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At least 757 records · Page 42

Indium–Poly(carboxylic acid) Ligand Interactions Modify InP Quantum Dot Nucleation and Growth

Size control through precursor reactivity in InP quantum dot (QD) synthesis has been difficult due to the presence of kinetically persistent InP clusters when using conventional indium carboxylate and tris(trimethylsilyl)phosphine chemistry. However, the advent of indium halide/aminophosphine-based synthesis creates new opportunities to harness precursor design to impact nucleation and growth. Driven to further explore indium coordination as a synthetic handle in InP QD synthesis, we examined the effect of a strongly chelating anion on the nucleation and growth of InP QDs. Increasing the equivalents of metal-chelating aminopoly(carboxylic acid) EDTA ([CH 2 N(CH 2 CO 2 H) 2 ] 2 ) (0–0.75 equiv per indium) is found to decrease the final diameter of InP QDs from 4.5 to 2.3 nm by lowering the initial InP growth rate. This size trend is rationalized by invoking a continuous nucleation model. Control experiments carried out with substoichiometric equivalents of indium do not exhibit a drastic size decrease, pointing to complex effects of EDTA on the indium precursor reactivity. By 1 H NMR spectroscopy, EDTA is identified to form an octahedral complex with indium that is less reactive. Furthermore, this competitive decrease in reactivity and in the effective concentration of indium precursor is proposed to suppress the initial InP growth rates and consequently decrease the final size of the nanocrystals.

36 MATERIALS SCIENCE↗

Unlocking the Potential of Marine Energy Using Hydrogen Generation Technologies

Marine energy, including ocean waves, ocean currents, ocean thermal gradients, tides, and river currents, is a vast and untapped resource that can be harnessed to help enable the transition to renewable energy. Marine energy is an attractive renewable resource because of its energy density, predictability, and persistence. Further, marine energy has the potential to provide energy for utility-scale applications, remote and distributed applications, and rapidly expanding maritime industries, such as aquaculture and shipping. Marine energy technologies are, however, at a nascent stage of development, and a significant amount of the resource is located far from population centers and transmission infrastructure. Accordingly, to unlock the full potential of marine energy, efficient methods of storing and transporting captured marine energy are needed so that the energy can be used when and where it is needed. A promising solution to these energy storage and transportation challenges is to combine marine energy and hydrogen generation technologies. Herein, we provide a high-level analysis of the unique value proposition and technical challenges of combining marine energy and hydrogen technologies. First, we review marine energy technologies, electrolysis technologies, and hydrogen storage methods. Next, we consider specific applications and opportunities for combining the two technologies. Finally, we identify critical R&D challenges that must be overcome to successfully combine marine energy and hydrogen generation technologies. As part of our fact-finding effort in this area, we held a workshop attended by marine energy and hydrogen technology experts from industry, academia, national labs, and government entities to explore the technical challenges and opportunities for combined marine energy and hydrogen generation systems. Our intent is that this document and the report from the workshop can be used in conjunction to help identify and direct research and development that is needed to realize the potential of marine energy-hydrogen systems.

08 HYDROGEN↗

Emergence of the Persistent Spin Helix in Semiconductor Quantum Wells

According to Noether's theorem, for every symmetry in nature there is a corresponding conservation law. For example, invariance with respect to spatial translation corresponds to conservation of momentum. In another well-known example, invariance with respect to rotation of the electron's spin, or SU(2) symmetry, leads to conservation of spin polarization. For electrons in a solid, this symmetry is ordinarily broken by spin-orbit (SO) coupling, allowing spin angular momentum to flow to orbital angular momentum. However, it has recently been predicted that SU(2) can be recovered in a two-dimensional electron gas (2DEG), despite the presence of SO coupling. The corresponding conserved quantities include the amplitude and phase of a helical spin density wave termed the 'persistent spin helix' (PSH). SU(2) is restored, in principle, when the strength of two dominant SO interactions, the Rashba ({alpha}) and linear Dresselhaus ({beta}{sub 1}), are equal. This symmetry is predicted to be robust against all forms of spin-independent scattering, including electron-electron interactions, but is broken by the cubic Dresselhaus term ({beta}{sub 3}) and spin-dependent scattering. When these terms are negligible, the distance over which spin information can propagate is predicted to diverge as {alpha} {yields} {beta}{sub 1}. Here we observe experimentally the emergence of the PSH in GaAs quantum wells (QW's) by independently tuning {alpha} and {beta}{sub 1}. Using transient spin-grating spectroscopy (TSG), we find a spin-lifetime enhancement of two orders of magnitude near the symmetry point. Excellent quantitative agreement with theory across a wide range of sample parameters allows us to obtain an absolute measure of all relevant SO terms, identifying {beta}{sub 3} as the main SU(2) violating term in our samples. The tunable suppression of spin-relaxation demonstrated in this work is well-suited for application to spintronics.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Is a Prescribed Fire Sufficient to Slow the Spread of Woody Plants in an Infrequently Burned Grassland? A Case Study in Tallgrass Prairie

