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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.

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At least 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Roads do not increase carrion use by a vertebrate scavenging community

Wildlife-vehicle collisions introduce a considerable amount of carrion into the environment, but scavenger use of this resource has not been extensively investigated. Scavengers may use roads for reliable foraging opportunities, but might also use roads for other purposes and encounter carrion opportunistically. We examined scavenging of carrion along linear features by placing 52 rabbit carcasses in each of three treatments in forested habitat during winter (Dec 2016-Mar 2017) in South Carolina, USA: roads, power line clearings (linear feature with fewer carcasses than roads due to lack of road kill), and forest interior. We used motion-activated cameras to compare arrival times and presence of vertebrate scavengers among treatments. There was no difference in proportion of carcasses scavenged or scavenger arrival time across treatments. No species arrived at roads quicker than other treatments. Turkey vultures (Cathartes aura) and coyotes (Canis latrans) scavenged equally across treatments, whereas gray foxes (Urocyon cinereoargenteus) scavenged along roads and power lines, but not in forests. We suggest that scavenger use of carrion near roads at this location during winter relates to factors other than carrion availability. Because some scavengers readily consumed carrion on roads, this resource has the potential to influence the ecology of these species.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Network structure of vertebrate scavenger assemblages at the global scale: drivers and ecosystem functioning implications

The organization of ecological assemblages has important implications for ecosystem functioning, but little is known about how scavenger communities organize at the global scale. Here, we test four hypotheses on the factors affecting the network structure of terrestrial vertebrate scavenger assemblages and its implications on ecosystem functioning. We expect scavenger assemblages to be more nested (i.e. structured): 1) in species-rich and productive regions, as nestedness has been linked to high competition for carrion resources, and 2) regions with low human impact, because the most efficient carrion consumers that promote nestedness are large vertebrate scavengers, which are especially sensitive to human persecution. 3) We also expect climatic conditions to affect assemblage structure, because some scavenger assemblages have been shown to be more nested in colder months. Finally, 4) we expect more organized assemblages to be more efficient in the consumption of the resource. We first analyzed the relationship between the nestedness of the scavenger assemblages and climatic variables (i.e. temperature, precipitation, temperature variability and precipitation variability), ecosystem productivity and biomass (i.e. NDVI) and degree of human impact (i.e. human footprint) using 53 study sites in 22 countries across five continents. Then, we related structure (i.e. nestedness) with its function (i.e. carrion consumption rate). We found a more nested structure for scavenger assemblages in regions with higher NDVI values and lower human footprint. Moreover, more organized assemblages were more efficient in the consumption of carrion. However, our results did not support the prediction that the structure of the scavenger assemblages is directly related to climate. Our findings suggest that the nested structure of vertebrate scavenger assemblages affects its functionality and is driven by anthropogenic disturbance and ecosystem productivity worldwide. Disarray of scavenger assemblage structure by anthropogenic disturbance may lead to decreases in functionality of the terrestrial ecosystems via loss of key species and trophic facilitation processes.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Carcass appearance does not influence scavenger avoidance of carnivore carrion

Abstract The selection or avoidance of certain carrion resources by vertebrate scavengers can alter the flow of nutrients in ecosystems. Evidence suggests higher trophic level carrion is scavenged by fewer vertebrate species and persists longer when compared to lower trophic level carrion, although it is unclear how scavengers distinguish between carcasses of varying species. To investigate carnivore carrion avoidance and explore sensory recognition mechanisms in scavenging species, we investigated scavenger use of intact and altered (i.e., skin, head, and feet removed) coyote— Canis latrans (carnivore) and wild pig— Sus scrofa (omnivore) carcasses experimentally placed at the Savannah River Site, SC, USA. We predicted carnivore carcasses would persist longer due to conspecific and intraguild scavenger avoidance. Further, we hypothesized visually modifying carcasses would not reduce avoidance of carnivore carrion, given scavengers likely depend largely on chemical cues when assessing carrion resources. As expected, mammalian carnivores largely avoided scavenging on coyote carcasses, resulting in carnivore carcasses having longer depletion times than wild pig carcasses at intact and altered trials. Therefore, nutrients derived from carnivore carcasses are not as readily incorporated into higher trophic levels and scavengers largely depend on olfactory cues when assessing benefits and risks associated with varying carrion resources.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2022

