Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “OXYGEN 18”

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 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Oxidation of glucose to glycolic acid using oxygen and pyrolyzed spent Li-ion battery electrode material as catalyst

A search for non-noble catalysts for biomass processing led to the discovery that pyrolyzed electrode coating of spent Li-ion batteries can be used as an excellent catalyst for oxidation of D-glucose to glycolic acid. New no/low-cost catalyst was prepared by pyrolyzing black electrode coatings of 18,650 Li-ion cells from a spent DELL 1525 laptop battery at 600 ºC. Catalyst was characterized using SEM, EDX and X-ray and was shown to contain lithium nickel manganese cobalt oxide (Li a Ni b Mn c Co d O e ) on carbon with Ni: Mn: Co 4.12: 2.10: 1.50. Here, the catalytic activity of this material was evaluated for oxidation of D-glucose in aq. NaOH and water; glycolic, tartaric, malic, succinic and 2-hydroxybutaric acid were identified as key degradation products. The highest glycolic acid yield of 94% was obtained for oxidation of D-glucose under 3.4 Atm. oxygen, 120 °C, 2.0 h in 0.5 M aq. NaOH using 10 g catalyst/mol glucose.

25 ENERGY STORAGE↗
DOE OSTI2026

Unraveling Defect-Dependent Conductivity-Type Switching in CuFe 2 O 4 for Enhanced Photoelectrocatalytic Reduction of Benzaldehyde

Photoelectrocatalytic (PEC) reduction provides a sustainable route for upgrading biomass-derived feedstocks with reduced energy requirements, yet remains largely unexplored beyond hydrogen evolution and CO 2 reduction due to the scarcity of stable photocathodes. Here, we report a defect-engineered CuFe 2 O 4 photocathode that enables directly quantified PEC reduction of benzaldehyde to benzyl alcohol using a singlecomponent, earth-abundant oxide. By controlling annealing temperature and oxygen partial pressure, CuFe 2 O 4 is systematically tuned from n-type to p-type conductivity. Electrochemical measurements, X-ray and ultraviolet photoelectron spectroscopy, and firstprinciples defect calculations collectively show that oxygen-rich annealing conditions suppress deep donor-type oxygen vacancies while stabilizing shallow acceptor-type copper vacancies, resulting in enhanced hole concentration and improved charge transport. In a mixed acetonitrile/water electrolyte employing 1,4-benzoquinone as a redox mediator, the optimized CuFe 2 O 4 photocathode achieves stable photoelectrochemical operation over 18 h under continuous illumination with a benzyl alcohol production rate of 2.57 μmol/h at −0.50 V vs Ag/AgNO 3 , corresponding to a Faradaic efficiency of 51.3%. This PEC approach lowers the required applied potential by ∼1 V compared to traditional electrocatalytic methods, offering a more energy-efficient route for carbonyl reduction. These findings establish CuFe 2 O 4 as a viable photocathode platform for sustainable photoelectrocatalytic organic transformations under mild reaction conditions.

benzaldehyde reduction↗
DOE OSTI2022

Spatial Microbial Respiration Variations in the Hyporheic Zones Within the Columbia River Basin

Abstract While the hyporheic zone (HZ) accounts for a significant portion of whole stream CO 2 concentrations, HZ respiration modeling studies are lacking in quantifying their contributions to the total CO 2 at large watershed/basin scales. Quantifying the contribution of anaerobic respiration is also underappreciated. This study used a carbon‐nitrogen‐coupled river corridor model to quantify HZ aerobic and anaerobic respiration and determined the key factors controlling their spatial variability within the Columbia River Basin (CRB). The modeled respiration patterns showed high spatial variability. Among the nine sub‐basins composing the CRB, the Lower Columbia and the Willamette, which receive higher precipitation, had higher respiration. Medium‐sized rivers (fourth to sixth orders) produced the highest aerobic and anaerobic respiration among reaches of different sizes. At the basin scale, aerobic respiration is dominant, representing approximately 98.7% of the total respiration across the CRB. While most of the reaches were dominant with aerobic respiration, reaches in agricultural land showed a relatively higher anaerobic respiration (18%) ratio. A variable importance analysis showed that hyporheic exchange flux controlled most of the spatial variability of HZ respiration, dominating over other physical variables such as residence time, stream dissolved organic carbon (DOC), nitrate, and dissolved oxygen (DO). The influence of substrate concentration (DOC and DO) is larger in modeling anaerobic respiration than aerobic respiration. Future efforts will focus on improving the estimation of the HZ exchange flux and the implementation of spatially explicit parameterizations for the reactions of interest to reduce model uncertainty.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Neonatal respiratory support strategies—short and long-term respiratory outcomes