In many mesic grasslands, such as the central Great Plains in North America, frequent fire is a key regulator of ecological processes. Long periods of infrequent fire facilitate the conversion of herbaceous-dominated grassland to woody-dominated shrubland or woodland. At the Konza Prairie Biological Station in northeast Kansas, one infrequently burned portion of the landscape has undergone transformation from grassland to woodland after nearly 30 yr without fire. In Spring 2017, a prescribed burn was implemented to assess fire effectiveness on woody plant mortality. A postfire census of 3 000+ individual woody plants identified the distribution of species by size (height), topographic position, and slope on the landscape. Mortality and canopy fire damage were calculated for each individual. In lowland locations with near-continuous shrub cover (30.7% of the landscape), woody plants were unaffected by fire. However, in upland and slope locations, where shrubs and trees were sparser, survival probability varied by topographic position and species. In these locations 68% of all woody individuals experienced 90% or greater fire damage to the canopy, with 56% of these individuals exhibiting new canopy regrowth within 2 mo after the fire. Here, the two most abundant woody shrubs, Cornus drummondii and Rhus aromatica, showed high survival at all height classes and landscape positions. The two abundant tree species, Gleditsia triacanthos and Juniperus virginiana, showed increased survival probability with tree height that varied by landscape position. Survival of J. virginiana also varied according to proximity and size of neighboring clonal shrubs, providing a mechanism for persistence of this fire-sensitive tree species even at small height classes. The probability survival curves developed here are useful for managers assessing when to prescribe fire to maximize mortality for J. virginiana and provide insight relevant for broader ecological understanding of woody encroachment within grasslands throughout the world.

54 ENVIRONMENTAL SCIENCES↗

A Comprehensive Method to Mitigate Forced Oscillations in Large Interconnected Power Grids

Multiple severe forced oscillation events have recently been observed across the North American interconnections and around the world. These forced oscillations have caused power swings, limited power transfer capability, damaged equipment, and persisted indefinitely until the driving source was located and removed. This paper proposes a comprehensive method to mitigate forced oscillations. Once a forced oscillation is detected, a new source location algorithm can be used to locate the source based on the oscillation mode angle without requiring system topology information. If the source cannot be quickly located and removed, a control strategy can be activated to modulate the active power of utility-scale inverterbased battery energy storage systems (BESSs) to reduce the energy of forced oscillations to a safe level and allow sufficient time for locating the exact source. The proposed source location algorithm is validated using measurements collected during the January 11, 2019 forced oscillation event in North America and other actual grid events, while the proposed control strategy is verified using the Eastern Interconnection dynamic model under the replicated January 11, 2019 forced oscillation event. The simulation results demonstrated that the proposed source location algorithm can accurately identify the forced oscillation source, and the proposed control strategy can significantly reduce forced oscillation energy.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Remediation Guidance for Major Airports after a Bioterrorist Attack

