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All sourcesNASA NTRSDOE OSTI
NASA NTRSDate not supplied

Effect of Pressure on Trace Element Activity Coefficients in Metal-Silicate Systems

The partitioning of trace elements between metal and silicate melts serves as the foundation for understanding the differentiation of a planetary body into a metallic core and silicate mantle. Element activity influences metal-silicate partitioning behavior. Activity coefficients are directly dependent on composition and temperature, and can be indirectly dependent on oxygen fugacity and pressure. Distinguishing the effect of pressure from other variables on the activity coefficients and partitioning is important for understanding the chemical evolution of different planetary bodies during differentiation. In this study, we investigated the influence of pressure on the activity coefficients of Cu, Mo, Pd, Pt, As, Sb, and Bi in Fe-Si metallic liquids. All of these elements exhibit moderate to high activity coefficients in Fe-Si liquids at low pressure, which significantly controls their metal-silicate partitioning behavior. Identifying whether this strong dependence persists at higher pressures is critical to modeling and understanding the chemical consequences of core formation. New experiments at 10 GPa were used to derive activity coefficients for these metals which can be compared to activity coefficients determined at 1 GPa. Experiments were conducted at 10 GPa and 2373K using a 10/5 assembly in the 880-ton multi-anvil press at NASA Johnson Space Center. The standard 10/5 COMPRES assembly was slightly modified to accommodate a sample capsule machined from single-crystal MgO that minimizes melt percolation out of the sample volume during the experiment. Experiment starting materials were comprised of 70 wt.% Knippa basalt and 30 wt.% metal. The metal mixture (~85 wt.% Fe) was created by adding the elements of interest (Cu, Mo, Pd, Pt, As, Sb, Bi) to Fe metal powder. Varied amounts of Si metal (0-10 wt.% Si) were added to the metal-silicate mixtures to generate a systematic series of starting materials. For each element, an epsilon interaction parameter in Fe-Si liquid was derived from the results of our 0-10 wt.% Si metal series. To investigate whether pressure influences the trace element activity coefficients in the 1-10 GPa pressure range, we compared our results at 10 GPa to those at 1-4 GPa [1-3]. Our results can also be directly compared to interaction parameters for Au, P, V, Mn, Ga, Zn, Cd, Sn, W, Pb, and Nb previously determined at 10 GPa and 2373K following the same methods [4]. Combined, this suite of interaction parameters will directly inform metal-silicate partitioning between 1 and 10 GPa, and assess whether these values can be extrapolated to modeling differentiation processes at pressures >10 GPa.

Kelsey Prissel↗
NASA NTRSDate not supplied

Active Volcanoes of Kamchatka as Suitable Terrestrial Analogs for Future Landing Missions and for Change Detection Analysis on Venus

The next decade will see the return to Venus due to a number of missions which have been recently selected and proposed for launch. The selected missions NASA DAVINCI and VERITAS, Roscosmos Venera-D, and ESA EnVision, along with the proposed missions ISRO Shukrayaan- 1, and CNSA VOICE, will open a new era for the exploration of the Earth’s hellish twin planet. These missions will shed new light on the science questions such as: (a) whether recent volcanic activity is locally constrained, or active volcanism occurs on a global scale; (b) the rate of the present-day volcanic activity; (c) the styles of volcanism on Venus, including possible occurrences of pyroclastic/explosive volcanism; and (d) how does the extreme environment on Venus effect volcanic activity. In preparation for these future missions to Venus, the Analogs for VENus’ GEologically Recent Surfaces (AVENGERS) initiative has the scope to select and analyze a number of active terrestrial volcanoes as suitable analogs for the identification and analysis of active volcanism on Venus. The Roscosmos Venera-D is the only mission, among the currently selected or planned mission, equipped with a lander to analyze the elemental and mineralogical composition of the surface. Therefore, it is crucial to find applicable volcanic areas on Earth to perform operational tests such as surface drilling and in-situ elemental composition analysis. To this regard, we propose the analysis of active volcanoes of the Kamchatka Peninsula, which is in a geodynamic setting (subduction) contrasting to that of the volcanic rises on Venus (hot spot). Thus, Kamchatka may represent a helpful geodynamic endmember to put the expected landing site of the Venera-D mission within the context of the entire variety of volcanic landforms and surface chemistry. The Kamchatka Peninsula is located on the eastern margin of the Eurasian plate, in proximity to the Kuril-Kamchatka subduction zone. The frequent eruptions characterizing the volcanoes of the Kamchatka Peninsula make them a suitable terrestrial analog for the possible detection of ongoing eruptions on Venus by future missions, which can be achieved by comparing a sequence of radar images of the same volcano and its surroundings taken at different times. Moreover, it is possible to collect samples of both unweathered and weathered volcanic deposits, to analyze their near infrared spectra in the laboratory for direct comparison with the spectra to be provided by the future missions to Venus. The chemical analyses of Venusian surface materials from the previous Soviet Venera and Vega missions are consistent with that of tholeiitic basalts. Since the volcanism of the Kamchatka Peninsula is characterized by both basaltic lava flows eruptions and pyroclastic activity, performing operational tests in the Kamchatka Peninsula also offers the unique opportunity to provide us the tools to potentially interpret the diverse output given by both effusive and explosive volcanic products.