Increased abundance of a common scavenger affects allocation of carrion but not efficiency of carcass removal in the Fukushima Exclusion Zone

Abstract The 2011 nuclear accident in Fukushima, Japan caused the evacuation of > 100,000 people and prompted studies on environmental impacts of radiological contamination. However, few researchers have explored how the human evacuation has affected ecosystem processes. Despite contamination, one common scavenger (wild boar, Sus scrofa ) is 2–3× more abundant inside the Fukushima Exclusion Zone (FEZ). Shifts in abundance of some scavenger species can have cascading effects on ecosystems, so our objective was to investigate impacts of the evacuation and the resulting increase in wild boar on vertebrate scavenger communities. We deployed cameras at 300 carcasses in the FEZ and a nearby inhabited area, and quantified carcass fate, scavenger species, and detection/persistence times. We also tested effects of carcass size and habitat on scavenger community composition and efficiency by balancing trials across two carcass sizes and habitats in each zone. Overall scavenger richness and carcass removal rates (73%) were similar in the FEZ and inhabited area, but species-specific carcass removal rates and occurrence differed between zones. Wild boar removed substantially more carcasses inside the FEZ, with implications for nutrient and contaminant distribution. Our results suggest carcass size affects scavenging dynamics more than human activity or habitat, and abundance changes of common scavengers can influence carrion resource allocation.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2017

Abiotic and biotic factors modulate carrion fate and vertebrate scavenging communities

Carrion is a valuable nutrient resource used by a diversity of vertebrates across the globe. However, vertebrate scavenging ecology remains an understudied area of science, especially in regards to how biotic and abiotic factors influence scavenging community composition. Here we elucidate how fundamental biotic and abiotic factors interact to modulate the efficiency and composition of vertebrate scavengers by investigating scavenging dynamics across a large gradient in carcass sizes and habitat types representative of many temperate ecosystems, as well as between two seasons reflecting differences in invertebrate activity. We found carcass size and season influenced carcass fate and persistence, as well as the richness and composition of vertebrate scavenger communities utilizing carrion resources. Species richness, which increased as carcass size increased and was higher during the cool season, had a significant effect on carcass persistence. In addition, habitat type influenced carcass detection times by vertebrates, and we observed relatively distinct scavenging communities associated with carcasses of differing sizes. This research highlights a pervasive limitation to the interpretation of results of previous studies as research failing to incorporate carcass size and habitat type could result in the over or underrepresentation of vertebrate scavengers in food web dynamics.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2016

Wet scavenging of soluble gases in DC3 deep convective storms using WRF-Chem simulations and aircraft observations

In this work, we examine wet scavenging of soluble trace gases in storms observed during the Deep Convective Clouds and Chemistry (DC3) field campaign. We conduct high-resolution simulations with the Weather Research and Forecasting model with Chemistry (WRF-Chem) of a severe storm in Oklahoma. The model represents well the storm location, size, and structure as compared with Next Generation Weather Radar reflectivity, and simulated CO transport is consistent with aircraft observations. Scavenging efficiencies (SEs) between inflow and outflow of soluble species are calculated from aircraft measurements and model simulations. Using a simple wet scavenging scheme, we simulate the SE of each soluble species within the error bars of the observations. The simulated SEs of all species except nitric acid (HNO 3 ) are highly sensitive to the values specified for the fractions retained in ice when cloud water freezes. To reproduce the observations, we must assume zero ice retention for formaldehyde (CH 2 O) and hydrogen peroxide (H 2 O 2 ) and complete retention for methyl hydrogen peroxide (CH 3 OOH) and sulfur dioxide (SO 2 ), likely to compensate for the lack of aqueous chemistry in the model. We then compare scavenging efficiencies among storms that formed in Alabama and northeast Colorado and the Oklahoma storm. Significant differences in SEs are seen among storms and species. More scavenging of HNO 3 and less removal of CH 3 OOH are seen in storms with higher maximum flash rates, an indication of more graupel mass. Graupel is associated with mixed-phase scavenging and lightning production of nitrogen oxides (NOx ), processes that may explain the observed differences in HNO 3 and CH 3 OOH scavenging.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2016

