All Hazards Analysis (AHA)
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54 ENVIRONMENTAL SCIENCES↗
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Characterization and modification of enzymes in the 2-ketoisovalerate biosynthesis pathway of Ralstonia eutropha H16
2-Ketoisovalerate is an important cellular intermediate for the synthesis of branched-chain amino acids as well as other important molecules, such as pantothenate, coenzyme A, and glucosinolate. This ketoacid can also serve as a precursor molecule for the production of biofuels, pharmaceutical agents, and flavor agents in engineered organisms, such as the betaproteobacterium Ralstonia eutropha. The biosynthesis of 2-ketoisovalerate from pyruvate is carried out by three enzymes: acetohydroxyacid synthase (AHAS, encoded by ilvBH), acetohydroxyacid isomeroreductase (AHAIR, encoded by ilvC), and dihydroxyacid dehydratase (DHAD, encoded by ilvD). In this study, enzymatic activities and kinetic parameters were determined for each of the three R. eutropha enzymes as heterologously purified proteins. AHAS, which serves as a gatekeeper for the biosynthesis of all three branched-chain amino acids, demonstrated the tightest regulation through feedback inhibition by l-valine (IC50 = 1.2 mM), l-isoleucine (IC50 = 2.3 mM), and l-leucine (IC50 = 5.4 mM). Intermediates in the valine biosynthesis pathway also exhibit feedback inhibitory control of the AHAS enzyme. In addition, AHAS has a very weak affinity for pyruvate (K-M = 10.5 mu M) and is highly selective towards 2-ketobutyrate (R = 140) as a second substrate. AHAIR and DHAD are also inhibited by the branched-chain amino acids, although to a lesser extent when compared to AHAS. Experimental evolution and rational site-directed mutagenesis revealed mutants of the regulatory subunit of AHAS (IlvH) (N11S, T34I, A36V, T104S, N11F, G14E, and N29H), which, when reconstituted with wild-type IlvB, lead to AHAS having reduced valine, leucine, and isoleucine sensitivity. The study of the kinetics and inhibition mechanisms of R. eutropha AHAS, AHAIR, and DHAD has shed light on interactions between these enzymes and the products they produce; it, therefore, can be used to engineer R. eutropha strains with optimal production of 2-ketoisovalerate for value-added materials.
Lu, JN↗
Overview of reductants utilized in nuclear fuel reprocessing/recycling
Most of the aqueous processes developed, or under consideration worldwide for the recycling of used nuclear fuel (UNF) utilize the oxido-reduction properties of actinides to separate them from other radionuclides. Generally, after acid dissolution of the UNF, (essentially in nitric acid solution), actinides are separated from the raffinate by liquid-liquid extraction using specific solvents, associated along the process, with a particular reductant that will allow the separation to occur. For example, the industrial PUREX process utilizes hydroxylamine as a plutonium reductant. Hydroxylamine has numerous advantages: not only does it have the proper attributes to reduce Pu(IV) to Pu(III), but it is also a non-metallic chemical that is readily decomposed to innocuous products by heating. However, it has been observed that the presence of high nitric acid concentrations or impurities (such as metal ions) in hydroxylamine solutions increase the likelihood of the initiation of an autocatalytic reaction. Recently there has been some interest in the application of simple hydrophilic hydroxamic ligands such as acetohydroxamic acid (AHA) for the stripping of tetravalent actinides in the UREX process flowsheet. This approach is based on the high coordinating ability of hydroxamic acids with tetravalent actinides (Np and Pu) compared with hexavalent uranium. Thus, the use of AHA offers a route for controlling neptunium and plutonium in the UREX process by complexant based stripping of Np(IV) and Pu(IV) from the TBP solvent phase, while U(VI) ions are not affected by AHA and remain solvated in the TBP phase. In the European GANEX process, AHA is also used to form hydrophilic complexes with actinides and strip them from the organic phase into nitric acid. However, AHA does not decompose completely when treated with nitric acid and hampers nitric acid recycling. In lieu of using AHA in the UREX + process, formohydroxamic acid (FHA), although not commercially available, hold promises as a replacement for AHA. FHA undergoes hydrolysis to formic acid which is volatile, thus allowing the recycling of nitric acid. Unfortunately, FHA powder was not stable in the experiments we ran in our laboratory. In addition, AHA and FHA also decompose to hydroxylamine which may undergo an autocatalytic reaction. Other reductants are available and could be extremely useful for actinides separation. The review presents the current plutonium reductants used in used nuclear fuel reprocessing and will introduce innovative and novel reductants that could become reducers for future research on UNF separation.
