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At least 217 records · Page 12

Bridge Connectivity Dictates Spin Interactions and Triplet Pair Dynamics in Intramolecular Singlet Fission

Electron spin plays a critical role in determining the structure, dynamics, and reactivities of molecular excited states, including multiexciton processes such as singlet fission. These systems exhibit triplet pair states whose excited state dynamics can be widely tuned through molecular engineering. For example, the electronic coupling between covalently linked chromophores can be readily modulated using chemical bridges to control proximity, quantum interference, or resonance effects. However, less is known about how spin coupling interactions are impacted by chromophore architecture, and how this influences triplet pair recombination dynamics. Here, in this study, we investigate the role of bridge connectivity and chromophore identity in modulating interchromophore exchange and dipolar coupling interactions for a series of pentacene and tetracene dimers bridged by alternant hydrocarbons (phenylene, naphthalene, anthracene). Using both time-resolved electron paramagnetic resonance and transient absorption spectroscopy, we find that the boundedness and recombination pathways of the triplet pair spins are highly sensitive to molecular architecture and chromophore-specific magnetic dipolar interactions. Notably, nominally ferromagnetic and antiferromagnetic eigenstates result in distinct spin state orderings, consistent with predictions from quantum interference-based graphical models. These findings establish new design principles for tuning spin dynamics in iSF materials, with implications for photonic and quantum information applications.

He, Guiying [City Univ. of New York (CUNY), NY (Un↗

The fate of organic carbon in marine sediments - New insights from recent data and analysis

Organic carbon in marine sediments is a critical component of the global carbon cycle, and its degradation influences a wide range of phenomena, including the magnitude of carbon sequestration over geologic timescales, the recycling of inorganic carbon and nutrients, the dissolution and precipitation of carbonates, the production of methane and the nature of the seafloor biosphere. Although much has been learned about the factors that promote and hinder rates of organic carbon degradation in natural systems, the controls on the distribution of organic carbon in modern and ancient sediments are still not fully understood. In this review, we summarize how recent findings are changing entrenched perspectives on organic matter degradation in marine sediments: a shift from a structurally-based chemical reactivity viewpoint towards an emerging acceptance of the role of the ecosystem in organic matter degradation rates. That is, organic carbon has a range of reactivities determined by not only the nature of the organic compounds, but by the biological, geochemical, and physical attributes of its environment. This shift in mindset has gradually come about due to a greater diversity of sample sites, the molecular revolution in biology, discoveries concerning the extent and limits of life, advances in quantitative modeling, investigations of ocean carbon cycling under a variety of extreme paleo-conditions (e.g. greenhouse environments, euxinic/anoxic oceans), the application of novel analytical techniques and interdisciplinary efforts. Adopting this view across scientific disciplines will enable additional progress in understanding how marine sediments influence the global carbon cycle.

Organic carbon↗

Interactions between molecular-scale biogeochemical processes and hyporheic exchange for understanding coupled Fe-S-C cycling in iron-rich riparian wetlands (Final Technical Report)

Riparian wetlands are dynamic interfaces that exert strong control over water quality, contaminant mobility, and greenhouse gas emissions. These systems are characterized by hyporheic exchange between oxic surface water and anoxic groundwater, which generates steep redox gradients and promotes spatially and temporally variable microbial activity. Despite growing recognition of tightly coupled iron (Fe), sulfur (S), and carbon (C) cycling in these environments, the mechanisms governing these interactions—particularly under low-sulfate freshwater conditions—remain poorly constrained. This project developed a mechanistic understanding of how hydrologic variability and microbial processes interact to control Fe–S–C cycling in iron-rich riparian wetlands. Using a multi-scale and multi-method approach integrating field observations, geochemical and spectroscopic analyses, metagenomics, and reactive transport modeling, we demonstrate that “cryptic” sulfur cycling—rapid sulfur transformations involving intermediate-valence species—plays a dominant and previously underrecognized role in freshwater wetlands. These processes persist despite low sulfate concentrations and significantly influence iron reduction, carbon mineralization, and methane dynamics. The results show that cryptic sulfur cycling enhances dissolved Fe 2+ production, regulates methane concentrations, and is strongly controlled by climate-driven hydrologic fluxes. By linking hydroclimate, subsurface flow, and biogeochemical reactions, this work provides a predictive framework for understanding how wetland systems respond to environmental change, with direct implications for water quality and carbon cycling.