Mechanical ventilation (MV), although life-saving, is associated with chronic respiratory morbidity in both preterm and term born infants. New ventilation modes have been developed with the aim of minimising lung injury. These include invasive and non-invasive respiratory support strategies, techniques for less invasive surfactant administration (LISA) and closed-loop automated oxygen control (CLAC) systems. Increasingly, newborn infants with signs of respiratory distress are stabilised on continuous positive airway pressure (CPAP) and receive LISA. Early CPAP when compared to mechanical ventilation reduced the incidence of BPD and respiratory morbidity at 18 to 22 months corrected age. Nasal intermittent positive pressure ventilation reduced treatment failure rates compared to CPAP, but not bronchopulmonary dysplasia (BPD). LISA compared with intubation and surfactant delivery reduced BPD, but there is no evidence from randomised trials regarding long-term respiratory and neurodevelopmental outcomes. Synchronisation of positive pressure inflations with the infant's respiratory efforts used with volume targeting should be applied for infants requiring intubation as this strategy reduces BPD. A large RCT with long term follow up data demonstrated that prophylactic high frequency oscillatory ventilation (HFOV) improved respiratory and functional outcomes at school age, but those effects were not maintained after puberty. CLAC systems appear promising, but their effect on long term clinical outcomes has not yet been explored in randomised trials. Further studies are required to determine the role of newer ventilation modes such as neurally adjusted ventilator assist (NAVA). All such respiratory support strategies should be tested in randomised controlled trials powered to assess long-term outcomes.

Kaltsogianni, Ourania↗
DOE OSTI2025

A high-resolution record of Late Holocene drought in the eastern Sierra Nevada (California, USA) from June Lake carbonate geochemistry

As historic drought conditions become more common in western North America, Late Quaternary hydroclimate records become vital for putting present anthropogenic conditions into a longer-term context. Here, we establish a high-resolution record of drought for the eastern Sierra Nevada (California) using lacustrine carbonates from well-dated sediment cores. We used oxygen and carbon stable-isotope ratios, combined with high-resolution scanning X-ray fluorescence counts of calcium (Ca) and titanium (Ti), to reconstruct the drought record over the last 4600 years in June Lake. We found elevated δ 18 O and δ 13 C carbonate isotope values coinciding with peaks in both total inorganic carbon and Ca/Ti, suggesting enhanced carbonate precipitation in response to evaporative concentration of lake water. At least six intervals of prolonged (centennial-scale) carbonate deposition were identified, including three pulses during the Late Holocene Dry Period (LHDP; ~3500–2000 cal yr BP), the Medieval Climate Anomaly (~1200–800 cal yr BP), and the Current Warm Period, which began around 100 cal yr BP. This record highlights the complexities of the LHDP, an interval that was more variable at June Lake than has been previously described in regional records.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2026

Tetrahedral Zn 2+ doping LiNi 0.6 Mn 0.2 Co 0.2 O 2 improves discharge capacity retention by altering surface Ni valence during cycling and preventing oxygen evolution