This document provides general guidelines for airport managers, local officials, and other stakeholders for developing a response and recovery plan for a major airport following the release of a biological warfare agent, with specific guidance for remediation. San Francisco International Airport was selected as the example airport during development of the guidance to illustrate specific details. The spore-forming bacterium Bacillus anthracis was selected as the biological agent of primary concern because it is the most difficult of known bioterrorism agents to inactivate and is considered to be one of the agents most likely to be used as a biological weapon. The focus of the guidance is on cleanup and disposal activities associated with the Characterization, Decontamination, and Clearance Phases that are defined herein. Activities associated with the Notification and First-Response Phases are brieÀy discussed in Appendixes A and B, respectively. In addition to the main text of this Remediation Guidance document and associated appendixes, a data supplement was developed specifically for San Francisco International Airport. Requests for the data supplement must be made directly to the Emergency Planning Operations Division of San Francisco International Airport. This document does not describe public health responses to release of a biological warfare agent. If laboratory analytical results confirm the presence of a biological agent, the responsible public health agency involved in the response will commence appropriate public health actions, such as treatment (CDC 2004) and decontamination of potentially contaminated individuals, distribution of prophylaxis, and medical examinations. See the Centers for Disease Control and Prevention web site for more information on emergency public health responses (http://www.bt.cdc.gov/). Effective communication with the media and the public is an essential component of airport remediation and recovery. Whereas such communication is beyond the scope of this document, many helpful resources are available. (See Section 1.1 for more information.) The concept of operations described in this document for cleanup of a Bacillus anthracis release at a major airport conforms to the National Response Framework (NRF) (DHS 2008) and implementation of the National Incident Management System (NIMS 2004). In most cases, a Unified Command would be formed to direct the cleanup process jointly and to take ultimate responsibility for all cleanup decisions. The Unified Command would likely include the Airport Manager or Airport Emergency Operations Manager, representatives from state and local public health and emergency management agencies, and Federal agencies, such as the U.S. Environmental Protection Agency. The Unified Command and Incident Command Staff would ideally be co-located in an Incident Command Post in an uncontaminated area of the airport. If a release is large or complex, co-location of all key players may not be possible. If a major incident is declared, a Principal Federal Official may be appointed by the Department of Homeland Security to facilitate Federal support to the Unified Command. In some facilities and jurisdictions, additional response plans or procedures (such as BioWatch or other emergency response plans, procedures, or protocols) may govern notification and first response. Facility personnel, responders, and emergency management coordinators should be aware of all applicable plans and procedures and how to implement them. Cleanups following the anthrax attacks of 2001 in the U.S. pre-dated the NRF and NIMS and did not make use of a NIMS Incident Command System as we know it today. Most Incident Commanders for the larger of those cleanups chose to convene a Technical Working Group (TWG) of multi-agency, multi-disciplinary, outside experts to advise in developing sampling and decontamination plans. Most of the Incident Commanders also convened a separate Environmental Clearance Committee (ECC) to independently review pre- and post decontamination sampling data as well as data on decontamination parameters, to evaluate whether the decontamination was effective, and to add credibility regarding a decision that decontaminated areas may be reoccupied. Use of such specialized technical expertise is strongly recommended, although it would now operate within the construct of the NIMS Incident Command System. The TWG, if convened, would act in an advisory capacity to the Environmental Unit within the Planning Section. Likewise, the ECC, if convened, would provide independent peer review of products and recommendations by the Environmental Unit. For maximum impartiality, the ECC could also provide recommendations directly to the Unified Command. Cleanup activities commence with site characterization. The principal goal of characterization is to define the extent of contamination and to gather information needed to design the decontamination approach. Initial sampling data collected by first responders are assessed to approximate the location(s) of contamination. Confirmation of the agent type and viability is obtained from a Laboratory Response Network laboratory. Additional characterization data are collected to determine the extent of contamination and where decontamination actions are needed. Areas suspected of being contaminated are contained and isolated to the degree possible to prevent further movement of an agent to uncontaminated areas or the environment, and to reduce the potential for future exposure from the agent or fumigant, if fumigation is needed. Agent air monitoring in areas adjacent to the contained contamination zones is done to ensure the protection of remediation personnel and to monitor any release from the contained zones. Various sampling approaches are considered. For example, wipe samples can be used to sample hard, nonporous surfaces. Swab samples can be used to sample nooks, crannies, joints, and seams. Appendix I is a template for preparing an incident-specific, operational characterization plan. Upon completion of the characterization plan, an internal review is initiated. Upon approval of the plan by the Unified Command, characterization commences. The Site Safety Officer develops a Health and Safety Plan to ensure that coordinated health and safety measures are in place for all responding personnel. This plan describes physical, chemical, and biological hazards at the site, personal protective equipment, personal decontamination procedures, and emergency procedures to be used by sampling and remediation personnel. An incident-specific Remediation Action Plan is developed, which describes the decontamination methods to be used and other details, including waste disposal. Under NIMS, this overall plan, as well as other plans described below, are implemented through a series of standardized, shorter-term Incident Action Plans, which describe specific activities that will take place during a shift or a day. The template in Appendix J is designed to facilitate preparation of the Remediation Action Plan. If fumigation will be done, a Sampling and Analysis Plan will be needed, as well as an Ambient Air Monitoring Plan, which can be a component of the Remediation Action Plan. These three plans are needed to obtain a crisis exemption from the U.S. Environmental Protection Agency for authorized use of an unregistered sterilant or pesticide during cleanup. If pesticide products become registered for inactivation of B. anthracis in the future, the three plans will likely be required by the product’s labeling, but the plans would no longer be submitted to the U.S. Environmental Protection Agency for approval; rather, the Incident Commander would approve them. If fumigation is used, an Emergency Response Plan is also recommended, although such a plan is not required for a crisis exemption. For some nonpersistent biological warfare agents, natural attenuation may be an adequate decontamination option. In cases where contamination is not extensive or an agent is not persistent, application of surface decontaminants or other methods of medical infection control may be effective. For extensive contamination by persistent agents, such as Bacillus anthracis, fumigation may be necessary. In those cases, the Decontamination Phase commences with source reduction, such as pre-cleaning surfaces to reduce the contaminant load. To expedite cleanup and prevent costs from escalating unnecessarily, a cost–benefit analysis should be incorporated in the decision process related to retention versus disposal of facility items and materials. Certain materials and structural components can be decontaminated for reuse, but it may not be feasible or cost-effective to decontaminate other items. Those items must be pre-treated, packaged (with the package decontaminated externally), and removed for disposal as waste. Site preparation includes sealing openings to prevent leaks and setting up equipment. Decontamination reagents and delivery systems are selected, and pre-testing all systems is done before carrying out chemical treatment(s). The important choice of decontamination technologies depends on characteristics of the agent, the nature and extent of contamination, and other site parameters identified during characterization. Decontamination-related decisions can have a major impact on waste-disposal costs, and it is necessary to develop a disposal plan that identifies a means of disposal, necessary approvals, transportation, and other details. A clearance strategy is developed to ensure that after decontamination, the risk of exposure to residual contamination is negligible. A clearance sampling plan is developed, which sets clearance criteria, specifies how to determine whether the criteria have been met, and describes how and where to collect clearance samples after decontamination. In most cases, clearance sampling includes both surface and aggressive air samples. Appendix K is a clearance plan template that identifies the types of required information. To determine whether the decontaminated area may be reoccupied, the Environmental Unit (and the ECC separately, if one is convened) evaluates the results of clearance samples. For the anthrax incidents to date, and given methods that have been used, cleanup was considered successful only when there was no growth of B. anthracis cultured from any environmental samples taken after decontamination. Other factors that will be considered include the decontamination process parameters (e.g., temperature, relative humidity, decontaminant concentration, and contact time) and the results from post-decontamination culture of biological indicators that may have been used during fumigation or sterilization processes. From such an evaluation the Environmental Unit or ECC, or both, recommend whether the area may be reoccupied, or whether further decontamination is necessary. The UC makes the final decision that a facility is appropriately decontaminated for reoccupancy. The facility owner or responsible public health agency makes the final decision to reopen a decontaminated facility. A theme that is emphasized throughout this document is that many activities can greatly reduce the time required to restore airport operations if those activities are conducted prior to an actual release of biological warfare agent. A summary of specific resources (such as Federal, state, and local agency contacts; contractors; prospective team members; subject-matter experts; laboratory facilities; and other entities) that should be identified in advance by airport officials is provided in each pertinent section of this document, and summary contact lists of such resources are provided in Appendix L. A summary of overall pre-planning actions that should be completed by airport officials is presented at the end of this document.