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
Process and Material Design for Micro-Encapsulated Ionic Liquids in Post-Combustion CO 2 Capture
Aprotic Heterocyclic Anion (AHA) Ionic Liquids (ILs) have been identified as promising new solvents for post-combustion carbon capture due to their high CO 2 uptake and the high tenability 1,2 of their binding energy with CO 2 . Some of these compounds change phase (solid to liquid) on absorption of CO 2 ; these Phase Change ILs (PCILs)3 offer the additional advantage that part of the heat needed to desorb the CO2 from the absorbent is provided by the heat of fusion as the PCIL solidifies upon release of CO 2 . However, the relatively high viscosity of AHA ILs and the occurrence of a phase change in PCILs present challenges for conventional absorption equipment. To overcome these challenges we are pursuing the use of new technology to micro-encapsulate the AHA ILs and PCILs. Our partners at Lawrence Livermore National Laboratory have successfully demonstrated this technology in the application of post-combustion carbon capture with sodium and potassium carbonate solutions,4 and have recently shown the feasibility of micro-encapsulation of an AHA IL for carbon capture.5 The large effective surface area and high CO 2 permeability of the micro-capsules is expected to offset the drawback of the high IL viscosity and to provide for a more efficient and cost-effective mass transfer operation involving AHA ILs and PCILs. These opportunities, however, present us with both process and materials design questions. For example, what is the target CO 2 absorption strength (enthalpy of chemical absorption) for the tunable AHA IL? What is the target for micro-capsule diameter in order to obtain a high mass transfer rate and good fluidization performance? What are the appropriate temperatures and pressures for the absorber and stripper? In order to address these and other questions, we have developed a rate-based model of a post-combustion CO 2 capture process using micro-encapsulated ILs. As a performance baseline, we have also developed a rate-based model of a standard packed bed absorber using an un-encapsulated AHA IL absorbent. Using such models we can determine optimal CO 2 capture performance and investigate the sensitivity of the optimum with respect to the key thermo-physical and transport properties of the IL (e.g., CO 2 binding energy, viscosity, etc.) and the micro-capsules (e.g. diameter, CO 2 permeability, etc.). Results of these process and material design studies will be presented, and the performance of this novel micro-encapsulation technology will be assessed.
20 FOSSIL-FUELED POWER PLANTS↗
Physical Properties and CO2 Reaction Pathway of 1-Ethyl-3-Methylimidazolium Ionic Liquids with Aprotic Heterocyclic Anions
Ionic liquids (ILs) with aprotic heterocyclic anions (AHA) are attractive candidates for CO2 capture technologies. In this study, a series of AHA ILs with 1-ethyl-3-methylimidazolium ([emim](+)) cations were synthesized, and their physical properties (density, viscosity, and ionic conductivity) were measured. In addition, CO2 solubility in each IL was determined at room temperature using a volumetric method at pressures between 0 and 1 bar. The AHAs are basic anions that are capable of reacting stoichiometrically with CO2 to form carbamate species. An interesting CO2 uptake isotherm behavior was observed, and this may be attributed to a parallel, equilibrium proton exchange process between the imidazolium cation and the basic AHA in the presence of CO2, followed by the formation of "transient" carbene species that react rapidly with CO2. The presence of the imidazolium-carboxylate species and carbamate anion species was verified using H-1 and C-13 NMR spectroscopy. While the reaction between CO2 and the proposed transient carbene resulted in cation-CO2 binding that is stronger than the anion-CO2 reaction, the reactions of the imidazolium AHA ILs were fully reversible upon regeneration at 80 degrees C with nitrogen purging. The presence of water decreased the CO2 uptake due to the inhibiting effect of the neutral species (protonated form of AHA) that is formed.