Carcasses of invasive species are predominantly utilized by invasive scavengers in an island ecosystem

Abstract Invasive species have significantly affected ecosystems, particularly islands, and species invasions continue with increasing globalization. Largely unstudied, the influence of invasive species on island ecosystem functions, especially scavenging and decomposition, could be substantive. Quantifying carcass utilization by different scavengers and shifts in community dynamics in the presence of invasive animals is of particular interest for understanding impacts on nutrient recycling. Invasive species could benefit greatly from carcass resources within highly invaded island ecosystems, through increased invasion success and population growth, subsequently exacerbating their impacts on native species. We quantified how experimentally placed invasive amphibian, reptile, small mammal, and bird carcasses were utilized by vertebrate and invertebrate scavengers on the Big Island of Hawai'i in three island habitats: a barren lava field, a vegetated lava field, and a rainforest. We used camera traps to record vertebrate scavengers removing carcasses and elapsed time until removal. We evaluated differences in scavenging between vertebrates and invertebrates and within the vertebrate community across different habitats and carcass types. Despite the small carcass sizes (<1 kg) used in this study, 55% of carcasses were removed by vertebrate scavengers, all invasive: mongoose, rodents, cats, pigs, and a common myna. Our data indicate that invasive vertebrate scavengers in this island ecosystem are highly efficient at assimilating a range of carrion resources across a variety of habitats. Carcasses of invasive animals could contribute substantially to energy budgets of other invasive vertebrate species. This may be a critical component contributing to successful invasions especially on islands and subsequent impacts on ecosystem function.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2021

Involvement of multiple scavenger receptors in advanced glycation end product-induced vessel tube formation in endothelial cells

Highlights: • Multiple scavenger receptors contribute to AGE-induced angiogenesis. • RAGE contributes to AGE-induced angiogenesis by upregulation of scavenger receptors. • AGE activates mTOR signaling. Toxic advanced glycation end products (toxic AGEs) derived from glycolaldehyde (AGE3) have been implicated in the development of diabetic vascular complications such as retinopathy characterised by excessive angiogenesis. Different receptor types, such as receptor for AGEs (RAGE), Toll like receptor-4 and scavenger receptors, are expressed in endothelial cells and contribute to AGE-elicited alteration of cell function. In the present study, we examined the involvement of AGE-related receptors on AGE-induced angiogenesis in endothelial cells. The effects of pharmacological inhibitors or receptor neutralizing antibodies on AGE3-induced tube formation were investigated using the in vitro Matrigel tube formation assay in b.End5 cells (mouse endothelial cells). AGE3-induced signalling pathways and receptor expression changes were analysed by Western blot analysis and flow cytometry, respectively. Both FPS-ZM1, a RAGE inhibitor, and fucoidan, a ligand for scavenger receptors, suppressed AGE3-induced tube formation. Cocktails of neutralizing antibodies against the scavenger receptors CD36, CD163 and LOX-1 prevented AGE3-induced tube formation. AGE3 activated mTOR signalling, resulting in facilitation of tube formation. Activation of the AGE-RAGE pathway also led to the upregulation of scavenger receptors. Taken together, our findings suggest that the scavenger receptors CD36, CD163 and LOX-1 in conjunction with the RAGE receptor work together to mediate toxic AGE-induced facilitation of angiogenesis.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2026

Electrochemical Characterization of Photo-Driven Hole-Scavenging by Cadmium Sulfide Quantum Dot-Nitrogenase Biohybrid Complexes

