Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “directivity”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 379 records · Page 21
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Direct reactions for astrophysical p-capture rates with ORRUBA and GODDESS

Understanding the nucleosynthesis and energy generation in quiescent and explosive stellar burning requires a detailed understanding of reaction rates on many unstable nuclides. Such reaction rates are often governed by the properties of low-lying, isolated proton resonances. Though direct measurements of resonance strengths are ultimately desired, and are a focus of rare isotope beam facilities worldwide, such tour-de-force experiments must be guided by indirect techniques, in order to know resonance energies, J π assignments, and estimated widths, to inform targeted measurements. Furthermore, some important low-lying resonances may be too weak for direct measurements with radioactive beams, and indirect techniques provide the only practical constraints. Additionally, there has been growing interest in the astrophysical role of isomeric states, which can influence the reaction flow in nucleosynthetic reaction networks, and hence impact the quantitative interpretation of astronomical observables, such as γ-ray signatures, and elemental and isotopic ratios. Properties of single-proton resonances can be obtained by exploiting the selectivity of direct reactions, such as single-nucleon transfer and charge-exchange reactions. Constraining proton-capture rates via direct reactions has been a focus of the astrophysics program at ORNL for over two decades, spurring the development of the ORRUBA and GODDESS detector systems. Herein, a review of recent developments in instrumentation and radioactive beam delivery (including isomeric beam experiments) is presented, along with some specific examples of astrophysically interesting sd-shell nuclides, which have been a target of recent ORRUBA and GODDESS experiments.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2025

Techno-Economic Analysis of Sorbent-Based Direct Air Capture Informed by EPC Input and Recent Technological Advancements

Direct air capture (DAC) technology has been developing at an accelerated rate. Independent, comprehensive, and transparent techno-economic analyses (TEAs) of DAC technologies are required to inform future development. NETL is publishing an update to the 2022 sorbent-based DAC case study report. This manuscript highlights select TEA results that will be presented in the upcoming NETL report. The analysis considers three sorbent-based DAC system configurations (direct steam temperature swing, indirect steam temperature swing, and direct steam temperature/vacuum swing) and two scenarios for providing the required electricity and steam (stand-alone system with a combined heat and power plant generating the required steam and electricity, and a purchased power case utilizing an electric boiler). Detailed sensitivity analyses are included and highlight the impact of external market factors, sorbent performance, and economies of scale. The potential for cost reductions by opting for temperature vacuum swing adsorption is highlighted. More detailed background and TEA results will be presented in the upcoming NETL report titled “Direct Air Capture Case Studies: Sorbent System (Revision 1)”.

carbon dioxide removal↗
DOE OSTI2024

Directly Fused Porphyrin‐Tetracyanopentacenequinone Conjugates: Role of the Cross‐Conjugated, Powerful Electron Acceptor in Promoting Highly Efficient Charge Separation

Tetracyanopentacenequinone, a powerful electron acceptor, is fused directly to the porphyrin π-system to create a new class of donor-acceptor conjugates. Owing to the direct fusion and electron-deficient property of tetracyanopentacenequinone, strong intramolecular charge transfer both in the ground and excited states was witnessed. As a control, porphyrin fused with pentacenequinone was also investigated. Upon complete spectral and electrochemical characterization, the excited state properties were initially probed by time-dependent DFT studies, and the occurrence of electron transfer from different excited states was established. Free-energy calculations revealed higher exothermic electron transfer (>600 mV) than the control pentacenequinone-porphyrin systems. Pump-probe studies covering broad spatial and temporal regions revealed efficient excited state charge separation. This was unlike the control pentacenequinone-porphyrin system, where slow charge separation was witnessed only in the case of the zinc derivatives but not the free-base ones, followed by the populating of the triplet excited state. The lifetimes of the charge-separated states ranged between 30–500 ps depending on the solvent and metal ion in the porphyrin cavity. Nanosecond transient absorption studies established the charge recombination path to populate the triplet state of porphyrin or directly to the ground state as a function of solvent polarity and the nature of the conjugate. Furthermore, the significance of cross-conjugated tetracyanopentacenequinone fused directly to the porphyrin π system in promoting highly exothermic and efficient charge separation, irrespective of its cross conjugation, is borne out from this study.