54 ENVIRONMENTAL SCIENCES↗

Manipulating Aromaticity to Redirect Topochemical Polymerization Pathways

Topochemical polymerization (TCP) represents an essential route to create regio- and stereoregular polymers through solid-state transformations. Herein, we present an innovative strategy for controlling topochemical polymerization pathways by tailoring the terminal group aromaticity in the para-azaquinodimethane (AQM) ring system. Substituting phenyl groups with less aromatic furyl units extends significant spin density delocalization across the conjugated core upon thermal activation, inducing significant diradicaloid characters at furyl positions and enabling unconventional reactivities in both solution and solid states. Thermal treatment in toluene yields a unique cyclophane dimer formed via furyl-methine C-C coupling, confirmed by X-ray crystallography, while solid-state reactions produce polymers formed via both intercolumnar furyl-methine coupling and intracolumnar methine-methine coupling. The spin-center-directed mechanism underlying these transformations is validated through theoretical modeling and isotopic labeling experiments. This study highlights the prowess of aromaticity modulation in functional pro-aromatic systems, which enables the synthesis of polymers with main chain structures that are otherwise difficult to access.

Zhang, Qingsong↗

Thin, nearly wireless adaptive optical device

A thin, nearly wireless adaptive optical device capable of dynamically modulating the shape of a mirror in real time to compensate for atmospheric distortions and/or variations along an optical material is provided. The device includes an optical layer, a substrate, at least one electronic circuit layer with nearly wireless architecture, an array of actuators, power electronic switches, a reactive force element, and a digital controller. Actuators are aligned so that each axis of expansion and contraction intersects both substrate and reactive force element. Electronics layer with nearly wireless architecture, power electronic switches, and digital controller are provided within a thin-film substrate. The size and weight of the adaptive optical device is solely dominated by the size of the actuator elements rather than by the power distribution system.

Knowles, Gareth↗

Thin, nearly wireless adaptive optical device

A thin, nearly wireless adaptive optical device capable of dynamically modulating the shape of a mirror in real time to compensate for atmospheric distortions and/or variations along an optical material is provided. The device includes an optical layer, a substrate, at least one electronic circuit layer with nearly wireless architecture, an array of actuators, power electronic switches, a reactive force element, and a digital controller. Actuators are aligned so that each axis of expansion and contraction intersects both substrate and reactive force element. Electronics layer with nearly wireless architecture, power electronic switches, and digital controller are provided within a thin-film substrate. The size and weight of the adaptive optical device is solely dominated by the size of the actuator elements rather than by the power distribution system.

Knowles, Gareth↗

Thin nearly wireless adaptive optical device

A thin nearly wireless adaptive optical device capable of dynamically modulating the shape of a mirror in real time to compensate for atmospheric distortions and/or variations along an optical material is provided. The device includes an optical layer, a substrate, at least one electronic circuit layer with nearly wireless architecture, an array of actuators, power electronic switches, a reactive force element, and a digital controller. Actuators are aligned so that each axis of expansion and contraction intersects both substrate and reactive force element. Electronics layer with nearly wireless architecture, power electronic switches, and digital controller are provided within a thin-film substrate. The size and weight of the adaptive optical device is solely dominated by the size of the actuator elements rather than by the power distribution system.

Knowles, Gareth J.↗

Altered Gravity Induces Oxidative Stress in Drosophila Melanogaster

Altered gravity environments can induce increased oxidative stress in biological systems. Microarray data from our previous spaceflight experiment (FIT experiment on STS-121) indicated significant changes in the expression of oxidative stress genes in adult fruit flies after spaceflight. Currently, our lab is focused on elucidating the role of hypergravity-induced oxidative stress and its impact on the nervous system in Drosophila melanogaster. Biochemical, molecular, and genetic approaches were combined to study this effect on the ground. Adult flies (2-3 days old) exposed to acute hypergravity (3g, for 1 hour and 2 hours) showed significantly elevated levels of Reactive Oxygen Species (ROS) in fly brains compared to control samples. This data was supported by significant changes in mRNA expression of specific oxidative stress and antioxidant defense related genes. As anticipated, a stress-resistant mutant line, Indy302, was less vulnerable to hypergravity-induced oxidative stress compared to wild-type flies. Survival curves were generated to study the combined effect of hypergravity and pro-oxidant treatment. Interestingly, many of the oxidative stress changes that were measured in flies showed sex specific differences. Collectively, our data demonstrate that altered gravity significantly induces oxidative stress in Drosophila, and that one of the organs where this effect is evident is the brain.