Light-driven biohybrid systems that couple semiconductor nanocrystals with enzymes offer a promising strategy for solar-to-chemical energy-conserving reduction reactions, yet are often limited by inefficient hole scavenging. Hole scavenging is critical for maintaining charge separation in the light-absorbing electron donor molecule and, thus, for sustaining catalytic turnover, making quantification essential to improving system efficiency. Here, we introduce a photoelectrochemical approach for real-time monitoring of hole scavenging in cadmium sulfide (CdS) quantum dot (QD)-nitrogenase MoFe protein biohybrids that catalyze the reduction of H+ and N2. Using hydroquinone (HQ) as the sacrificial electron donor (SED), oxidation of HQ to benzoquinone (BQ) by photogenerated valence-band holes is coupled to the electrochemical reduction of BQ at an electrode, enabling quantification of the hole-scavenging reaction via chronoamperometry. This approach provides a continuous, real-time readout of charge-transfer dynamics under illumination. Systematic variation of light intensity and donor concentration reveals that hole scavenging scales with photon flux and exhibits a non-linear dependence on SED concentration, with an optimum at intermediate HQ concentrations. These results establish chronoamperometry as a powerful tool for probing photoinduced charge transfer, advancing the quantitative understanding of hole-scavenging in biohybrid systems, and offering a generalizable framework for optimizing solar-driven biocatalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Quantifying Impacts of Aerosol Mixing State on Nucleation-Scavenging of Black Carbon Aerosol Particles

Recent observational studies suggest that nucleation-scavenging is the principal path to removing black carbon-containing aerosol from the atmosphere, thus affecting black carbon’s lifetime and radiative forcing. Modeling the process of nucleation-scavenging is challenging, since black carbon (BC) forms complex internal mixtures with other aerosol species. Here, we examined the impacts of black carbon mixing state on nucleation scavenging using the particle-resolved aerosol model PartMC-MOSAIC. This modeling approach has the unique advantage that complex aerosol mixing states can be represented on a per-particle level. For a scenario library that comprised hundreds of diverse aerosol populations, we quantified nucleation-scavenged BC mass fractions. Consistent with measurements, these vary widely, depending on the amount of BC, the amount of coating and coating material, as well as the environmental supersaturation. We quantified the error in the nucleation-scavenged black carbon mass fraction introduced when assuming an internally mixed distribution, and determined its bounds depending on environmental supersaturation and on the aerosol mixing state index χ . For a given χ value, the error decreased at higher supersaturations. For more externally mixed populations (χ <20%), the nucleation-scavenged BC mass fraction could be overestimated by more than 1000% at supersaturations of 0.1%, while for more internally mixed populations (χ >75%), the error was below 100% for the range of supersaturations (from 0.02% to 1%) investigated here. Thus, accounting for black carbon mixing state and knowledge of the supersaturation of the environment are crucial when determining the amount of black carbon that can be incorporated into clouds.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2016

The effect of a Ta oxygen scavenger layer on HfO 2 -based resistive switching behavior: Thermodynamic stability, electronic structure, and low-bias transport

Reversible resistive switching between high-resistance and low-resistance states in metal-oxide-metal heterostructures makes them very interesting for applications in random access memories. While recent experimental work has shown that inserting a metallic "oxygen scavenger layer'' between the positive electrode and oxide improves device performance, the fundamental understanding of how the scavenger layer modifies the heterostructure properties is lacking. We use density functional theory to calculate thermodynamic properties and conductance of TiN/HfO 2 /TiN heterostructures with and without a Ta scavenger layer. First, we show that Ta insertion lowers the formation energy of low-resistance states. Second, while the Ta scavenger layer reduces the Schottky barrier height in the high-resistance state by modifying the interface charge at the oxide-electrode interface, the heterostructure maintains a high resistance ratio between high-and low-resistance states. Lastly, we show that the low-bias conductance of device on-states becomes much less sensitive to the spatial distribution of oxygen removed from the HfO 2 in the presence of the Ta layer. By providing a fundamental understanding of the observed improvements with scavenger layers, we open a path to engineer interfaces with oxygen scavenger layers to control and enhance device performance. In turn, this may enable the realization of a non-volatile low-power memory technology with concomitant reduction in energy consumption by consumer electronics and offering significant benefits to society.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2022