Piero D'Incecco↗
DOE OSTI2018

Decontamination and Decommissioning Activities of a Radiopharmaceuticals Production Facility - 18067

On May 2012, Best Medical Belgium S.A. (BMB), a manufacturer of pharmaceutical products located on the nuclear site of Fleurus, was declared bankrupt. According to the Belgian law, ONDRAF/NIRAS (Belgian Radioactive Waste Management Agency) was entrusted with the clean-up and decommissioning operations of the former BMB facilities, nowadays known as 'ONDRAF Site Fleurus' (ONSF). In June 2015, ONSF launched a Decontamination and Decommissioning (D and D) program, for which Tractebel: - Supports the definition of the clean-up and decommissioning strategies; - Drafts the Final Decommissioning Plan (FDP) and Safety Analysis Report (SAR) that will be submitted to FANC/AFCN (Belgian Federal Agency for Nuclear Control) in order to get the License for decommissioning; - Drafts the technical specifications of the public tendering process related to the D and D program; - Ensures the day to-day follow-up of the D and D activities on site. Four nuclear buildings are part of the D and D activities. One of them, building 14 (B14), represents the most challenging and extensive task with the clean-up of highly contaminated areas and its further decommissioning up to the final state. This building features two cyclotrons (CGR and IBA cyclotrons) successively used to produce radioisotopes, as well as hot cells and glove boxes used for their purification and the conditioning of the final pharmaceutical product. The present paper aims at presenting the most recent development steps of the clean-up phase regarding the adaptations of existing facilities and the upcoming activities in preparation of the decommissioning activities. To allow the sorting and the treatment of the radioactive material identified in the physical and radiological inventory, several workshops have been implemented within the B14 building in order to deal with radioactive materials arising from the clean-up and D and D activities. Following the conceptual design phase, Tractebel has actively monitored the on-site activities for the construction of those workshops such as: - The modification of the civil works; - The revamping of the ventilation system; - The installation of dedicated lifting equipment and workstations equipped with cutting devices; - The assembly of a docking station for filling the radioactive packages. The removal of the activated concrete surrounding the IBA cyclotron requires the erection of a containment structure and an extension structure. The containment structure, composed of light metallic beams, is located above the cyclotron and its irradiation zones. For operational security reasons and working efficiency, the cutting process of the concrete ceilings and walls will be performed from the top inside the containment structure by means of an eight tons overhead bridge crane. Concrete blocks resulting from the cutting process will then be lifted, without any loss of containment, towards the extension zone of the nuclear zone of the IBA cyclotron for further resizing, sorting and evacuation towards the identified waste routes. To prepare this task which will be performed during the decommissioning phase, Tractebel sets up the necessary technical specifications. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2018

Characterization of Highly Active Cells in Preparation for Post Operational Clean Out at Sellafield - 18139