5 mol-% Zn 2+ was added to the co-precipitation synthesis of LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622) to understand Zn's effect on the structural and electronic properties of NMC622. Zn is determined to successfully dope into the NMC crystal lattice as there is an increase in d-spacing along the [003], [104], and [110] directions and an increase in molar volume (100.75 cm 3 mol -1 for NMC622 and 101.00 cm 3 mol -1 for Zn-NMC). Through XPS, Zn is determined to dope on the tetrahedral 6c Wyckoff site in the NMC structure and TEM-EDS reveals that despite a slight ZnO impurity phase, 1.4 mol-% Zn successfully dopes into the crystal structure. Furthermore, cyclic voltammetry shows a suppressed anodic wave associated with oxygen evolution and EIS demonstrates that Zn-doped NMC decreases charge transfer resistance and increases Li diffusion by an order of magnitude. After the formation cycles, NMC has a higher 1 C accessible capacity, 141 mAh/g, over Zn-NMC (132 mAh/g), but after long term cycling Zn-NMC has a higher accessible capacity (117 mAh/g compared to 96 mAh/g for NMC) and increases discharge capacity retention by 18% leading to longer cycle life.

Electrochemistry↗
DOE OSTI2024

Simulated plant-mediated oxygen input has strong impacts on fine-scale porewater biogeochemistry and weak impacts on integrated methane fluxes in coastal wetlands

Methane (CH 4 ) emissions from wetland ecosystems are controlled by redox conditions in the soil, which are currently underrepresented in Earth system models. Plant-mediated radial oxygen loss (ROL) can increase soil O 2 availability, affect local redox conditions, and cause heterogeneous distribution of redox-sensitive chemical species at the root scale, which would affect CH 4 emissions integrated over larger scales. In this study, we used a subsurface geochemical simulator (PFLOTRAN) to quantify the effects of incorporating either spatially homogeneous ROL or more complex heterogeneous ROL on model predictions of porewater solute concentration depth profiles (dissolved organic carbon, methane, sulfate, sulfide) and column integrated CH 4 fluxes for a tidal coastal wetland. From the heterogeneous ROL simulation, we obtained 18% higher column averaged CH 4 concentration at the rooting zone but 5% lower total CH 4 flux compared to simulations of the homogeneous ROL or without ROL. This difference is because lower CH 4 concentrations occurred in the same rhizosphere volume that was directly connected with plant-mediated transport of CH 4 from the rooting zone to the atmosphere. Sensitivity analysis indicated that the impacts of heterogeneous ROL on model predictions of porewater oxygen and sulfide concentrations will be more important under conditions of higher ROL fluxes or more heterogeneous root distribution (lower root densities). Despite the small impact on predicted CH 4 emissions, the simulated ROL drastically reduced porewater concentrations of sulfide, an effective phytotoxin, indicating that incorporating ROL combined with sulfur cycling into ecosystem models could potentially improve predictions of plant productivity in coastal wetland ecosystems.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Radiation-Enhanced Anion Transport in Hematite

The influence of radiation-induced (1 MeV energy H+ to ~0.1 dpa at 450°C), non-equilibrium point defect populations on mass transport is studied with an integrated campaign of experimental and theoretical methods. Using epitaxial thin films of hematite with embedded 18O tracer layers and nanoscale atom probe tomography measurements, it is shown that anion self-diffusion is enhanced by at least 2 orders of magnitude under irradiation compared to thermal diffusion alone. Complementary scanning transmission electron microscopy of vacuum annealed specimens, reveals associated microstructural changes in the oxide films, including local phase transformation to Fe3O4 and the development of nanoscale voids from vacancy coalescence. Point defect formation and migration energies were computed from density functional theory and applied within the context of chemical rate theory to analyze contributions from both interstitial and vacancy mechanisms to self-diffusion in thermal and irradiation conditions. Comparisons are made between calculated, literature and newly measured self-diffusion values, revealing good agreement on the magnitude of radiation-enhanced anion diffusion. Further, the model suggests a transition from vacancy to interstitialcy mechanisms at low temperatures and high oxygen activity, consistent with the varied activation energies reported from prior studies.

iron oxides, isotopic tracers, atom probe tomograp↗
DOE OSTI2021

The Low-Lying Electronic States of NO 2 : Potential Energy and Dipole Surfaces, Bound States, and Electronic Absorption Spectrum