Effects of Port Angle on Scavenging of an Opposed Piston Two-Stroke Engine

Opposed-piston 2-stroke (OP-2S) engines have the potential to achieve higher thermal efficiency than a typical diesel engine. However, the uniflow scavenging process is difficult to control over a wide range of speeds and loads. Scavenging performance is highly sensitive to pressure dynamics, port timings, and port design. This study proposes an analysis of the effects of port vane angle on the scavenging performance of an opposed-piston 2-stroke engine via simulation. A CFD model of a three-cylinder opposed-piston 2-stroke was developed and validated against experimental data collected by Achates Power Inc. One of the three cylinders was then isolated in a new model and simulated using cycle-averaged and cylinder-averaged initial/ boundary conditions. This isolated cylinder model was used to efficiently sweep port angles from 12 degrees to 29 degrees at different pressure ratios. Results indicate that scavenging performance is correlated with the bulk swirl ratio generated by these port angles. Scavenging performance is also sensitive to the pressure ratio across the engine. It was concluded that, for a given pressure ratio, the smallest port angle produces the best scavenging; however, previous work indicates lower bulk swirl ratio during combustion can have an impact on emissions formation.

33 ADVANCED PROPULSION SYSTEMS↗
DOE OSTI2015

Mathematically determined scavenger impacts during ozonolysis of oxalic acid waste slurries - 15600

A basic oxidant balance, including the primary chemical reactions associated with ozone, hydroxyl radical generation, scavengers and oxalate decomposition reactions was constructed and used to develop mathematical models to represent both steady state and time dependent changes in ozone concentrations, hydroxyl radical concentrations, scavenger concentrations and oxalate concentrations. Using the results from previous spent 1 wt% oxalic acid decomposition testing, a plot of 1/(oxalate reaction rate ) vs. 1/[C{sub 2}O{sub 4}{sup 2-}]) was used to estimate the initial hydroxyl radical generation values (i.e., g values) at time = 0. These g values are then compared for the different slurries to determine if the changes in g values are consistent with the scavenger dilution between the sequentially created slurries. Also considered as a potential scavenger is the CO{sub 2} arising from the oxalate decomposition. In this case the scavenger concentration and the carbon dioxide concentrations would be the same, and k{sub s2} =k{sub sc}. Since the CO{sub 2} is created from the decomposition of oxalate, a standard equation can be used to compensate for time dependence of [C{sub 2}O{sub 4}{sup 2-}]. Using the results from previous spent 1 wt% oxalic acid decomposition testing, plots of oxalate concentration over time were used to determine time specific g values. The g values are then compared to determine how the values change throughput the oxalate decomposition. Using the results from previous spent 1 wt% oxalic acid decomposition testing, time dependent values are developed for 'k{sub g}/k{sub a}' to show the relative significance of hydroxyl radical reacting with the scavenger vs decomposition of the oxalate. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2017

Scavenger removal of bird carcasses at simulated wind turbines: Does carcass type matter?

Abstract Wind energy development can negatively impact bird populations due to bird–turbine collisions. To accurately estimate bird mortality at wind farms, the number of dead birds found under turbines is commonly corrected for carcass removal by scavengers, which is quantified by measuring persistence of experimental carcasses through time. These studies often use domestic birds as surrogates because carcasses of wild birds (e.g., raptors) are difficult to obtain. We assessed scavenger removal of carcasses from five bird species at simulated turbines to determine whether domestic surrogates are scavenged at a different rate than raptors, species of interest for wind turbine mortality. The percentage of carcasses scavenged during 14‐d rounds ranged from 34.6% for American kestrels ( Falco sparverius ) to 65.4% for chickens ( Gallus gallus ), and the percentage of carcasses completely removed ranged from 13.5% for red‐tailed hawks ( Buteo jamaicensis ) to 67.3% for northern bobwhites ( Colinus virginianus ). Carcass type (i.e., species) was the only predictor included in the best‐fit logistic regression model of complete carcass removal, and a survival analysis indicated carcass type influenced elapsed time to scavenging events. Our results suggest the use of surrogate species to quantify carcass removal at wind turbines could lead to inaccurate mortality estimates.