59 BASIC BIOLOGICAL SCIENCES↗

Characterizing model uncertainties in simulated coast-to-offshore wind over the northeast U.S. using multi-platform measurements from the TCAP field campaign

Numerical weather prediction (NWP) models, such as the Weather Research and Forecasting (WRF) model, are widely used to provide estimates of the offshore wind energy resource owing to their large spatial coverage compared to available observations. Nevertheless, spatiotemporal distribution of model biases is highly dependent on factors including model configuration, location, and the interplay of multi-scale physical processes. Here, in this study, we focus on the characterization of model uncertainties in simulated coast-to-offshore winds over the northeast U.S., by varying sea surface temperature (SST) forcings, surface layer (SL) and planetary boundary layer (PBL) parameterizations, as well as identifying biases that may be directly passed from initial and boundary conditions. Multiple measurements, including aircraft data collected during the U.S. Department of Energy's Two-Column Aerosol Project (TCAP) experiment, are used to constrain the model results and facilitate quantitative comparisons. Our analysis indicates while SST forcing has notable impacts on simulated air temperature and moisture within PBL, the modeled winds are in general more sensitive to the choices of SL and PBL physics than to SST. The model’s forcing data not only controls the vertical dependence of wind speed errors, but also alters regional variability in wind speed’s spatial correlation. Bias comparisons between ERA5 reanalysis and ensemble simulations revealed significant similarity, particularly in wind speed biases during winter, underscoring their dependency on initial and boundary conditions. Coastal and offshore near-surface wind speed biases tend to exhibit much higher similarity in winter than in summer due to the presence of much stronger and more persistent synoptic wind conditions. This study highlights the importance of accurate atmospheric forcing and parameterization choices in improving wind forecasts and suggests the potential for extrapolating coastal wind biases to offshore locations, aiding wind energy forecasting and informing the Wind Forecast Improvement Project-3 (WFIP3).