Oxidative Stress↗

Flattop-HEU Benchmark Reevaluation Summary

The Flattop critical assembly was first constructed in the 1950’s at Los Alamos National Laboratory as a follow-on to the Topsy experiment. Flattop is composed of a sphere of special nuclear material (SNM) surrounded by a thick spherical reflector made of natural uranium (NU). Two SNM cores currently exist: a highly-enriched-uranium (HEU) core and a plutonium core. The reflector is composed of three parts: a stationary hemisphere and two movable quarter spheres. For fine reactivity control, there are three control rods of NU that are inserted into the stationary hemisphere from underneath the assembly. The final components that allow for reactivity adjustment are the glory hole pieces, mass adjustment buttons, and hemispherical caps. These pieces can be loaded in various configurations to change the available reactivity loaded in the system.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

NASA Tech Briefs, September 2010

Topics covered include: Instrument for Measuring Thermal Conductivity of Materials at Low Temperatures; Multi-Axis Accelerometer Calibration System; Pupil Alignment Measuring Technique and Alignment Reference for Instruments or Optical Systems; Autonomous System for Monitoring the Integrity of Composite Fan Housings; A Safe, Self-Calibrating, Wireless System for Measuring Volume of Any Fuel at Non-Horizontal Orientation; Adaptation of the Camera Link Interface for Flight-Instrument Applications; High-Performance CCSDS Encapsulation Service Implementation in FPGA; High-Performance CCSDS AOS Protocol Implementation in FPGA; Advanced Flip Chips in Extreme Temperature Environments; Diffuse-Illumination Systems for Growing Plants; Microwave Plasma Hydrogen Recovery System; Producing Hydrogen by Plasma Pyrolysis of Methane; Self-Deployable Membrane Structures; Reactivation of a Tin-Oxide-Containing Catalys; Functionalization of Single-Wall Carbon Nanotubes by Photo-Oxidation; Miniature Piezoelectric Macro-Mass Balance; Acoustic Liner for Turbomachinery Applications; Metering Gas Strut for Separating Rocket Stages; Large-Flow-Area Flow-Selective Liquid/Gas Separator; Counterflowing Jet Subsystem Design; Water Tank with Capillary Air/Liquid Separation; True Shear Parallel Plate Viscometer; Focusing Diffraction Grating Element with Aberration Control; Universal Millimeter-Wave Radar Front End; Mode Selection for a Single-Frequency Fiber Laser; Qualification and Selection of Flight Diode Lasers for Space Applications; Plenoptic Imager for Automated Surface Navigation; Maglev Facility for Simulating Variable Gravity; Hybrid AlGaN-SiC Avalanche Photodiode for Deep-UV Photon Detection; High-Speed Operation of Interband Cascade Lasers; 3D GeoWall Analysis System for Shuttle External Tank Foreign Object Debris Events; Charge-Spot Model for Electrostatic Forces in Simulation of Fine Particulates; Hidden Statistics Approach to Quantum Simulations; Reconstituted Three-Dimensional Interactive Imaging; Determining Atmospheric-Density Profile of Titan; Digital Microfluidics Sample Analyzer; Radiation Protection Using Carbon Nanotube Derivatives; Process to Selectively Distinguish Viable from Non-Viable Bacterial Cells; and TEAMS Model Analyzer.