The Highly Active Liquor Evaporation and Storage (HALES) Plant at Sellafield receives highly active (HA) raffinate liquors from the Magnox and Thermal Oxide (THoRP) Reprocessing Plants. These liquors are concentrated through evaporation into Highly Active Liquor (HAL), conditioned and stored in HALES before immobilisation in glass in the Waste Vitrification Plant (WVP). Reprocessing operations at Sellafield are nearing completion and hence these liquor feeds will soon cease. Therefore, HALES is starting its planning and preparation phases for Post Operational Clean Out (POCO) and decommissioning. POCO is a transitional phase between operations and decommissioning and encompasses activities undertaken to remove residual inventory and activity from the facility. Key drivers for POCO include risk and hazard reduction and facilitating subsequent decommissioning activities (including potential surveillance and maintenance or care and maintenance regimes). Characterization is a critical enabler for development and implementation of effective POCO. In addition to the key drivers above characterization within HALES will be used to: - Define the start and end points of POCO (radiological condition, inventory sources and location, configuration, etc.); - Develop and technically underpin the wash out strategy (volumes, rates, reagent types, etc.; - Monitor the effectiveness of POCO activities (reduction in inventory/activity, points of diminishing return, confirmation of end points for POCO). There are a number of significant challenges that present to characterization of the HALES facilities. Perhaps the most significant of these is the radiological status of the facility. HALES is an HA facility meaning that the high dose rates limit not only the technology selection for characterization (i.e. those with a very high radiation tolerance) but also place constraints on the access and deployment for the selected technology. Additionally, parts of the facility are circa 60 years old which brings its own challenges such as poor quality construction drawings and limited operational knowledge. Finally, limited sampling capability and minimal data regarding historic operations has resulted in uncertainties that will need to be addressed in order to undertake POCO as efficiently and effectively as possible. The solution to this challenge requires a novel and innovative approach and an example of this is the technique which is described in this paper. This is a radiometric characterization technique which utilizes remotely deployed dosimetry to determine the activity distribution within the vessels of interest to POCO. The results to date have been extremely promising, and the ability to produce concise visual representation of these results has already begun to facilitate better informed discussions around the POCO of the facility. It is expected that in the future this technique will be applicable to other areas of Sellafield which face similar characterization challenges. This paper presents a summary of the development and implementation of the solution along with the results obtained so far. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2025

Polymer Size–Catalytic Activity Relationships in Solution by Fluorescence Correlation Spectroscopy

Measuring the catalytic activity of specific sizes of polymers with active catalysts in solution is typically challenging, due to limited instrument detection sensitivity and/or dynamic range. Here, a fluorescence correlation spectroscopy (FCS) method is developed to determine the catalytic activity of living polymers of a specific apparent size in solution. Deviation from a single-component FCS data fitting, as assessed by χ2, is also introduced and developed as a “speciation index”—a method to evaluate and track changes in the relative amount of distinct polymer sizes with reaction progress. These methods are enabled by incorporating a selectively reactive fluorescent monomer into growing polydicyclopentadiene or polynorbornene during ring-opening metathesis polymerization (ROMP). Compared to polynorbornene, data showed that catalysts in aggregates of polyDCPD retained higher activity for longer—outcomes not directly inferable from simple diffusional-access predictions. Here, the ability to assign catalytic activity to polymers of specific sizes, and then to determine how this activity evolves with reaction progress, support long-term goals in the development and measurement of nano-objects that possess size-dependent catalytic activity.

Active catalyst↗
DOE OSTI2023

Detecting Permafrost Active Layer Thickness Change From Nonlinear Baseflow Recession