Cross conjugation↗
DOE OSTI2024

Direct Synthesis of Layer-Tunable and Transfer-Free Graphene on Device-Compatible Substrates Using Ion Implantation Toward Versatile Applications

Direct synthesis of layer-tunable and transfer-free graphene on technologically important substrates is highly valued for various electronics and device applications. State of the art in the field is currently a two-step process: a high-quality graphene layer synthesis on metal substrate through chemical vapor deposition (CVD) followed by delicate layer transfer onto device-relevant substrates. Here, we report a novel synthesis approach combining ion implantation for a precise graphene layer control and dual-metal smart Janus substrate for a diffusion-limiting graphene formation to directly synthesize large area, high quality, and layer-tunable graphene films on arbitrary substrates without the post-synthesis layer transfer process. Carbon (C) ion implantation was performed on Cu–Ni film deposited on a variety of device-relevant substrates. A well-controlled number of layers of graphene, primarily monolayer and bilayer, is precisely controlled by the equivalent fluence of the implanted C-atoms (1 monolayer ~4 × 10 15 C-atoms/cm 2 ). Upon thermal annealing to promote Cu-Ni alloying, the pre-implanted C-atoms in the Ni layer are pushed toward the Ni/substrate interface by the top Cu layer due to the poor C-solubility in Cu. As a result, the expelled C-atoms precipitate into a graphene structure at the interface facilitated by the Cu-like alloy catalysis. After removing the alloyed Cu-like surface layer, the layer-tunable graphene on the desired substrate is directly realized. The layer-selectivity, high quality, and uniformity of the graphene films are not only confirmed with detailed characterizations using a suite of surface analysis techniques but more importantly are successfully demonstrated by the excellent properties and performance of several devices directly fabricated from these graphene films. Molecular dynamics (MD) simulations using the reactive force field (ReaxFF) were performed to elucidate the graphene formation mechanisms in this novel synthesis approach. With the wide use of ion implantation technology in the microelectronics industry, this novel graphene synthesis approach with precise layer-tunability and transfer-free processing has the promise to advance efficient graphene-device manufacturing and expedite their versatile applications in many fields.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Computational models of direct and indirect X‐ray breast imaging detectors for in silico trials

Abstract Background To facilitate in silico studies that investigate digital mammography (DM) and breast tomosynthesis (DBT), models replicating the variety in imaging performance of the DM and DBT systems, observed across manufacturers are needed. Purpose The main purpose of this work is to develop generic physics models for direct and indirect detector technology used in commercially available systems, with the goal of making them available open source to manufacturers to further tweak and develop the exact in silico replicas of their systems. Methods We recently reported on an in silico version of the SIEMENS Mammomat Inspiration DM/DBT system using an open‐source GPU‐accelerated Monte Carlo x‐ray imaging simulation code (MC‐GPU). We build on the previous version of the MC‐GPU codes to mimic the imaging performances of two other Food and Drug Administration (FDA)‐approved DM/DBT systems, such as Hologic Selenia Dimensions (HSD) and the General Electric Senographe Pristina (GSP) systems. In this work, we developed a hybrid technique to model the optical spread and signal crosstalk observed in the GSP and HSD systems. MC simulations are used to track each x‐ray photon till its first interaction within the x‐ray detector. On the other hand, the signal spread in the x‐ray detectors is modeled using previously developed analytical equations. This approach allows us to preserve the modeling accuracy offered by MC methods in the patient body, while speeding up secondary carrier transport (either electron–hole pairs or optical photons) using analytical equations in the detector. The analytical optical spread model for the indirect detector includes the depth‐dependent spread and collection of optical photons and relies on a pre‐computed set of point response functions that describe the optical spread as a function of depth. To understand the capabilities of the computational x‐ray detector models, we compared image quality metrics like modulation transfer function (MTF), normalized noise power spectrum (NNPS), and detective quantum efficiency (DQE), simulated with our models against measured data. Please note that the purpose of these comparisons with measured data would be to gauge if the model developed as part of this work could replicate commercially used direct and indirect technology in general and not to achieve perfect fits with measured data. Results We found that the simulated image quality metrics such as MTF, NNPS, and DQE were in reasonable agreement with experimental data. To demonstrate the imaging performance of the three DM/DBT systems, we integrated the detector models with the VICTRE pipeline and simulated DM images of a fatty breast model containing a spiculated mass and a calcium oxalate cluster. In general, we found that the images generated using the indirect model appeared more blurred with a different noise texture and contrast as compared to the systems with direct detectors. Conclusions We have presented computational models of three commercially available FDA‐approved DM/DBT systems, which implement both direct and indirect detector technology. The updated versions of the MC‐GPU codes that can be used to replicate three systems are available in open source format through GitHub.