17 WIND ENERGY↗

Potential biological control agents of Geosmithia morbida restrict fungal pathogen growth via mycoparasitism and antibiosis

Abstract Thousand cankers disease of Juglans (walnut) and Pterocarya (wingnut) spp. (Fagales: Juglandaceae) is caused by the fungal pathogen Geosmithia morbida Kolarík, Freeland, Utley, and Tisserat (Hypocreales: Bionectriaceae) and bark beetle pest/vector, Pityophthorus juglandis Blackman (Coleoptera: Curculionidae). To further the development of biological management strategies for thousand cankers disease, we assessed the ability of 14 endophytic Trichoderma (Hypocreales: Hypocreaceae) isolates and the commercially available isolate T. afroharzianum strain KRL-AG2 to inhibit the in vitro growth of three different G. morbida isolates via mycoparasitism and antibiosis. To identify factors that may affect field success of candidate biological control agents, we quantified the growth responses of Trichoderma spp. and the commercially available entomopathogenic fungus, Beauveria bassiana (Bals.-Criv.) Vuill. (Hypocreales: Cordycipitaceae) strain GHA, to the plant secondary metabolite and antimicrobial compound, juglone in vitro. A total of 12 Trichoderma isolates (from six different Trichoderma species) demonstrated antagonistic activity towards G. morbida in dual-plate assays. Juglone consistently reduced the growth of B. bassiana strain GHA and 14 of the 15 screened Trichoderma isolates in vitro. Additionally, one metabolite-producing Trichoderma isolate, TN4-47, completely inhibited the growth of all three G. morbida isolates across all tested metabolite concentrations and had comparatively greater tolerance to juglone compared to other Trichoderma isolates. Future lines of research should focus on characterizing the active antagonistic compound present in the metabolite filtrates, determine the mode of action of the active component(s), and elucidate how abiotic and biotic factors may influence the growth, persistence, and antagonistic activity of candidate biological control agents in planta .

59 BASIC BIOLOGICAL SCIENCES↗

Final Report: Sublinear Algorithms for In-situ and In-transit Data Analysis at Exascale.

Post-Moore's law scaling is creating a disruptive shift in simulation workflows, as saving the entirety of raw data to persistent storage becomes expensive. We are moving away from a post-process centric data analysis paradigm towards a concurrent analysis framework, in which raw simulation data is processed as it is computed. Algorithms must adapt to machines with extreme concurrency, low communication bandwidth, and high memory latency, while operating within the time constraints prescribed by the simulation. Furthermore, in- put parameters are often data dependent and cannot always be prescribed. The study of sublinear algorithms is a recent development in theoretical computer science and discrete mathematics that has significant potential to provide solutions for these challenges. The approaches of sublinear algorithms address the fundamental mathematical problem of understanding global features of a data set using limited resources. These theoretical ideas align with practical challenges of in-situ and in-transit computation where vast amounts of data must be processed under severe communication and memory constraints. This report details key advancements made in applying sublinear algorithms in-situ to identify features of interest and to enable adaptive workflows over the course of a three year LDRD. Prior to this LDRD, there was no precedent in applying sublinear techniques to large-scale, physics based simulations. This project has definitively demonstrated their efficacy at mitigating high performance computing challenges and highlighted the rich potential for follow-on re- search opportunities in this space.

97 MATHEMATICS AND COMPUTING↗

Detection of mycoplasma infection in circulating tumor cells in patients with hepatocellular carcinoma

Highlights: • This study generates a monoclonal antibody CA27 against the mycoplasmal p37 protein. • CA27 isolates circulating tumor cells (CTCs) from the blood of liver cancer patients. • Results show the first evidence for mycoplasma infected-CTCs in cancer patients. - Abstract: Many studies have shown that persistent infections of bacteria promote carcinogenesis and metastasis. Infectious agents and their products can modulate cancer progression through the induction of host inflammatory and immune responses. The presence of circulating tumor cells (CTCs) is considered as an important indicator in the metastatic cascade. We unintentionally produced a monoclonal antibody (MAb) CA27 against the mycoplasmal p37 protein in mycoplasma-infected cancer cells during the searching process of novel surface markers of CTCs. Mycoplasma-infected cells were enriched by CA27-conjugated magnetic beads in the peripheral blood mononuclear cells in patients with hepatocellular carcinoma (HCC) and analyzed by confocal microscopy with anti-CD45 and CA27 antibodies. CD45-negative and CA27-positive cells were readily detected in three out of seven patients (range 12–30/8.5 ml blood), indicating that they are mycoplasma-infected circulating epithelial cells. CA27-positive cells had larger size than CD45-positive hematological lineage cells, high nuclear to cytoplasmic ratios and irregular nuclear morphology, which identified them as CTCs. The results show for the first time the existence of mycoplasma-infected CTCs in patients with HCC and suggest a possible correlation between mycoplasma infection and the development of cancer metastasis.