We report permafrost underlies about one fifth of the global land area and affects ground stability, freshwater runoff, soil chemistry, and surface-atmosphere gas exchange. The depth of thawed ground overlying permafrost (active layer thickness) has broadly increased across the Arctic in recent decades, coincident with a period of increased streamflow, especially the lowest flows (baseflow). Mechanistic links between active layer thickness and baseflow have recently been explored using linear reservoir theory, but most watersheds behave as nonlinear reservoirs. We derive theoretical nonlinear relationships between long-term average saturated soil thickness $\bar{η}$(proxy for active layer thickness) and long-term average baseflow. When applied to 38 years of daily streamflow data for the Kuparuk River basin on the North Slope of Alaska, the theory predicts $\bar{η}$ increased 0.17 ± 0.22[2σ] cm a -1 between 1983 and 2020 (6.4 ± cm total). The rate of increase nearly doubled to 0.29 ± 0.31 cm a -1 between 1990 and 2020, during which time local field measurements from Circumpolar Active Layer Monitoring sites indicate the active layer increased 0.31 ± 0.22 cm a -1 . The predicted rate of increase more than doubled again between 2002 and 2020, outpacing a near doubling of observed active layer thickening, consistent with trends in terrestrial water storage inferred from Gravity Recovery and Climate Experiment satellite gravimetry and Modern-Era Retrospective Analysis for Research and Applications climate reanalysis. Overall, hydrologic change is accelerating in the Kuparuk River basin, and we provide a theoretical framework for estimating basin-scale changes in active layer water storage from streamflow measurements.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Potential Activities and Long Lifetimes of Organic Carbon-Degrading Extracellular Enzymes in Deep Subsurface Sediments of the Baltic Sea

Heterotrophic microorganisms in marine sediments produce extracellular enzymes to hydrolyze organic macromolecules, so their products can be transported inside the cell and used for energy and growth. Therefore, extracellular enzymes may mediate the fate of organic carbon in sediments. The Baltic Sea Basin is a primarily depositional environment with high potential for organic matter preservation. The potential activities of multiple organic carbon-degrading enzymes were measured in samples obtained by the International Ocean Discovery Program Expedition 347 from the Little Belt Strait, Denmark, core M0059C. Potential maximum hydrolysis rates (V max ) were measured at depths down to 77.9mbsf for the following enzymes: alkaline phosphatase, β- d -xylosidase, β- d -cellobiohydrolase, N-acetyl-β- d -glucosaminidase, β-glucosidase, α-glucosidase, leucyl aminopeptidase, arginyl aminopeptidase, prolyl aminopeptidase, gingipain, and clostripain. Extracellular peptidase activities were detectable at depths shallower than 54.95mbsf, and alkaline phosphatase activity was detectable throughout the core, albeit against a relatively high activity in autoclaved sediments. β-glucosidase activities were detected above 30mbsf; however, activities of other glycosyl hydrolases (β-xylosidase, β-cellobiohydrolase, N-acetyl-β-glucosaminidase, and α-glucosidase) were generally indistinguishable from zero at all depths. These extracellular enzymes appear to be extremely stable: Among all enzymes, a median of 51.3% of enzyme activity was retained after autoclaving for an hour. We show that enzyme turnover times scale with the inverse of community metabolic rates, such that enzyme lifetimes in subsurface sediments, in which metabolic rates are very slow, are likely to be extraordinarily long. A back-of-the-envelope calculation suggests enzyme lifetimes are, at minimum, on the order of 230days, and may be substantially longer. These results lend empirical support to the hypothesis that a population of subsurface microbes persist by using extracellular enzymes to slowly metabolize old, highly degraded organic carbon.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Permafrost Active Layer Microbes From Ny Ålesund, Svalbard (79°N) Show Autotrophic and Heterotrophic Metabolisms With Diverse Carbon-Degrading Enzymes