Sengupta, Aunnasha↗
DOE OSTI2024

Harmonizing direct and indirect anthropogenic land carbon fluxes indicates a substantial missing sink in the global carbon budget since the early 20th century

Inconsistencies in the calculation of the two anthropogenic land flux terms of the global carbon cycle are investigated. The two terms—the direct anthropogenic flux (caused by direct human disturbance in anthromes, currently a carbon source to the atmosphere) and the indirect anthropogenic flux (caused indirectly by human activities that lead to global change and affecting all biomes, currently an atmospheric carbon sink)—are typically calculated independently, resulting in inconsistent underlying assumptions. We harmonize the estimation of the two anthropogenic land flux terms by incorporating previous estimates of these inconsistencies. We recalculate the global carbon budget (GCB) and apply change-point analysis to the cumulative budget imbalance. Cumulative over 1850–2018 (1959–2018), harmonization results in a 13% lesser (4% greater) land use source from anthromes and a 20% (23%) lesser land sink. This recalculation yields a greater non-closure of the GCB, indicating a missing carbon sink averaging 0.65 Pg C year -1 since the early 20th century. The imbalance likely results from a combination of method discontinuity and structural errors in the assessment of the direct anthropogenic land use flux, greater ocean carbon uptake, structural errors in land models, and in how these land terms are quantified for the budget. We caution against overconfidence in considering the GCB a solved problem and recommend further study of methodological discontinuities in budget terms. We strongly recommend studies that quantify the direct and indirect anthropogenic land fluxes simultaneously to ensure consistency, with a deeper understanding of human disturbance and legacy effects in anthromes.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Investigation of Remanufacturing Methods Utilizing Mechanically-Generated and Gas-Atomized Feedstock Production for Directed Energy Deposition Processing Through Specific Energy Consumption Modeling

The goal of this work was to assess the energy consumption of a novel remanufacturing method that utilizes mechanically-generated feedstock for directed energy deposition. Gas-atomization is the state-of-the-art production process for directed energy deposition feedstock, and for this work was incorporated into a remanufacturing process path to provide a comparison method. Specific energy consumption models of remanufacturing utilizing both of these proposed process paths were developed and applied to a case study to investigate energy saving opportunities for future manufacturing paradigms. The energy modelling was done in three stages. First, the mechanically-generated feedstock production energy consumption model was generated from experimental observation. Second, the gas-atomized feedstock production energy consumption model was generated from a combination of experimental observation, reported estimates from the manufacturer, and data found in the literature. Lastly, the energy consumption model of directed energy deposition was derived from experimental observation and compares favorably with reported estimates in the literature. With the models, the specific energy consumption in the two process paths were compared and their application was demonstrated by estimating the energy consumption to remanufacture a bracket. The two feedstock production methods had similar specific energy consumptions. The specific energy consumption of the directed energy deposition process was the greatest component in the respective remanufacturing paths by an order of magnitude; increasing deposition rate is the most important factor for lowering the overall specific energy consumption. The analyzed remanufacturing technologies were estimated to consume less energy than replacement when repairing up to approximately 15% of the original part’s mass.