60 APPLIED LIFE SCIENCES↗

3D cloud detection and tracking system for solar forecast using multiple sky imagers

We propose a system for forecasting short-term solar irradiance based on multiple total sky imagers (TSIs). The system utilizes a novel method of identifying and tracking clouds in three-dimensional space and an innovative pipeline for forecasting surface solar irradiance based on the image features of clouds. First, we develop a supervised classifier to detect clouds at the pixel level and output cloud mask. In the next step, we design intelligent algorithms to estimate the block-wise base height and motion of each cloud layer based on images from multiple TSIs. Thus, this information is then applied to stitch images together into larger views, which are then used for solar forecasting. We examine the system’s ability to track clouds under various cloud conditions and investigate different irradiance forecast models at various sites. We confirm that this system can 1) robustly detect clouds and track layers, and 2) extract the significant global and local features for obtaining stable irradiance forecasts with short forecast horizons from the obtained images. Finally, we vet our forecasting system at the 32-megawatt Long Island Solar Farm (LISF). Compared with the persistent model, our system achieves at least a 26% improvement for all irradiance forecasts between one and fifteen minutes.

97 MATHEMATICS AND COMPUTING↗

Coupled machine learning–ecosystem ensemble models substantially improve predictions of nitrous oxide (N 2 O) fluxes from US croplands

Nitrous oxide (N 2 O) is a potent and persistent greenhouse gas, with rising atmospheric concentrations driven in part by inefficient use of synthetic nitrogen (N) fertilizers in agriculture. Predicting soil N 2 O emissions is challenging due to high spatial and temporal variability arising from complex soil biogeochemical processes. Process-based ecosystem models and standalone machine learning (ML) approaches without extensive site-specific calibration often miss high-emission episodes. Here, we show how an Ensemble Modeling System (EMS) based on outputs from an ensemble of ecosystem models coupled to an ensemble of ML models can improve predictions and understanding of N 2 O fluxes from US cropland. Trained and validated on ~12,000 N 2 O chamber measurements at 17 US Midwest sites (six crops, 35 management practices), the EMS accurately predicted daily fluxes of N 2 O at both training (R 2 = 0.84, RMSE = 16.4 g N ha −1 d −1 ) and held-out testing sites (R 2 = 0.84, RMSE = 6.2 g N ha −1 d −1 ). Analyses identified six dominant N 2 O drivers: soil organic carbon (SOC), NH 4 + , NO 3 - , water-filled pore space, temperature, and aboveground biomass production. Wet, warm soils produced large N 2 O peaks only with sufficient SOC and mineral N; in low-SOC soils, fluxes remained low. Incorporating these drivers into process-based models might significantly improve their predictive capacity. The EMS demonstrates a strong potential to predict N 2 O fluxes at unseen sites, enabling more reliable regional inventories, improved gap-filling where measurements are sparse, and enhanced understanding of mechanisms to advance targeted mitigation strategies in food, feed, and bioenergy crops.

AI↗

On the effects of reactant stratification and wall curvature in non-premixed rotating detonation combustors

The optimization of non-premixed rotating detonation combustors (RDCs) requires improved understanding of the coupled effects of reactant stratification, fluid property gradients, and complex shock-wave interactions on the detonation wave structure within annular geometries. In the current work, simultaneous orthogonal views of chemiluminescence and hydroxyl planar laser-induced fluorescence (PLIF) are utilized to establish the existence of a dual-wave system characterized by leading and trailing detonation waves that are closely coupled by the local flow physics. These features are persistent over a wide range of mass flow rates and are consistent with prior observations of non-premixed rotating detonations in annular geometries. The detailed instantaneous time sequences are compared with a 3D reactive unsteady Reynolds averaged Navier-Stokes (URANS) simulation to more clearly elucidate the in-situ combustion dynamics and the sensitivity to reactant inlet conditions. It is found that the dual-wave system results from unburned reactants that survive the leading detonation wave in the injector near field and are consumed within a trailing azimuthal reflected-shock combustion (ARSC) zone. By contrast, the injector far field is characterized by rapid mixing due to a sudden drop to subsonic conditions, and the bifurcated detonation wave structure collapses into a stronger, single-wave detonation front with higher overall pressure ratio as compared with the dual-wave system. While each RDC will have different inflow, mixing, and combustion characteristics, the underlying interactions between the stratified reactants and azimuthal wave dynamics identified through the combination of advanced MHz-rate diagnostics and 3D numerical simulations have important implications for the study of detonation wave stability, mode transition, and combustion efficiency in non-premixed annular RDCs.