The active layer of permafrost in Ny Ålesund, Svalbard (79°N) around the Bayelva River in the Leirhaugen glacier moraine is measured as a small net carbon sink at the brink of becoming a carbon source. In many permafrost-dominating ecosystems, microbes in the active layers have been shown to drive organic matter degradation and greenhouse gas production, creating positive feedback on climate change. However, the microbial metabolisms linking the environmental geochemical processes and the populations that perform them have not been fully characterized. In this paper, we present geochemical, enzymatic, and isotopic data paired with 10 Pseudomonas sp. cultures and metagenomic libraries of two active layer soil cores (BPF1 and BPF2) from Ny Ålesund, Svalbard, (79°N). Relative to BPF1, BPF2 had statistically higher C/N ratios (15 ± 1 for BPF1 vs. 29 ± 10 for BPF2; n = 30, p < 10 –5 ), statistically lower organic carbon (2% ± 0.6% for BPF1 vs. 1.6% ± 0.4% for BPF2, p < 0.02), statistically lower nitrogen (0.1% ± 0.03% for BPF1 vs. 0.07% ± 0.02% for BPF2, p < 10 –6 ). The d 13 C values for inorganic carbon did not correlate with those of organic carbon in BPF2, suggesting lower heterotrophic respiration. An increase in the δ 13 C of inorganic carbon with depth either reflects an autotrophic signal or mixing between a heterotrophic source at the surface and a lithotrophic source at depth. Potential enzyme activity of xylosidase and N-acetyl-β-D-glucosaminidase increases twofold at 15°C, relative to 25°C, indicating cold adaptation in the cultures and bulk soil. Potential enzyme activity of leucine aminopeptidase across soils and cultures was two orders of magnitude higher than other tested enzymes, implying that organisms use leucine as a nitrogen and carbon source in this nutrient-limited environment. Besides demonstrating large variability in carbon compositions of permafrost active layer soils only ∼84 m apart, results suggest that the Svalbard active layer microbes are often limited by organic carbon or nitrogen availability and have adaptations to the current environment, and metabolic flexibility to adapt to the warming climate.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2026

Origin of Electrochemical Activation Leading to Enhanced Cycling Stability of Li‐ and Mn‐Rich Cathodes

Electrochemical activation is a critical step for optimal functioning of Li- and Mn-rich (LMR) cathodes, yet the underlying mechanism for such activation remains elusive. Here, by using scanning/transmission electron microscopy (S/TEM) combined with the associated energy-dispersive x-ray spectroscopy (EDS) and electron energy-loss spectroscopy (EELS), we decipher the origin of the activation enhanced electrochemical properties. We reveal that activation induces the formation of a spinel-like phase within the C2/m domains of the LMR cathode, where the transition-metal ions partially occupy both the tetrahedral (8a) and octahedral (16c) sites of the $Fd\bar{3}m$ spinel lattice, distinguishing the spinel-like phase from the conventional high-voltage spinel. Systematic varying the cycling voltage reveals a critical activation voltage above which this spinel-like phase forms, while lower voltages preserve the layered bulk structure. As the spinel-like phase is a stable structure for electrochemical cycling, the present findings provide direct mechanistic insight into the voltage-dependent activation process and explain how the C2/m to spinel-like transformation upon activation contributes to the electrochemical performance of LMR cathodes, providing guidance for the rational design of Li-rich cathodes with enhanced cycling durability.

Li-rich and Mn-rich cathode↗
DOE OSTI2022

Hydrodynamically Controlled Self‐Organization in Mixtures of Active and Passive Colloids

Abstract Active particles are known to exhibit collective behavior and induce structure in a variety of soft‐matter systems. However, many naturally occurring complex fluids are mixtures of active and passive components. The authors examine how activity induces organization in such multi‐component systems. Mixtures of passive colloids and colloidal micromotors are investigated and it is observed that even a small fraction of active particles induces reorganization of the passive components in an intriguing series of phenomena. Experimental observations are combined with large‐scale simulations that explicitly resolve the near‐ and far‐field effects of the hydrodynamic flow and simultaneously accurately treat the fluid–colloid interfaces. It is demonstrated that neither conventional molecular dynamics simulations nor the reduction of hydrodynamic effects to phoretic attractions can explain the observed phenomena, which originate from the flow field that is generated by the active colloids and subsequently modified by the aggregating passive units. These findings not only offer insight into the organization of biological or synthetic active–passive mixtures, but also open avenues to controlling the behavior of passive building blocks by means of small amounts of active particles.