42 ENGINEERING↗
DOE OSTI2023

Direct comparison between experiments and dislocation dynamics simulations of high rate deformation of single crystal copper

A long standing challenge in computational materials science is to establish a quantitative connection between the macroscopic properties of plastic deformation with the microscopic mechanisms of dislocations in crystalline materials. Although the discrete dislocation dynamics (DDD) simulation method has been developed for several decades with the goal of addressing this challenge, a one-to-one comparison between the DDD predictions on single crystal stress–strain curves and experimental measurements under identical conditions has not been possible to date. Such a comparison is an essential step towards establishing a dislocation-physics based theory of plasticity and a multiscale framework of the plastic behaviors of crystalline materials. Here we provide direct comparisons between the stress–strain curves of Cu single crystals under high strain rate loading in the [0 0 1] and [0 1 1] directions obtained from miniaturized desktop Kolsky bar experiments and those from DDD simulations under identical loading conditions. With an appropriate set of parameters, DDD simulations can produce stress–strain curves that are in reasonable agreement with the experimental results. However, the dislocation mobility values needed to achieve this agreement are an order of magnitude lower than expected based on previous measurements and atomistic simulations. We hypothesize that this discrepancy could be caused by drag forces from jogs and point defects produced during the plastic deformation. Cross-slip of screw dislocations is also found to be necessary to capture the experimental stress–strain behavior, especially for the [0 1 1] loading direction. Finally, this work provides an example of how direct comparisons between DDD simulations and experimental measurements can provide new insight into the fundamental mechanisms of plastic deformation.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Wave energy resource characterization employing joint distributions in frequency-direction-time domain

Joint and marginal distributions in the frequency, direction, and time domain are employed to demonstrate their value for wave energy resource characterization when full spectra are available. Insights gained through analysis of these distributions support wave energy converter concept design, operation and maintenance. Spatial trends in the wave energy resource and contributing wave energy systems along the continental shelf of the West Coast of the United States are investigated using the most recent two-dimensional wave spectra measurements at four buoys over an eleven year period (2008 to 2018). Resource hot spots and dominant resolved energy resource bands in the frequency-direction-time domain are delineated. Resource attributes, including frequency and directional spreading, and seasonal variability, are characterized using joint distributions and marginal distributions of wave power spectra. North Pacific westerly swells in the winter season, augmented by Aleutian low-pressure southwesterly swells, are the principal suppliers of the dominant resource and main drivers influencing resource attributes. In conclusion, the modification of these systems southward, especially the North Pacific westerly swells, explains the observed spatial resource trends. The dominant resource wave period shifts two seconds to higher wave periods, thirty degrees in the dominant direction band to a more northward orientation, and forward by one month.

16 TIDAL AND WAVE POWER↗
DOE OSTI2024

Effective direct steam regeneration of bis-iminoguanidine solid sorbent used for carbon dioxide capture

A cost-effective, energy-efficient sorbent regeneration process for phase-changing guanidines used for CO 2 capture was developed based on direct-steam stripping. This approach enhances the regeneration rate, simplifies the overall CO 2 capture process, and reduces the energy cost compared to conventional conductive thermal regeneration. A direct-steam sorbent regeneration reactor was developed, demonstrating that aqueous bis(iminoguanidines) (BIG) sorbents, e.g., methylglyoxal-bis(iminoguanidine) (MGBIG) and glyoxal-bis(iminoguanidine) (GBIG), could be efficiently regenerated with up to ~ 99 % CO 2 recovery through direct-steam stripping. Using low-temperature steam at 100 °C, a 4.5 times faster regeneration rate for GBIG carbonate sorbent (e.g., 30 min for 10 g) was demonstrated compared to conductive-heating (e.g., 135 min for 10 g) at 130 °C. Additionally, fully regenerated MGBIG converts into an aqueous MGBIG solution when the steam condenses onto the sorbent surface. Condensed steam with the guanidine can be easily recycled as an aqueous solution into the gas–liquid contactor to achieve a continuous-flow CO 2 -capture process. Molecular dynamics simulation was employed to provide a better understanding of the process. Higher heat transfer rates from steam to guanidine carbonate, compared to air heating, were attributed to the vibration resonance of water molecules within MGBIG with that of vapor molecules and the effective transfer of kinetic energy from vapor to solid. Technoeconomic analysis demonstrated that direct-steam stripping significantly decreases the CO 2 capture cost by 50 % compared to traditional conductive heating methods. Further, enhanced mass transfer facilitated by low-temperature steam and subsequent condensation effectively heats up the H 2 O-containing BIG-carbonate crystals, facilitating the desorption of CO 2 from the solid crystals, thereby leading to fast, effective, and energy-efficient sorbent regeneration.