Source record↗

Biconjugate Impedance Matching Control of the HERO WEC: Preprint

Effective control strategies are essential for maximizing the power output of wave energy converters (WECs). In this study, we explore the methodology of port-based modelling which can be used for bi-conjugate impedance matching, a type of reactive control that involves maximizing power transfer by setting the load (PTO) impedance to be the complex conjugate of the source impedance (WEC). Despite its foundational role in electrical engineering, this method has seen limited application in wave energy and has not yet been demonstrated in wave-powered desalination systems. We represent our complex multidisciplinary system as an equivalent circuit to explore frequency-based relations. The HERO WEC, a small-scale, modular point absorber (PA) designed for reverse osmosis desalination is used as a case study to demonstrate port-based modelling for control applications. Improving the performance of wave-powered water desalination systems could play a critical role in addressing freshwater scarcity for coastal communities, especially those in remote or disaster-prone regions.

16 TIDAL AND WAVE POWER↗

An In Situ Feed Monitoring System for Molten Salt Reactors with Fast Neutron Energy Spectrum Molten Salt Reactor Applications

Molten salt reactors (MSRs) are one of the six promising advanced reactor technologies selected for further research and development by the Generation IV International Forum. More than twenty MSR designs are actively being developed around the world. Several of these designs are liquid-fueled and intended for operation within the fast neutron energy spectrum.1 National regulations will require liquid-fueled MSRs to control and account for nuclear material within licensed facilities. Additionally, states with comprehensive safeguards agreements with the International Atomic Energy Agency (IAEA) are obligated to declare nuclear material quantities within facilities. In return, the IAEA Department of Safeguards independently verifies these quantities and provides assurance that the nuclear material and facility are being used only for peaceful purposes. One key distinction of liquid-fueled MSRs compared with other types of reactors is that in portions of the facility, the nuclear material is in bulk form rather than discrete items. Traditional nuclear material accounting techniques such as physical item counting and verification of serial numbers on fresh fuel assemblies do not translate directly to all process streams within liquid-fueled reactors. Liquid-fueled MSRs are typically designed with low excess reactivity. This feature provides safety benefits but also means that most MSRs require the addition of makeup fuel salt while a reactor is operational. The nuclear material in the initial fuel salt and in any makeup fuel salt must be quantified. Additionally, distinct nuclear material diversion and reactor misuse scenarios form the basis of the detection methods and monitoring systems developed for liquid-fueled MSRs. For example, the IAEA provides assurance that fuel salt containing nuclear material is not being diverted from the system, that the feed salt matches the reported actinide concentrations and uranium enrichment, and that no additional fertile material is being introduced into the system. Measurement systems currently used for nuclear material control and accounting are not directly applicable to achieving MSR safeguards goals. This paper concerns a system being designed to account for the nuclear material added to liquid-fueled MSRs and monitor for diversion and misuse scenarios related to MSR feed systems.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

High rate reactive sputtering of MoN(x) coatings

High rate reactive sputtering of MoN(x) films was performed using feedback control of the nitorgen partial pressure. Coatings were made at four different target powers: 2.5, 5.0, 7.5 and 10 kW. No hysteresis was observed in the nitrogen partial pressure vs. flow plot, as is typically seen for the Ti-N system. Four phases were determined by X-ray diffraction: molybdenum, Mo-N solid solution, Beta-Mo2N and gamma-Mo2N. The hardness of the coatings depended upon composition, substrate bias, and target power. The phases present in the hardest films differed depending upon deposition parameters. For example, the Beta-Mo2N phase was hardest (load 25 gf) at 5.0 kW with a value of 3200 kgf/sq mm, whereas the hardest coatings at 10 kW were the gamma-Mo2N phase (3000 kgf/sq mm). The deposition rate generally decreased with increasing nitrogen partial pressure, but there was a range of partial pressures where the rate was relatively constant. At a target power of 5.0 kW, for example, the deposition rates were 3300 A/min for a N2 partial pressure of 0.05 - 1.0 mTorr.

