaptation for survival during infection, Mycobacterium tuberculosis becomes dormant, reducing its metabolism and growth. Two types of citrate synthases have been identified in Mycobacterium tuberculosis, GltA2 and CitA. Previous work shows that overexpression of CitA, the secondary citrate synthase, stimulates the growth of Mycobacterium tuberculosis under hypoxic conditions without showing accumulation of triacylglycerols and makes mycobacteria more sensitive to antibiotics, suggesting that CitA may play a role as a metabolic switch during infection and may be an interesting TB drug target. To assess the druggability and possible mechanisms of targeting CitA with small-molecule compounds, the CitA crystal structure was solved to 2.1 Å by X-ray crystallography. The solved structure shows that CitA lacks an NADH binding site that would afford allosteric regulation, which is atypical of most citrate synthases. However, a pyruvate molecule is observed within the analogous domain, suggesting pyruvate may instead be the allosteric regulator for CitA. Further, the R149 and R153 residues forming the charged portion of the pyruvate binding pocket were mutated to glutamate and methionine, respectively, to assess the effect of mutations on activity. Protein thermal shift assay shows thermal stabilization of CitA in the presence of pyruvate compared to the two CitA variants designed to decrease pyruvate affinity. Solved crystal structures of both variants show no significant structural changes. However, the catalytic efficiency of the R153M variant increases by 2.6-fold. Additionally, we show that covalent modification of C143 of CitA by Ebselen completely arrests enzyme activity. Similar inhibition is observed using two spirocyclic Michael acceptor containing compounds, which inhibit CitA with IC app 50 values of 6.6 and 10.9 μM. A crystal structure of CitA modified by Ebselen was solved, but significant structural changes were lacking. Considering that covalent modification of C143 inactivates CitA and the proximity of C143 to the pyruvate binding site, this suggests that structural and/or chemical changes in this sub-domain are responsible for regulating CitA enzymatic activity.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2025

Evidence for I 2 loss from the perovskite–gas interface upon light-induced halide segregation

Sunlight-induced halide segregation in (CH 3 NH 3 )Pb(Br x I 1−x ) 3 (1 > x > 0.2), which limits obtainable voltages from solar cells with these perovskite absorbers, reverses upon resting in the dark. However, sustained illumination at ca. 1 sun opens a new decomposition pathway, leading to irreversible I 2 loss in an open system. We conclusively show I 2 off-gassing from halide-segregated (CH 3 NH 3 )Pb(Br 0.75 I 0.25 ) 3 by trapping gaseous I 2 and tracking the electronic conductivity of the perovskite, which increases from electron-doping as iodides are oxidized to iodine. Importantly, we show that this reaction occurs across the perovskite-air solid–gas interface, without confounding effects from solvent or reactive solid interfaces. This characterization was conducted under a nitrogen atmosphere, avoiding vacuum- and oxygen-driven I 2 loss pathways. Consistent observations of I 2 loss upon light-soaking CsPb(Br 0.75 I 0.25 ) 3 films show that this reaction is intrinsic to the inorganic framework. We propose that the disruption of iodide-rich domains in the halide-segregated films through I 2 loss can masquerade as a light-induced healing or apparent remixing of the segregated film, when in fact it leads to irreversible decomposition. Although I 2 off-gassing is less likely in bromide-rich solid solutions, light-induced halide segregation brings the iodides into proximity and forms electronic states that are energetically poised to trap and accumulate holes, providing a driving force for I 2 loss. Thus, even bromide-rich mixed-halide perovskite absorbers will benefit from I 2 -impermeable encapsulation for long-term stability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