Nitrogen dioxide, NO 2 , is a free radical composed of the two most abundant elements in Earth’s atmosphere, nitrogen and oxygen, and is relevant to atmospheric and combustion chemistry. The electronic structure of even its lowest-lying states is remarkably complex, with various conical intersections and Renner–Teller pairings, giving rise to complex and perturbed vibronic states. Here we report some analysis of the 18 molecular states of doublet spin-multiplicity formed by combining ground-state N( 4 S u ) and O( 3 P g ) atoms. In this work, three-dimensional potential energy surfaces were fit at the MRCI(Q)-F12/VTZ-F12 level, describing the lowest four ($\tilde X$, $\tilde A$, $\tilde B$, and $\tilde C$) electronic states. A properties-based diabatization procedure was applied to accommodate the intersections, producing energies in a quasidiabatic representation and yielding couplings that were also fit into surfaces. The low-lying vibrational levels on the ground $\tilde X$ state were computed and compared with experimental measurements. Compared to experiment, the lowest 125 calculated vibrational levels (up to 8500 cm –1 above the zero-point energy) have a root-mean-squared error of 16.5 cm –1 . In addition, dipole moments for each of the lowest four electronic states—and the transition dipoles between them—were also computed and fit. With the coupled energy and dipole surfaces, the electronic spectrum was calculated in absolute intensity and compared with experimental measurements. Detailed structure in the experimental spectrum was successfully reproduced, and the total integrated intensity matches experiment to an accuracy of ~1.5% with no empirical adjustments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Evaluation of Histone Deacetylase Inhibitors as Radiosensitizers for Proton and Light Ion Radiotherapy

Significant opportunities remain for pharmacologically enhancing the clinical effectiveness of proton and carbon ion-based radiotherapies to achieve both tumor cell radiosensitization and normal tissue radioprotection. We investigated whether pretreatment with the hydroxamate-based histone deacetylase inhibitors (HDACi) SAHA (vorinostat), M344, and PTACH impacts radiation-induced DNA double-strand break (DSB) induction and repair, cell killing, and transformation (acquisition of anchorage-independent growth in soft agar) in human normal and tumor cell lines following gamma ray and light ion irradiation. Treatment of normal NFF28 primary fibroblasts and U2OS osteosarcoma, A549 lung carcinoma, and U87MG glioma cells with 5–10 µM HDACi concentrations 18 h prior to cesium-137 gamma irradiation resulted in radiosensitization measured by clonogenic survival assays and increased levels of colocalized gamma-H2AX/53BP1 foci induction. We similarly tested these HDACi following irradiation with 200 MeV protons, 290 MeV/n carbon ions, and 350 MeV/n oxygen ions delivered in the Bragg plateau region. Unlike uniform gamma ray radiosensitization, effects of HDACi pretreatment were unexpectedly cell type and ion species-dependent with C-12 and O-16 ion irradiations showing enhanced G0/G1-phase fibroblast survival (radioprotection) and in some cases reduced or absent tumor cell radiosensitization. DSB-associated foci levels were similar for proton-irradiated DMSO control and SAHA-treated fibroblast cultures, while lower levels of induced foci were observed in SAHA-pretreated C-12 ion-irradiated fibroblasts. Fibroblast transformation frequencies measured for all radiation types were generally LET-dependent and lowest following proton irradiation; however, both gamma and proton exposures showed hyperlinear transformation induction at low doses (≤25 cGy). HDACi pretreatments led to overall lower transformation frequencies at low doses for all radiation types except O-16 ions but generally led to higher transformation frequencies at higher doses (>50 cGy). The results of these in vitro studies cast doubt on the clinical efficacy of using HDACi as radiosensitizers for light ion-based hadron radiotherapy given the mixed results on their radiosensitization effectiveness and related possibility of increased second cancer induction.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Building Electron/Proton Nanohighways for Full Utilization of Water Splitting Catalysts