36 MATERIALS SCIENCE↗
DOE OSTI2019

The Effect of Persistent Heavy Metal Exposure on Some Antioxidant Enzyme Activities and Lipid Peroxidation of the Freshwater snail, Lymnaea natalensis

This study investigated the effect of persistent heavy metal exposure on the activity of superoxide dismutase (SOD), catalase (CAT) and glutathione peroxidase (GPx) of the freshwater snail, Lymnaea natalensis. Malondialdehyde (MDA) levels were also measured as an index of lipid peroxidation. The snails were exposed to cadmium, copper, lead and mercury for a total of 28 days at 0.1 mg/L, 0.1 mg/L, 0.2 mg/L and 0.1 mg/L respectively. Samples were collected at 1, 7, 14, 21 and 28 days intervals. Analysis of SOD showed significant initial increases in enzyme activity following exposure to copper, lead and mercury, while cadmium exposures caused increases from Day 14 onwards. Copper, cadmium and lead caused significant initial increases in CAT activity and mercury caused an increase only on Day 28. Copper caused a significant increase in GPx activity on Day 28 while MDA levels diminished significantly at Days 7–28. Similarly, cadmium caused significant increases of GPx activity on Day 28 whereas MDA levels were significantly reduced. Lead also caused a significant increase in GPx activity on Days 14–28 whilst no significant changes occurred in MDA levels. Mercury exposures caused significant increases in GPx activity on Days 7 and 21, whilst MDA levels were significantly reduced on Days 7 and 14. These findings suggest that persistent exposure of snails to heavy metals induces the antioxidant defence system, and decreases lipid peroxidation.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2018

Blood Pressure Changes After Exposures Increasing Angiotensin-Converting Enzyme Activity and After Its Normalization with Dihydroquercetin in Male Wistar Rats

Changes in BP and HR were assessed after exposures increasing activity of angiotensin-converting enzyme: ionizing radiation, NO synthase inhibitor (L-NAME), and dexamethasone. Effects of dihydroquercetin and angiotensin-converting enzyme inhibitor enalapril on activity of this enzyme, BP, and HR were also evaluated under these exposures. Wistar male rats were subjected to X-ray irradiation in a dose of 2.5 Gy. Angiotensin-converting enzyme activity in the aorta sections was determined by Hip-His-Leu hydrolysis. BP and HR were recorded using a non-invasive tail-cuff method and PowerLab 8/35 software. BP and HR were not altered with the increase in activity of angiotensin-converting enzyme after irradiation. In case of prolonged (7 days) treatment with NO synthase inhibitor and dexamethasone, the increase in enzyme activity was accompanied by elevation of BP and, in the case of NO synthase inhibitor, HR reduction. Dihydroquercetin normalized the enzyme activity and lowered BP, but not to the normal level. Enalapril normalized BP, increased by NO synthase inhibitor solution intake; at the same time, the angiotensinconverting enzyme activity decreased more than 2-fold in comparison with the normal.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2023

Study of cosmogenic activation above ground for the DarkSide-20k experiment

The activation of materials due to exposure to cosmic rays may become an important background source for experiments investigating rare event phenomena. DarkSide-20k, currently under construction at the Laboratori Nazionali del Gran Sasso, is a direct detection experiment for galactic dark matter particles, using a two-phase liquid-argon Time Projection Chamber (TPC) filled with 49.7 tonnes (active mass) of Underground Argon (UAr) depleted in 39 Ar. Despite the outstanding capability of discriminating γ / β background in argon TPCs, this background must be considered because of induced dead time or accidental coincidences mimicking dark-matter signals and it is relevant for low-threshold electron-counting measurements. Here, the cosmogenic activity of relevant long-lived radioisotopes induced in the experiment has been estimated to set requirements and procedures during preparation of the experiment and to check that it is not dominant over primordial radioactivity; particular attention has been paid to the activation of the 120 t of UAr used in DarkSide-20k. Expected exposures above ground and production rates, either measured or calculated, have been considered in detail. From the simulated counting rates in the detector due to cosmogenic isotopes, it is concluded that activation in copper and stainless steel is not problematic. The activity of 39 Ar induced during extraction, purification and transport on surface is evaluated to be 2.8% of the activity measured in UAr by DarkSide-50 experiment, which used the same underground source, and thus considered acceptable. Other isotopes in the UAr such as 37 Ar and 3 H are shown not to be relevant due to short half-life and assumed purification methods.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2016