3D URANS↗

Breast Cancer Mortality vs. Exercise and Breast Size in Runners and Walkers

Purpose: Identify predictors of breast cancer mortality in women who exercised below (,7.5 metabolic equivalent hours/ week, MET-hours/wk), at (7.5 to 12.5 MET-hours/wk), or above ($12.5 MET-hours/wk) recommended levels. Methods: Cox proportional hazard analyses of baseline pre-diagnosis MET-hours/wk vs. breast cancer mortality adjusted for follow-up age, race, baseline menopause, and estrogen and oral contraceptive use in 79,124 women (32,872 walkers, 46,252 runners) from the National Walkers’ and Runners’ Health Studies. Results: One-hundred eleven women (57 walkers, 54 runners) died from breast cancer during the 11-year follow-up. The decline in mortality in women who exercised $7.5 MET-hours/wk was not different for walking and running (P = 0.34), so running and walking energy expenditures were combined. The risk for breast cancer mortality was 41.5% lower for $7.5 vs. ,7.5 MET-hours/wk (HR: 0.585, 95%CI: 0.382 to 0.924, P = 0.02), which persisted when adjusted for BMI (HR: 0.584, 95%CI: 0.368 to 0.956, P = 0.03). Other than age and menopause, baseline bra cup size was the strongest predictor of breast cancer mortality, i.e., 57.9% risk increase per cup size when adjusted for MET-hours/wk and the other covariates (HR: 1.579, 95%CI: 1.268 to 1.966, P,0.0001), and 70.4% greater when further adjusted for BMI (HR: 1.704, 95%CI: 1.344 to 2.156, P = 1025 ). Breast cancer mortality was 4.0-fold greater (HR: 3.980, 95%CI: 1.894 to 9.412, P = 0.0001) for C-cup, and 4.7-fold greater (HR: 4.668, 95%CI: 1.963 to 11.980, P = 0.0004) for $D-cup vs. A-cup when adjusted for BMI and other covariates. Adjustment for cup size and BMI did not eliminate the association between breast cancer mortality and $7.5 MET-hour/wk walked or run (HR: 0.615, 95%CI: 0.389 to 1.004, P = 0.05). Conclusion: Breast cancer mortality decreased in association with both meeting the exercise recommendations and smaller breast volume.

59 BASIC BIOLOGICAL SCIENCES↗

Data-Driven Discovery of Linear Molecular Probes with Optimal Selective Affinity for PFAS in Water

Approaches to tackle the wide and growing variety of highly persistent per- and polyfluoroalkyl substances (PFAS) are of pressing global need because of their detrimental human health effects, such as cancer, birth defects, and hormone imbalance. Sensitive, selective, and easy-to-use real-time sensors to monitor and detect PFAS and sorbents to extract them are critical to meeting government-mandated environmental concentrations. In this work, we combine all-atom molecular dynamics simulations, enhanced sampling, deep representational learning, and Bayesian optimization to perform high-throughput virtual screening for highly sensitive and selective molecular probes. Our molecular design space consists of 3850 linear hydrocarbon chains with varying degrees of halogenation with and without amine- and phosphine-based headgroups. By employing a data-driven search process, we efficiently explore the molecular design space to optimize the sensitivity to perfluorooctanesulfonic acid (PFOS) as a prototypical PFAS analyte and selectivity relative to a sodium dodecyl sulfate (SDS) interferent. We calculate 504 Gibbs free energies of probe-analyte and probe-interferent interactions and identify probes with PFOS association free energies of up to (-ΔG PFOS ) = 9.8 ± 0.2 kJ/mol and selectivities relative to SDS of (-ΔΔG PFOS–SDS ) = 3.1 ± 1.5 kJ/mol. A C 11 Br 23 P(CH 3 ) 2 probe containing 11 backbone brominated carbons and a tertiary phosphine headgroup possesses the most sensitive binding constant to PFOS within the defined search space of K b PFOS = 177.4 ± 12.7, and a semibrominated probe C 5 H 11 C 7 Br 14 N(CH 3 ) 2 containing 12 backbone carbons and a tertiary amine headgroup possesses the highest selectivity relative to SDS of K b PFOS /K b SDS = 4.6 ± 1.7. A retrospective analysis of our data to extract interpretable design rules reveals that the sensitivity of linear hydrogenated probes increases by approximately 1 kJ/mol per C–C bond. The addition or removal of halogen atoms and amine or phosphine headgroups produces nonmonotonic changes in both sensitivity and selectivity with changes to the sensitivity of up to 2.5 kJ/mol. Finally, this work places empirical limitations on the performance of a wide range of linear probes for PFOS detection and offers a generic strategy for high-throughput computational screening to promote selective and sensitive binding.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Formation and Evolution of Metallocene Single-Molecule Circuits with Direct Gold-π Links