Low electron/proton conductivities of electrochemical catalysts, especially earth-abundant nonprecious metal catalysts, severely limit their ability to satisfy the triple-phase boundary (TPB) theory, resulting in extremely low catalyst utilization and insufficient efficiency in energy devices. In this study, an innovative electrode design strategy is proposed to build electron/proton transport nanohighways to ensure that the whole electrode meets the TPB, therefore significantly promoting enhance oxygen evolution reactions and catalyst utilizations. It is discovered that easily accessible/tunable mesoporous Au nanolayers (AuNLs) not only increase the electrode conductivity by more than 4000 times but also enable the proton transport through straight mesopores within the Debye length. The catalyst layer design with AuNLs and ultralow catalyst loading (≈0.1 mg cm -2 ) augments reaction sites from 1D to 2D, resulting in an 18-fold improvement in mass activities. Furthermore, using microscale visualization and unique coplanar-electrode electrolyzers, the relationship between the conductivity and the reaction site is revealed, allowing for the discovery of the conductivity-determining and Debye-length-determining regions for water splitting. These findings and strategies provide a novel electrode design (catalyst layer + functional sublayer + ion exchange membrane) with a sufficient electron/proton transport path for high-efficiency electrochemical energy conversion devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Unravelling the water oxidation mechanism on NaTaO 3 -based photocatalysts

Understanding the detailed kinetics and mechanisms of water oxidation is crucial because water oxidation is the bottleneck reaction in overall water splitting. In this work, we investigated photocatalytic water oxidation on NaTaO 3 -based photocatalysts. With in situ FT-IR spectroscopy, two new water oxidation intermediates with IR absorption peaks centered at 1058 and 935 cm –1 were observed and assigned to Ta(VI)=O and Ta(O 2 ) peroxo species, respectively. With H 2 18 O as the reactant and NaTa 16 O 3 as the photocatalyst, both 16 O 18 O and 18 O 2 were evolved continuously from overall water splitting as analyzed by mass spectroscopy (MS), demonstrating that the lattice O atoms in NaTaO 3 -based photocatalysts participate in the formation of O 2 during the reaction. DFT results are consistent with the formation of Ta=O, 16 O 18 O and 18 O 18 O intermediates and products, while predicting that several water oxidation pathways are thermodynamically accessible for water oxidation on NaTaO 3 . Based on these observations, we propose a three-step two-site mechanism for photocatalytic water oxidation on NaTaO 3 -based photocatalysts in which lattice oxygen plays a key role. The elucidation of the present mechanism should help in broadly understanding water oxidation on semiconductor-based photocatalysts.

14 SOLAR ENERGY↗
DOE OSTI2024

Additive manufacturing of multiscale NiFeMn multi-principal element alloys with tailored composition

Nanostructured multi-principal element alloys (MPEAs) have been explored as next-generation engineering materials due to unique mechanical and functional properties which have significant advantages over traditional dilute alloys. However, the practical applications of nanostructured MPEAs are still limited due to the lack of scalable processing approaches to prepare a large quantity of nanostructured MPEAs, as well as lack of an efficient pathway for high-throughput discovery of better functional nanostructured MPEAs within their vast compositional space. Here we tackle these challenges by presenting an integrated approach by combining direct-ink-writing-based additive manufacturing, solid-state sintering, and chemical dealloying to manufacture hierarchically porous MPEAs. The hierarchical structure is comprised of macro- and micro-scale pores introduced via extrusion printing and polymer decomposition during sintering, as well as nanoscale pores formed via chemical dealloying. The macro- and micro-scale pores allow efficient dealloying of a large mass of material as the diffusion length that the corroding medium must penetrate remains at the scale of the ligaments formed after sintering (∼10 μm), despite the large volume of the 3D-printed samples. In addition, this integrated approach enables versatile control of the alloy composition via precisely tuning the ratio of elemental powders in the starting ink, thus offering a pathway for high-throughput discovery of novel functional MPEAs. As a case study, multiscale macro/micro/nanoporous NiFeMn MPEAs with three different compositions were investigated as catalysts to reduce the overpotential of oxygen evolution reaction (OER), where NiFeMn-based electrocatalysts display composition-dependent performance such that the overpotential measured at a current of 0.5 A g −1 for OER increases in the order of Ni 58 Fe 29 Mn 13 ⩽ Ni 64 Fe 26 Mn 10 < Ni 76 Fe 18 Mn 6 . This introduced manufacturing process offers new opportunities for scalable fabrication and rapid screening of nanostructured multi-component complex alloys.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Deuterium retention in MeV ion-irradiated beryllium