Direct measurement of catalase activity in living cells and tissue biopsies

Spatiotemporal regulation of enzyme-substrate interactions governs the decision-making steps in biological systems. Enzymes, being functional units of every living cell, contribute to the macromolecular stability of cell survival, proliferation and hence are vital windows to unraveling the biological complexity. Experimental measurements capturing this dynamics of enzyme-substrate interactions in real time add value to this understanding. Furthermore these measurements, upon validation in realistic biological specimens such as clinical biopsies – can further improve our capability in disease diagnostics and treatment monitoring. Towards this direction, we describe here a novel, high-sensitive measurement system for measuring diffusion-limited enzyme-substrate kinetics in real time. Using catalase (enzyme) and hydrogen peroxide (substrate) as the example pair, we demonstrate that this system is capable of direct measurement of catalase activity in vitro and the measured kinetics follows the classical Michaelis-Menten reaction kinetics. We further demonstrate the system performance by measuring catalase activity in living cells and in very small amounts of liver biopsies (down to 1 μg total protein). Catalase-specific enzyme activity is demonstrated by genetic and pharmacological tools. Finally we show the clinically-relevant diagnostic capability of our system by comparing the catalase activities in liver biopsies from young and old mouse (liver and serum) samples. We discuss the potential applicability of this system in clinical diagnostics as well as in intraoperative surgical settings. - Highlights: • A novel, direct measurement of Catalase enzyme activity via, oxygen sensing method. • Steady-stateprofiles of Catalase activity follow the Michaelis-Menten Kinetics. • Catalase-specific activity demonstrated using genetic and pharmacological tools. • Overcomes limitations of spectroscopic methods and indirect calorimetric approaches. • Clear demonstration of the applicability in cancer cells and aging animal tissues.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2020

Linking low and high temperature NO oxidation mechanisms over Brønsted acidic chabazite to dynamic changes of the active site

The oxidation of NO over Brønsted acid sites in chabazite (CHA) zeolites shows an atypical temperature dependence; at low temperature the apparent activation energy is negative, but it becomes positive as the temperature exceeds a transition temperature. To explain this behavior we used density functional theory and statistical mechanics to investigate high and low temperature mechanisms for this reaction and propose a dynamic active site change in response to temperature variation. Our simulations show that the apparent activation barrier in the low temperature regime is more negative over Brønsted acidic CHA as compared to the siliceous zeolite framework. This effect is attributed to further enthalpic stabilization of the transition states by physical interaction with the H-CHA Brønsted acid sites. At elevated temperature, our calculations support both the existence and the significant catalytic role of NO+ in providing a modified active site. The temperature dependent transformation of the active site from H-CHA to NO-CHA sites may occur via two plausible ion-exchange mechanisms that define a transition temperature for the reaction. This transition temperature can be tuned by incorporating different trivalent metal atoms (B, Al, Ga or In) within the CHA framework. We found the lowest transition temperature for H-[In] CHA and H-[Ga]CHA. Here, the ability to control the dynamic response of the active site and the associated switch between low and high temperature mechanism with negative and positive apparent activation energy, respectively, is of fundamental interest for the design of zeolite catalysts operating in the presence of NO.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Probing surface-adsorbate interactions through active particle dynamics