17 WIND ENERGY↗
DOE OSTI2011

A superoxide anion-scavenger, 1,3-selenazolidin-4-one suppresses serum deprivation-induced apoptosis in PC12 cells by activating MAP kinase

Synthetic organic selenium compounds, such as ebselen, may show glutathione peroxidase-like antioxidant activity and have a neurotrophic effect. We synthesized 1,3-selenazolidin-4-ones, new types of synthetic organic selenium compounds (five-member ring compounds), to study their possible applications as antioxidants or neurotrophic-like molecules. Their superoxide radical scavenging effects were assessed using the quantitative, highly sensitive method of real-time kinetic chemiluminescence. At 166 {mu}M, the O{sub 2}{sup -} scavenging activity of 1,3-selenazolidin-4-ones ranged from 0 to 66.2%. 2-[3-(4-Methoxyphenyl)-4-oxo-1,3-selenazolidin-2-ylidene]malononitrile (compound b) showed the strongest superoxide anion-scavenging activity among the 6 kinds of 2-methylene-1,3-selenazolidin-4-ones examined. Compound b had a 50% inhibitory concentration (IC{sub 50}) at 92.4 {mu}M and acted as an effective and potentially useful O{sub 2}{sup -} scavenger in vitro. The effect of compound b on rat pheochromocytome cell line PC12 cells was compared with that of ebselen or nerve growth factor (NGF) by use of the MTT [3-(4, 5-dimethyl-2-thiazolyl)-2,5-diphenyl-2H-tetrazolium bromide] assay. When ebselen was added at 100 {mu}M or more, toxicity toward PC12 cells was evident. On the contrary, compound b suppressed serum deprivation-induced apoptosis in PC12 cells more effectively at a concentration of 100 {mu}M. The activity of compound b to phosphorylate mitogen-activated protein kinase/extracellular signal-regulated protein kinase (ERK) 1/2 (MAP kinase) in PC12 cells was higher than that of ebselen, and the former at 100 {mu}M induced the phosphorylation of MAP kinase to a degree similar to that induced by NGF. From these results, we conclude that this superoxide anion-scavenger, compound b, suppressed serum deprivation-induced apoptosis by promoting the phosphorylation of MAP kinase. -- Highlights: Black-Right-Pointing-Pointer We newly synthesized 1,3-selenazolidin-4-ones to study their possible applications. Black-Right-Pointing-Pointer Among new compounds, compound b showed the strongest SOSA. Black-Right-Pointing-Pointer Compound b suppressed serum deprivation-induced apoptosis in PC12 cells. Black-Right-Pointing-Pointer Compound b suppressed apoptosis by promoting the activation of MAP kinase.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2014

Effect of Si substrate on interfacial SiO{sub 2} scavenging in HfO{sub 2}/SiO{sub 2}/Si stacks

The scavenging kinetics of an ultra-thin SiO{sub 2} interface layer (SiO{sub 2}-IL) in an HfO{sub 2}/SiO{sub 2}/Si stack is discussed by focusing on the substrate effect in addition to oxygen diffusion. {sup 18}O tracing experiments demonstrate that the O-atom moves from the SiO{sub 2}-IL to the HfO{sub 2} layer during scavenging. SiO{sub 2}-IL scavenging with various substrates (Si, SiC, and sapphire) has been found to be significantly different, which suggests that the Si in the substrate is also necessary to continuously cause the scavenging. Based on these findings and thermodynamic considerations, a kinetic model where oxygen vacancy (V{sub O}) transferred from the HfO{sub 2} reacts with the SiO{sub 2}, which is in contact with the Si-substrate, is proposed for the SiO{sub 2}-IL scavenging.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2017

Manganoporphyrin-Polyphenol Multilayer Capsules as Radical and Reactive Oxygen Species (ROS) Scavengers