Beryllium, as the material of choice for the ITER first wall, will be subject to high energy neutrons during the operation of the fusion device. Such irradiation will create displacement damage in the crystal lattice, which is known to influence hydrogen isotope retention, e.g. in iron and tungsten. Here in our study, we irradiated beryllium samples with high-energy oxygen ions up to various dpa levels (0.01 dpa, 0.1 dpa, and 1 dpa) and subsequently exposed the samples to deuterium plasma at 370 K and 573 K. The amount of retained deuterium was measured by thermal desorption spectroscopy and nuclear reaction analysis and was found to decrease by about 18% in the samples damaged up to 0.1 dpa compared to the undamaged ones. Further damaging up to 1 dpa did not show any additional effects on deuterium retention. Transmission electron microscopy was used to check for the existence of bubbles after plasma exposure.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Geochemical-hydromechanical couplings during water-serpentinized harzburgite interactions at 20° C and 30 bars

Interaction of groundwater with the serpentinized harzburgites of the upper mantle plays an important role in the geologic carbon cycle and serpentinization processes. Here, in this study, an intact serpentinized harzburgite with more than 60% lizardite from the Semail ophiolite in Oman was reacted with water at near neutral pH and low PCO 2 to observe its dissolution behavior and reaction path within the CaO-MgO-SiO 2 -CO 2 -H 2 O system at 20 °C and 30 bars. In the experiment, mass (i.e. H 2 O, ions) transfer is by diffusion and the selected temperature and pressure conditions mimic water-rock interactions at the shallow portions of most ultramafic rock hosted aquifers. Equilibrium activity-activity diagrams and thermodynamic data were used to compare the experimentally determined reaction path with the theoretical stability boundaries for minerals involved to investigate the evolution of bulk chemical composition, mineralogy, and water composition. The experiments demonstrated that (i) the water-rock interactions increased the pH of the aqueous phase from 5.9 to 7.5 over a period of 18 weeks; (ii) the dissolution of lizardite, orthopyroxene (enstatite), and clinopyroxene (diopside and augite) increased the concentration of Mg, Ca, and Si in the aqueous phase; (iii) the dissolution was incongruent with respect to Mg and Si, favoring Si release at pH > 6 due to (a) breaking of more reactive cation‑oxygen bonds that is consistent with the stoichiometry of magnesium for proton exchange reaction which favors a surface that is enriched in Mg at basic conditions, and (b) preferential dissolution of clinopyroxene Mg 1.30 Ca 0.52 Fe 0.06 Si 2 O 6 ; (iv) the aqueous phase was undersaturated with respect to carbonate (e.g. calcite, magnesite, and hydromagnesite) and hydrous (e.g. lizardite, chrysotile, brucite, and talc) minerals; (v) the bulk chemical composition and mineralogy of the intact serpentinized harzburgite matrix did not change; (vi) the thermodynamic data can successfully predict water-intact serpentinized harzburgite behavior if the water chemical composition can be constrained; and (vii) no detectable macroscopic form of damage (e.g. microcracks forming as a result of differential stress fields due to changes in volume during chemical reaction) was observed.