Adsorbate molecules present in a reaction mixture may bind to and block catalytic sites. Measurement of the surface coverage of these molecules via adsorption isotherms is critical for modeling and design of catalytic reactions on surfaces. However, it is challenging to measure isotherms in solution in a way that is directly relevant to catalytic activity under reaction conditions, particularly since adsorbates may bind with an enormous range of surface affinity parameters. Here we used the motion of self-propelled catalytic Janus particles, which employ the decomposition of hydrogen peroxide fuel as a propulsion mechanism, to determine the effective surface coverage of thioglycerol, furfural, and ethanol on a platinum surface as a function of concentration in aqueous solution by measuring the decrease in active motion due to the blocking of active sites. For strongly adsorbing thioglycerol, this effective coverage was compared and contrasted to the total adsorbed amount measured using inductively-coupled plasma analysis. Demonstrating the broad applicability of this approach, the surface affinity of the three adsorbates spanned more than four orders of magnitude. For each species, the adsorbate-mediated attenuation of active motion occurred over a wide concentration range and was well-described by a Langmuir isotherm. The strongly interacting thioglycerol had the highest affinity towards the surface (K a = 15.5 ± 4.3 mM –1 ) and fully deactivated the active particle motion at surface saturation. Furfural had an intermediate affinity (K a = 0.42 ± 0.07 mM –1 ) but did not fully block H 2 O 2 access to the surface at apparent saturation, consistent with a maximum fractional surface coverage of θ max = 0.67. Ethanol exhibited even lower affinity (K a = 0.0025 ± 2x10 -4 mM –1 ) and its coverage saturated at only θ max = 0.38. Analysis of isotherms at elevated temperatures enabled direct extraction of the enthalpies of adsorption. The degree of surface coverage at adsorbate saturation appeared to correlate with the relative energies of adsorption for the different adsorbate species and was consistent with adsorbate saturation of one of multiple active site populations towards H 2 O 2 decomposition. Furthermore, computational investigations into solvent effects on furfural adsorption showed good quantitative agreement with the experimental results. This work leverages unique properties of active particles to explore fundamental catalysis questions and demonstrates a novel paradigm for significant and experimentally accessible multidisciplinary research.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Uncovering the Role of Sgf73 in Maintaining SAGA Deubiquitinating Module Structure and Activity

The SAGA (Spt-Ada-Gcn5-acetyltransferase) complex performs multiple functions in transcription activation including deubiquitinating histone H2B, which is mediated by a subcomplex called the deubiquitinating module (DUBm). The yeast DUBm comprises a catalytic subunit, Ubp8, and three additional subunits, Sgf11, Sus1 and Sgf73, all of which are required for DUBm activity. A portion of the non-globular Sgf73 subunit lies between the Ubp8 catalytic domain and the ZnF-UBP domain and has been proposed to contribute to deubiquitinating activity by maintaining the catalytic domain in an active conformation. We report structural and solution studies of the DUBm containing two different Sgf73 point mutations that disrupt deubiquitinating activity. We find that the Sgf73 mutations abrogate deubiquitinating activity by impacting the Ubp8 ubiquitin-binding fingers region and have an unexpected effect on the overall folding and stability of the DUBm complex. Finally, taken together, our data suggest a role for Sgf73 in maintaining both the organization and ubiquitin-binding conformation of Ubp8, thereby contributing to overall DUBm activity.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2014

Optically active substituted polyacetylene@carbon nanotube hybrids: Preparation, characterization and infrared emissivity property study

Optically active substituted polyacetylene@multiwalled carbon nanotubes (SPA@MWCNTs) nanohybrids were fabricated by wrapping helical SPA copolymers onto the surface of modified nanotubes through ester bonding linkage. SPA copolymer based on chiral phenylalanine and serine was pre-polymerized by a rhodium zwitterion catalyst in THF, and evidently proved to possess strong optical activity and adopt a predominately one-handed helical conformation. Various characterizations including Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and transmission electron microscopy (TEM) demonstrated that the SPA had been covalently grafted onto the nanotubes without destroying their original graphite structure. The wrapped SPA was found to exhibit an enhancement in thermal stability and still maintained considerable optical activity after grafting. The infrared emissivity property of the nanohybrids at 8–14 μm was investigated in addition. The results indicated that the SPA@MWCNTs hybrid matrix could possess a much lower infrared emissivity value (ε=0.707) than raw MWCNTs, which might be due to synergistic effect of the unique helical conformation of optically active SPA and strengthened interfacial interaction between the organic polymers and inorganic nanoparticles. - Graphical abstract: Optically active SPA@MWCNTs nanohybrids with low infrared emissivity. - Highlights: • Synthesis of optically active SPA copolymer derived from serine and phenylalanine. • Preparation and characterization of optically active SPA@MWCNTs nanohybrids. • Application study of the SPA@MWCNTs nanohybrids (ε=0.707) in lowering the infrared emissivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