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

Analysis of direct and indirect noise in a next-generation aviation gas turbine combustor

A large-eddy simulation (LES) of a next-generation combustor is performed to examine effects of this combustor concepts on direct and indirect combustion noise characteristics. Direct noise is computed considering the unsteady heat release predictions while entropy fluctuations in the downstream part of the combustor are used to estimate indirect noise through the transfer function of the outlet nozzle. A low-order acoustic reconstruction technique, which utilizes the Green’s function of the configuration, is developed to compute the acoustics inside the combustor. Comparisons to experimental results are reported, showing the reasonable accuracy of the LES and combustion noise computations. The direct noise spectrum peaks at frequencies around 3 kHz because of the fast timescales associated with the chemical reactions inside the combustor. In addition, the indirect noise is dominant at low frequencies, i.e., less than 400 Hz, because of the characteristics of the entropy spectrum at the outlet nozzle. Further, compared to a conventional rich-quench-lean (RQL) combustor configuration, significant differences in the acoustics are observed, and are explained by two specific technological novelties. Firstly, the direct noise spectrum peaks at significantly higher frequencies due to the combustor’s compactness. Secondly, the entropy inhomogeneties downstream of the combustion region are an order of magnitude smaller in amplitude due to the lack of dilution with cold air. This leads to a significant reduction in the indirect noise amplitude at low frequencies, where it is the dominant source of noise. These results suggest opportunities for advanced combustion technologies to achieve substantial reductions in combustion-related noise.

42 ENGINEERING↗
DOE OSTI2022

A deep learning-based direct forecasting of CO 2 plume migration

Accurate and timely forecasts of CO 2 plume evolution in geological reservoirs are crucial for CO 2 migration detection, leakage risk assessment, and operation decision support. Conventional forecasting usually adopts a two-step strategy, first calibrating reservoir model parameters against observations using iterative inverse modeling (or history matching) and then applying the calibrated model for predictions. This method impedes real-time forecasts due to the heavy computational demand in inverse modeling and may suffer from poor prediction accuracy because of the limited observation data. In this work, we propose a deep learning-based latent space mapping framework to forecast CO 2 plume migration directly by avoiding the inverse modeling. We first use the convolutional autoencoder to map the high-dimensional complex plume extents onto low-dimensional latent space. Next, we use neural networks to learn the relationship between the observation variables and the prediction latent variables. And then for given observation data, we infer the prediction values directly. This one-step direct forecasting is computationally efficient which requires a few number of parallelizable reservoir simulations and it can provide accurate predictions with limited observations by learning the observation-prediction relationship in the reduced dimension. Therefore, our proposed method enables an in-time forecast of dynamic CO 2 plume distributions. In this work, we demonstrate the effectiveness and accuracy of our method in predicting the CO 2 plume migration using four metrics such as plume area, centroid movement distance, and plume spreading in the primary and secondary directions. And the spatio-temporal evolution patterns of plume migration under diverse geological complexities are also accurately quantified.