Carbonation↗
DOE OSTI2022

Peroxide-Selective Reduction of O 2 at Redox-Inactive Rare-Earth(III) Triflates Generates an Ambiphilic Peroxide

Metal peroxides are key species involved in a range of critical biological and synthetic processes. Rare-earth (group III and the lanthanides; Sc, Y, La–Lu) peroxides have been implicated as reactive intermediates in catalysis; however, reactivity studies of isolated, structurally characterized rare-earth peroxides have been limited. Herein, we report the peroxide-selective (93–99% O22-) reduction of dioxygen (O 2 ) at redox-inactive rare-earth triflates in methanol using a mild metallocene reductant, decamethylferrocene (Fc*). The first molecular praseodymium peroxide ([Pr III 2( O 2 2- )(18C6) 2 (EG)2][OTf]4; 18C6 = 18-crown-6, EG = ethylene glycol, - OTf = - O 3 SCF 3 ; 2-Pr) was isolated and characterized by single-crystal X-ray diffraction, Raman spectroscopy, and NMR spectroscopy. 2-Pr displays high thermal stability (120 °C, 50 mTorr), is protonated by mild organic acids [pK a1 (MeOH) = 5.09 ± 0.23], and engages in electrophilic (e.g., oxygen atom transfer) and nucleophilic (e.g., phosphate-ester cleavage) reactivity. Our mechanistic studies reveal that the rate of oxygen reduction is dictated by metal-ion accessibility, rather than Lewis acidity, and suggest new opportunities for differentiated reactivity of redox-inactive metal ions by leveraging weak metal–ligand binding events preceding electron transfer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Enriched East Asian oxygen isotope of precipitation indicates reduced summer seasonality in regional climate and westerlies

Speleothem oxygen isotope records over East Asia reveal apparently large and rapid paleoclimate changes over the last several hundred thousand years. However, what the isotopic variation actually represent in terms of the regional climate and circulation is debated. We present an answer that emerges from an analysis of the interannual variation in amount-weighted annual δ 18 O of precipitation over East Asia as simulated by an isotope-enabled model constrained by large-scale atmospheric reanalysis fields. 18 O-enriched years have reduced summer seasonality both in terms of precipitation isotopes and in the large-scale circulation. Changes occur between June and October, where the δ 18 O of precipitation (δ 18 O p ) transitions from the isotopically heavier winter to the lighter summer regime. For 18 O-enriched years, this transition is less pronounced. Variations in precipitation amount alone are insufficient to explain the amount-weighted annual δ 18 O p between 18 O-enriched and 18 O-depleted years. Reduced summer seasonality is also expressed in the low-level monsoonal southerlies and upper-level westerlies; for the latter, the northward migration across the Tibetan Plateau in the summer is less pronounced. Our result thus implicates the westerlies across the plateau as the proximate cause of East Asian paleomonsoon changes, manifested as a modulation of its summer peak.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Physiological Adaptations to Progressive Endurance Exercise Training in Adult and Aged Rats: Insights from the Molecular Transducers of Physical Activity Consortium (MoTrPAC)

While regular physical activity is a cornerstone of health, wellness, and vitality, the impact of endurance exercise training on molecular signaling within and across tissues remains to be delineated. The Molecular Transducers of Physical Activity Consortium (MoTrPAC) was established to characterize molecular networks underlying the adaptive response to exercise. Here, we describe the endurance exercise training studies undertaken by the Preclinical Animal Sites Studies component of MoTrPAC, in which we sought to develop and implement a standardized endurance exercise protocol in a large cohort of rats. To this end, Adult (6-mo) and Aged (18-mo) female (n = 151) and male (n = 143) Fischer 344 rats were subjected to progressive treadmill training (5 d/wk, ~70%–75% VO 2 max) for 1, 2, 4, or 8 wk; sedentary rats were studied as the control group. A total of 18 solid tissues, as well as blood, plasma, and feces, were collected to establish a publicly accessible biorepository and for extensive omics-based analyses by MoTrPAC. Treadmill training was highly effective, with robust improvements in skeletal muscle citrate synthase activity in as little as 1–2 wk and improvements in maximum run speed and maximal oxygen uptake by 4–8 wk. For body mass and composition, notable age- and sex-dependent responses were observed. This work in mature, treadmill-trained rats represents the most comprehensive and publicly accessible tissue biorepository, to date, and provides an unprecedented resource for studying temporal-, sex-, and age-specific responses to endurance exercise training in a preclinical rat model.

60 APPLIED LIFE SCIENCES↗