Local modulation of oxidative stress is crucial for a variety of biochemical events including cellular differentiation, apoptosis, and defense against pathogens. Currently employed natural and synthetic antioxidants exhibit a lack of biocompatibility, bioavailability, and chemical stability, resulting in limited capability to scavenge reactive oxygen species (ROS). To mediate these drawbacks, we have developed a synergistic manganoporphyrin-polyphenol polymeric nanothin coating and hollow microcapsules with efficient antioxidant activity and controllable ROS modulation. These materials are produced by multilayer assembly of a natural polyphenolic antioxidant, tannic acid (TA), with a synthesized copolymer of polyvinylpyrrolidone containing a manganoporphyrin modality (MnP-PVPON) which mimics the enzymatic antioxidant superoxide dismutase. The redox activity of the copolymer is demonstrated to dramatically increase the antioxidant response of MnP-PVPON/TA capsules versus unmodified PVPON/TA capsules through reduction of a radical cationic dye and to significantly suppress the proliferation of superoxide via cytochrome C competition. Inclusion of MnP-PVPON as an outer layer enhances radical-scavenging activity as compared to localization of the layer in the middle or inner part of the capsule shell. In addition, we demonstrate that TA is crucial for the synergistic radical-scavenging activity of the MnP-PVPON/TA system which exhibits a combined superoxide dismutase-like ability and catalase-like activity in response to the free radical superoxide challenge. The MnP-PVPON/TA capsules exhibit a negligible, 8% loss of shell thickness upon free radical treatment, while PVPON/TA capsules lose 39% of their shell thickness due to the noncatalytic free-radical-scavenging of TA, as demonstrated by small angle neutron scattering (SANS). Finally, we have found the manganoporphyrin-polyphenol capsules to be nontoxic to splenocytes from NOD mice after 48 h incubation. In conclusion, our study illustrates the strong potential of combining catalytic activity of manganoporphyrins with natural polyphenolic antioxidants to design efficient free-radical-scavenging materials that may eventually be used in antioxidant therapies and as free radical dissipating protective carriers of biomolecules for biomedical or industrial applications.

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

Changing chemistry of particulate manganese in the near- and far-field hydrothermal plumes from 15°S East Pacific Rise and its influence on metal scavenging

Dissolved Mn(II) in the hydrothermal plume is known to be microbially oxidized to form Mn(III/IV) oxides, and the Mn oxides scavenge other trace elements in seawater. In the GEOTRACES GP16 cruise, dissolved Mn (dMn) and particulate Mn (pMn) were found to be transported over 4000 km westwards from the Southern Eastern Pacific Rise. Previous studies in this plume showed different removal rates of dMn and pMn as well as pMn size distribution between the near-field (<80 km from the ridge axis) and far-field (>80 km) plumes. In order to understand Mn cycling in these plumes, spatial distribution, oxidation states, and mineral structures of Mn in small size fraction (SSF; 0.8–51 μm) and large size fraction (LSF; >51 μm) particles from the near-field and far-field plumes were examined using micro X-ray fluorescence spectrometry (μ-XRF), X-ray absorption near-edge structure spectroscopy (XANES), chemical species mapping, and extended X-ray absorption fine-structure spectroscopy (EXAFS). In the near-field plume, pMn in the SSF is dominated by oxidized Mn with Mn(III) fractions of ~30%. They are a mixture of δ-MnO 2 and triclinic birnessites that is known to be formed as a result of autocatalytic Mn(II) oxidation at the surface of freshly-formed δ-MnO2, suggesting that both microbial and autocatalytic Mn oxidation occur in the near-field plume. The LSF pMn in the near-field plume is also oxidized and often found in large aggregates several hundreds of μm in size. These aggregates settle out in the near-field and during transport, and are not found in the far-field plume. In the far-field plume where Mn oxides are not newly formed, pMn in the SSF is oxidized, but their Mn(III) fractions are smaller than in the near-field pMn. Unlike the SSF, the far-field plume LSF pMn is dominated by reduced Mn, implying very slow aggregation of pMn in the far-field plume. The different characteristics of pMn between the near-field and far-field plumes affect its scavenging of other trace elements. In the near-field plume, Co, Mo, 231 Pa are associated with pMn, but not in the far-field plume. 231 Pa is adsorbed to pFe rather than pMn in the far-field plume, and Pb is adsorbed to pFe in the entire plume. The result shows that freshly-formed Mn oxides in the near-field plume have higher scavenging capacity than the far-field plume pMn. Our findings suggest that the mineralogical age of Mn oxides may be an important parameter that controls the scavenging of many other trace elements and isotopes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