15 GEOTHERMAL ENERGY↗
DOE OSTI2021

SANDD: A directional antineutrino detector with segmented 6 Li-doped pulse-shape-sensitive plastic scintillator

We present a characterization of a small (9-liter) and mobile 0.1% 6 Li-doped pulse-shape-sensitive plastic scintillator antineutrino detector called SANDD (Segmented AntiNeutrino Directional Detector), constructed for the purpose of near-field reactor monitoring with sensitivity to antineutrino direction. SANDD comprises three different types of module. A detailed Monte Carlo simulation code was developed to match and validate the performance of each of the three modules. The combined model was then used to produce a prediction of the performance of the entire detector. Analysis cuts were established to isolate antineutrino inverse beta decay events while rejecting large fraction of backgrounds. The neutron and positron detection efficiencies are estimated to be 34.8% and 80.2%, respectively, while the coincidence detection efficiency is estimated to be 71.7%, resulting in inverse beta decay detection efficiency of 20.0% ± 0.2%(stat.) ± 2.1%(syst.). Finally, the predicted directional sensitivity of SANDD produces an uncertainty of 20° in the azimuthal direction per 100 detected antineutrino events.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2025

Estimation of intensity, footprint, and capacity of surface urban heat islands using a direction-enhanced adaptive synchronous extraction (DEASE) method

Here, the surface urban heat island (SUHI) effect, assessed through remotely sensed land surface temperature (LST), remains a focal point in urban climate research. Conventional indicators like SUHI intensity (SUHII) and footprint (SUHIF) capture peak values and spatial extent but fail to account for the cumulative thermal load—a critical dimension reflecting the total heat exposure imposed by spatially continuous warming, which directly limits a holistic assessment of ecological and societal impacts of the SUHI effect. Therefore, this study introduces an indicator termed SUHI capacity (SUHIC), designed to quantify the aggregated SUHI effect by integrating the magnitude of the warming signal across all affected areas, thereby enabling a more comprehensive evaluation of urban thermal environments. Furthermore, a direction-enhanced adaptive synchronous extraction (DEASE) method is proposed for the quantification of SUHIC. This method can dynamically identify the optimal background reference area based on the urban-rural LST gradients in various directions within the city, without relying on predefined mathematical models as previously. The results from 102 European cities first confirm that the directional variations in urban-rural LST gradients, and the DEASE method can effectively capture these distinctions for the simultaneous estimation of SUHII, SUHIF, and SUHIC. Secondly, the spatial patterns of absolute SUHIC values show strong associations with those of SUHIF (R2>0.86), while its relative values (normalized by the area of urban) align more closely with SUHII (R2 > 0.64). More importantly, SUHIC can serve as a crucial reference for assessing the urban thermal signal when SUHII and SUHIF diverge. The proposed method and framework contribute to standardizing the quantification of the SUHI effect.

Indicator↗
DOE OSTI2022

Ultra-fast microwave regeneration of CO 2 solid sorbents for energy-efficient direct air capture

Large-scale deployment of direct air capture (DAC) technologies has become critical for mitigating climate change. Towards this end, energy-efficient regeneration of the sorbents used in the process of carbon capture from air is very important to significantly reduce the high operational cost of DAC. Guanidine compounds can be used with environmentally friendly aqueous amino acids (e.g., potassium sarcosinate) for fast and effective CO 2 capture from air, and have a strong potential for low-energy CO 2 release and sorbent regeneration. In this process, the amino acid absorbs the CO 2 from the air, and the guanidine compounds react with the CO 2 -rich amino acid solution and crystallize as an insoluble carbonate salt. Separation and thermal regeneration of the precipitated guanidine carbonate salt leads to an overall low-temperature and low-energy direct air capture process. Effective CO 2 release from the solid guanidine compound can be achieved by mild heating at 120 °C. Here, in this study, to overcome the relatively inefficient traditional conductive heating of the crystalline solid (i.e., Methylglyoxal-bis(iminoguanidine) carbonate, MGBIG carbonate), we evaluated the feasibility of microwave heating of MGBIG carbonate in terms of power requirement, radiation time, and solids mass for efficient CO 2 desorption. The energy consumption needed by a microwave oven and a conventional oven to regenerate the same mass of the sorbent was directly measured to compare the total energy required per unit mass of regenerated sample and provide an understanding of the potential benefits of microwave regeneration. We found that microwave heating effectively regenerates MGBIG carbonate, which may be facilitated by the water molecules that are co-crystallized with carbonate in the guanidine crystals. Microwave heating at 2.54 GHz with 1250 W is up to 17 times faster than conventional conductive heating at 160 °C, resulting in 40 % electrical energy reduction. These results indicate that microwave regeneration may be an energy-efficient method for fast regeneration of solid sorbents used for direct air capture.