Rudnik, Paul J.↗

Transient fuel performance analysis for the preliminary fuel concept of general atomics fast modular reactor

This study investigates the transient fuel performance of General Atomics Fast Modular Reactor (GA-FMR) during accident scenarios, focusing on the behavior of its innovative fuel system that combines high-assay low enriched uranium dioxide (HALEUO2) fuel with SiGA® ceramic matrix composite silicon carbide cladding. The preliminary fuel design’s response was analyzed during reactivity-initiated accidents (RIA) and loss of coolant accidents (LOCA) using BISON fuel performance analysis code, which included both the diffusion enhanced and BISON-FASTGRASS coupled UO 2 models. The RIA analysis demonstrated that effective reactivity control reduced fuel temperature, though with transient fission gas release resulting in additional tensile stress state on the cladding. LOCA simulations revealed differing predictions between the two models: the BISON UO 2 model showed more transient fission gas release but minimal pellet expansion, while the BISON-FASTGRASS UO 2 model predicted less pronounced fission gas release but more fuel swelling and thermal expansion, potentially leading to pellet-cladding mechanical interaction. Here, these findings highlight critical areas for fuel design optimization and identify knowledge gaps requiring further experimental and computational investigation to advance GA-FMR fuel development.

Lee, Soon K. [Argonne National Laboratory (ANL), A↗

A Preliminary Investigation of the E-Beam Induced Polymerization of Maleimide and Norbornene End-capped Polyimides

A research area of high activity in connection with aerospace engineering has been the development of polymer thermosetting resins that can resist temperature as high as 300 C while maintaining adequate toughness, and providing ease of processing to enable low temperature and low cost composite fabrication methods. In order to meet such requirements, sequential interpenetrating polymer networks (IPNs) based on bismaleimide (BMI) and cyanate ester (CE) monomers were investigated. In these systems, a polycyanurate network is first formed in the presence of BMI and appropriate reactive diluent monomers and in a second step, a network based on the BMI is created in the presence of a fully formed polycyanurate network. The materials developed can be processed at relatively low temperature (less than 150 C) and with the aid of electron beam (EB) curing. Of major importance to the success of this work was the identification of a reactive diluent that improves ease of processing and has tailored reactivity to allow for the controlled synthesis of CE-BMI sequential IPNs. Based on solubility and reactivity of a number of reactive diluents, N-acryloylmorpholine (AMP) was selected as a comonomer for BMI copolymerization. A donor-acceptoreaction mechanism was suggested to explain the relative reactivity of a variety of reactive diluents towards maleimide functionality. The optimum processing parameters for the formation of the first network were determined through the study of metal catalyzed cure and hydrolysis of cyanate esters, whereas the reaction behavior for second network formation in terms of the influence of EB dose rate and temperature was elucidated through an in-situ kinetics study of maleimide and AMP copolymerization. Structure-property relationships were developed which allowed for the design of improved resin systems. In particular, appropriate network coupler possessing cyanate ester and maleimide functionality was synthesized to link the polycyanurate first network to the BMI/AMP second network and thus form linked sequential IPNs (LIPNs). Consequently, Tg as high as 370 C was achieved and a fracture toughness of 120 Joules per square meters was obtained for resin systems that possess adequately low viscosity for processing using liquid molding techniques at low temperature.

Palmese, Giuseppe R.↗

Venting of a Water/Inhibited Propylene Glycol Mixture in a Vacuum Environment-Characterization and Representative Test Results

A planned use of the Orion space vehicle involves its residence at the International Space Station for six months at a time. One concept of operations involves temporarily venting portions of the idle Orion active thermal control system (ATCS) during the docked phase, preventing freezing. The venting would have to be reasonably complete with few, if any, completely filled pockets of frozen liquid. Even if pockets of frozen liquid did not damage the hardware during the freezing process, they could prevent the system from filling completely prior to its reactivation. The venting of single component systems in a space environment has been performed numerous times and is well understood. Local nucleation occurs at warm, relatively massive parts of the system, which creates vapor and forces the bulk liquid out of the system. The remnants of the liquid will freeze, then evaporate over time through local heating. Because the Orion ATCS working fluid is a 50/50 mixture of water and inhibited propylene glycol, its boiling behavior was expected to differ from that of a pure fluid. It was thought that the relatively high vapor pressure water might evaporate preferentially, leaving behind a mixture enriched with the low vapor pressure propylene glycol, which would be vaporization ]resistant. Owing to this concern, a test was developed to compare the evaporation behavior of pure water, a 50/50 mixture of water and inhibited propylene glycol, and inhibited propylene glycol. The test was performed using room temperature fluids in an instrumented thin walled stainless steel vertical tube. The 1 in x 0.035 in wall tube was instrumented with surface thermocouples and encased in closed cell polyurethane foam. Reticulated polyurethane foam was placed inside the tube to reduce the convection currents. A vacuum system connected to the top of the tube set the pressure boundary condition. Tests were run for the three fluids at back pressures ranging from 1 to 18 torr. During each test, the mass of the test article was measured as it changed over time, as was its temperature and backpressure. The tests were successful. Somewhat surprisingly, the results showed that the evaporation behavior of the three fluids had more similarities than differences. The 50/50 mixture evaporated similarly to the pure water - albeit at a slower rate. The test results indicate that our extensive space - based experience with venting of single component fluids can be applied to the problem of Orion ATCS venting as long as the appropriate puts, takes, and caveats are applied.