Single molecule circuits with group 8 metallocenes are formed without additional linker groups in Scanning Tunnelling Microscope-based break junction (STMBJ) measurements at cryogenic and room temperature conditions with gold (Au) electrodes. We investigate the nature of this direct gold-π binding motif and its affect on molecular conductance and persistence characteristics during junction evolution. The measurement technique under cryogenic conditions tracks molecular plateaus through the full cycle of extension and compression. Analysis reveals that junction persistence when the metal electrodes are pushed together correlates with whether electrodes are locally sharp or blunt, suggesting distinct scenarios for metallocene junction formation and evolution. The top and bottom surfaces of the "barrel" shaped metallocenes present the electron-rich π system of cyclopentadienyl rings which interacts with the gold electrodes in two distinct ways. An undercoordinated gold atom on a sharp tip forms a donor-acceptor bond to a specific carbon atom in the ring. However, a small, flat patch on a dull tip can bind more strongly to the ring as a whole through Van der Waals interactions. Density functional theory (DFT) based calculations of model electrode structures provide an atomic-scale picture of these scenarios, demonstrating the role of these bonding motifs during junction evolution and showing that the conductance is relatively independent of tip atomic-scale structure. Furthermore, the non-specific interaction of the cyclopentadienyl rings with the electrodes enables extended conductance plateaus, a mechanism distinct from that identified for the more commonly studied, rod-shaped organic molecular wires.

25 ENERGY STORAGE↗

Microstructural Assessment of Molybdenum Disulfide Coatings Using Nanoindentation Hardness

MoS 2 coatings are used extensively in aerospace and defense applications due to their ultralow friction and high wear resistance. Burnished and resin-bonded MoS 2 coatings are commonly used in these applications due to simplicity in deposition and history of use, despite issues with consistency in coating properties and performance. Physical vapor deposition (PVD) of MoS 2 thin films has emerged as a process alternative in the past 50 years, promising far greater control over film structure and composition but at a greater cost. Despite PVD’s benefits, hesitance to adoption persists in high-consequence applications, not only due to increased costs but variability in resulting coating properties. These variations in properties and subsequent performance are in part due to the complexity of the PVD process and the sensitive interplay between coating process-structure-property relationships. This work aims to demystify the remaining uncertainties of the process-structure-property relationships in PVD MoS 2 . The microstructure and mechanical and tribological properties of 61 different PVD pure MoS 2 coatings are examined herein. Emphasis has been placed on developing performance-based (i.e., hardness, modulus) metrics that can assess microstructural changes (density, orientation, and crystallinity) and be utilized to accelerate process development and coating optimization. Relationships established within suggest that nanoindentation hardness can be used to infer coating performance (i.e., wear rate) and properties (i.e., density, crystalline texture, and stoichiometry). Furthermore, this work demonstrates that PVD MoS 2 coatings close to the theoretical density of MoS 2 consistently have the best tribological performance and can be reliably identified by their hardness.

MoS2↗

Higher-order space-charge stability in anisotropic beams: Vlasov-Poisson derivation, refined dispersion relations, and stability charts

The Hofmann stability chart is used to screen working points in space-charge-dominated linacs. We identify two errors in its published higher-order dispersion relations: missing $(1\mp2\hatη^2/α)$ factors in the third-order $S^4$ coupling residues, and a sign error in the stated isotropic reduction of the fourth-order relation. Both corrections follow from Hofmann's Vlasov-Poisson equations without fitted parameters. They reproduce coherent tune-shift coefficients in the author's later monograph that the printed forms miss by 24% and 127%. Mode-resolved figures from a published application agree with the corrected relations and reject the printed forms, indicating an inconsistency between the 1998 equations and the calculations underlying those tested figures. We quantify the effect on the non-oscillatory stability chart. Inside the adopted $S^2\le10$ comparison domain, printed and corrected forms disagree on 0.73-2.11% of cells, with no preferred direction. Among excluded cells, disagreement reaches 22%, and the printed relation over-predicts instability at every sampled anisotropy. This concentration may help explain why the errors persisted, although it does not establish their historical cause. For PIP-II, the corrected chart flags four of thirty-two evaluable periods, including one on a third-order odd branch missed by a second-order screen. This count covers non-oscillatory modes only and remains conditional on an unresolved factor-five disagreement between two codes on transverse emittance growth.

Pathak, Abhishek [Fermilab] (ORCID:000000021704208↗