42 ENGINEERING↗
DOE OSTI2023

Microextraction–TQ–ICP–MS for the Direct Analysis of U and Pu from Cotton Swipes

Here, the microextraction sampling technique was integrated with triple quadrupole–inductively coupled plasma–mass spectrometry (TQ–ICP–MS) to directly sample and measure the isotopic compositions of uranium (U) and plutonium (Pu) from cotton swipes. Once extracted, the U/Pu were directed into the TQ–ICP–MS instrument for isotopic determination. Carbon dioxide (CO 2 ) and helium (He) gases were delivered to a collision reaction cell within the ICP–MS system for ion separation. The CO 2 reacts with the U + forming UO + which is ultimately separated from the Pu + ions of interest in the third quadrupole. This study demonstrates direct liquid extraction of U/Pu from a solid surface and subsequent measurement by TQ–ICP–MS in <60 s. Flow rates were optimized (0.3 mL min –1 CO 2 and 5 mL min –1 He) in the reaction cell of the ICP–MS system to maximize the Pu signal while minimizing U interferences (i.e., 238 U + tail and 238 UH + ) at m/z 239. Low levels of Pu (~2 pg) were deposited on a cotton swipe along with U at concentrations ranging from 20 to 200 ng. The 240 Pu/ 239 Pu ratio was measured with <7% relative difference from the certified value at all U concentrations. Major and minor U isotope ratios were also measured with <4% relative difference. This highlights that the microextraction–TQ–ICP–MS method can extract a mixed U/Pu sample directly from a cotton swipe and measure both isotopic systems without chemical separation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

RNA–Polymer Conjugates via Direct Incorporation of the Chain Transfer Agent and PET–RAFT Polymerization

Covalent conjugation of RNA with synthetic polymers has emerged as a powerful approach for creating bioconjugates with synergistically enhanced properties. However, conventional methods require solid-phase synthesis to preinstall functional groups in RNA, significantly limiting practical applications. Here, we present a novel approach for synthesizing RNA–polymer conjugates via direct incorporation of chain transfer agent (CTA) into RNA through acylation chemistry and reversible addition–fragmentation chain transfer (RAFT) polymerization. A CTA-functionalized acyl imidazole reagent was synthesized to facilitate direct and covalent modification of various RNAs by reacting with their 2′-hydroxyl groups. Subsequent RAFT polymerization using RNA–CTA as a macro-CTA enabled direct grafting-from RNA, yielding RNA conjugates with controlled molecular weight and low dispersity. Notably, this postsynthetic modification strategy was successfully extended to modify biomass RNA, yielding thermoresponsive conjugates and biodegradable hydrogels. Overall, this advance allowed for the direct modification of synthetic and biomass RNAs, significantly enhancing the accessibility of functional RNA–polymer materials.

biomass↗
DOE OSTI2020

Direct Observation of Methylmercury and Auranofin Binding to Selenocysteine in Thioredoxin Reductase

Selenoenzymes, containing a selenocysteine (Sec) residue, fulfill important roles in biology. The mammalian thioredoxin reductase selenoenzymes are key regulators of antioxidant defense and redox signaling and are inhibited by methylmercury species and by the gold-containing drug auranofin. It has been proposed that such inhibition is mediated by metal binding to Sec in the enzyme. However, direct structural observations of these classes of inhibitors binding to selenoenzymes have been few to date. Here we therefore have used extended X-ray absorption fine structure as a direct structural probe to investigate binding to the selenium site in recombinant rat thioredoxin reductase 1 (TrxR1). The results demonstrate for the first time the direct and complete binding of the metal atom of the inhibitors to the selenium atom in TrxR1 for both methylmercury and auranofin, indicating that TrxR1 inhibition indeed can be attributed to such direct metal–selenium binding.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