Ungar, Eugene K.↗

Gas-Cooled High-Temperature Pebble-Bed Reactor Reference Plant Model Updates

This work presents the latest improvements to, and investigations performed with, the pebble-bed high-temperature gas-cooled reactor (PB-HTGR) reference plant models for the United States Nuclear Regulatory Commission. These models serve as the foundation for the future development of detailed design evaluation models based on license applications. The reference plant models have been developed with the Comprehensive Reactor Analysis Bundle, or BlueCRAB, which is the code suite proposed for non-light-water reactor systems safety analysis. It incorporates various simulation tools developed by the Nuclear Energy Advanced Modeling and Simulation program, including the Griffin code for reactor physics, the Pronghorn and SAM codes for core thermal fluids, the BISON code for solid conduction and fuel performance, and the SAM code for system analysis. The primary objective of the work that was performed was to assess BlueCRAB’s level of readiness for modeling a PB-HTGR. To do so, we first developed numerical models in BlueCRAB that include the key physics for this technology to ensure an adequate level of fidelity for modeling PB-HTGR core performance and for performing multiphysics simulations for equilibrium core conditions and different accident scenarios. Then we simulated transient scenarios, including depressurized and pressurized loss of forced cooling accidents, over-cooling, and control rod withdrawal events with delayed and prompt supercritical reactivity insertions. The analysis in this report includes comparisons of the 2D thermal fluid porous media models in Pronghorn and SAM, and comparisons of coupled SAM/Griffin/SAM and coupled Pronghorn/Griffin for depressurized and pressurized loss of forced cooling, over-cooling, and control rod withdrawal events. In addition, we compare 3D, 2D, and 0D/PKE neutronic models for the two control rod withdrawal scenarios with coupled Pronghorn/Griffin. The comparisons show that the BlueCRAB models lead to physically intuitive solutions for the scenarios examined. The changes in the various scalar and vector fields, such as neutron flux, power, temperature, density, pressure, and velocity, are within the expected ranges, and their distributions can be explained by the system response of the transients and the geometric and material variations. Several comparisons suggest that the porous media models in Pronghorn and SAM can lead to similar solutions, even though they are based on different methodologies. This work further highlights the need for flexible tools with various levels of fidelity to cover the breadth and depth of needs that may arise in future technical evaluations of the PB-HTGR. We believe that the BlueCRAB capabilities will be a significant asset for confirmatory analyses in order to resolve important safety questions.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Cortical neuronal cytoskeletal changes associated with FIV infection

HIV-1 infection is often complicated by central nervous system (CNS) dysfunction. Degenerative neuronal changes as well as neuronal loss have been documented in individuals with AIDS. Feline immunodeficiency virus (FIV) infection of cats provides a model for both the immune and the central nervous system manifestations of HIV infection of humans. In this study we have examined neurons in the frontal cortex of feline immunodeficiency virus-infected cats and controls for immunoreactivity with SMI 32, an antibody recognizing a non-phosphorylated epitope on neurofilaments. We noted a significant increase in the number of immunoreactive pyramidal cells in infected animals compared to controls. The changes seen in the neuronal cytoskeleton as a consequence of the inoculation with FIV were similar to those seen in humans undergoing the normal aging process as well as those suffering from neurological diseases, including Alzheimer's and dementia pugilistica. The changes we noted in the feline brain were also similar to that reported in animals with traumatic injuries or with spontaneously occurring or induced motor neuron diseases, suggesting that the increase in reactivity represents a deleterious effect of FIV on the central nervous system.

Non-NASA Center↗