Seo, S↗
Reduction of Plutonium(VI) to (V) by Hydroxamate Compounds at Environmentally Relevant pH
Natural organic matter is known to influence the mobility of plutonium (Pu) in the environment via complexation and reduction mechanisms. Hydroxamate siderophores have been specifically implicated due to their strong association with Pu. Hydroxamate siderophores can also break down into di and mono-hydroxamates and may influence Pu oxidation state, and thereby its mobility. In this study we explored the reactions of Pu(VI) and Pu(V) with a mono-hydroxamate compound (acetohydroxamic acid, AHA) and a tri-hydroxamate siderophore desferrioxamine B (DFOB) at environmentally relevant pH (5.5-8.2). Pu(VI) was instantaneously reduced to Pu(V) upon reaction with AHA. The presence of hydroxylamine was not observed at these pHs; however, AHA was consumed during the reaction. This suggests that the reduction of Pu(VI) to Pu(V) by AHA is facilitated by direct one electron transfer. Importantly, further reduction to Pu(IV) or Pu(III) was not observed, even with excess AHA. We believe that further reduction of Pu(V) did not occur because Pu(V) does not form a strong complex with hydroxamate compounds at circum-neutral pH. Experiments performed using desferrioxamine B (DFOB) yielded similar results. Broadly, this suggests that Pu(V) reduction to Pu(IV) in the presence of natural organic matter is not facilitated by hydroxamate functional groups and that other natural organic matter moieties likely play a more prominent role.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Unexpected dependence of the anomalous Hall angle on the Hall conductivity in amorphous transition metal thin films
The anomalous Hall effect (AHE), and magnetic and electronic transport properties were investigated in a series of amorphous transition metal thin films— Fe x S i –x , Fe x Ge 1-x , Co x Ge 1–x , Co x Si 1–x , and Fe 1–y Co y Si. The experimental results are compared with density functional theory calculations of the density of Berry curvature and intrinsic anomalous Hall conductivity. In all samples, the longitudinal conductivity (σ xx ), magnetization (M), and Hall resistivity (ρ xy ) increase with increasing transition metal concentration; due to the structural disorder σ xx is lower in all samples than a typical crystalline metal. In the systems with Fe as the transition metal (including Fe 1–y Co y Si), the magnetization and AHE are large and in some cases greater than the crystalline analog. In all samples, the AHE is dominated by the intrinsic mechanism, arising from a nonzero, locally derived Berry curvature. The anomalous Hall angle (AHA) (= σ xy /σ xx ) is as large as 5% at low temperature. These results are compared with the AHAs reported in a broad range of crystalline and amorphous materials. Previous work has shown that in a typical crystalline ferromagnet the Hall conductivity (σ xy ) and σ xx are correlated and are usually either both large or both small, resulting in an AHA that decreases with increasing σ xy . By contrast, the AHA increases linearly with increasing σ xy in the amorphous systems. This trend is attributed to a generally low σ xx , while σ xy varies and can be large. In the amorphous systems, σ xx and σ xy are not coupled, and there may thus exist the potential to further increase the AHA by increasing σ xy .
36 MATERIALS SCIENCE↗
Metronome Use for Coordination of Breaths and Cardiac Compressions Delivered by Minimally-Trained Caregivers During Two-Person CPR
Astronaut crew medical officers (CMO) aboard the International Space Station (ISS) receive 40 hours of medical training over 18 months before each mission, including two-person cardiopulmonary resuscitation (2CPR) as recommended by the American Heart Association (AHA). Recent studies have concluded that the use of metronomic tones improves the coordination of 2CPR by trained clinicians. 2CPR performance data for minimally-trained caregivers has been limited. The goal of this study was to determine whether use of a metronome by minimally-trained caregivers (CMO analogues) would improve 2CPR performance. 20 pairs of minimally-trained caregivers certified in 2CPR via AHA guidelines performed 2CPR for 4 minutes on an instrumented manikin using 3 interventions: 1) Standard 2CPR without a metronome [NONE], 2) Standard 2CPR plus a metronome for coordinating compression rate only [MET], 3) Standard 2CPR plus a metronome for coordinating both the compression rate and ventilation rate [BOTH]. Caregivers were evaluated for their ability to meet the AHA guideline of 32 breaths-240 compressions in 4 minutes. All (100%) caregivers using the BOTH intervention provided the required number of ventilation breaths as compared with the NONE caregivers (10%) and MET caregivers (0%). For compressions, 97.5% of the BOTH caregivers were not successful in meeting the AHA compression guideline; however, an average of 238 compressions of the desired 240 were completed. None of the caregivers were successful in meeting the compression guideline using the NONE and MET interventions. This study demonstrates that use of metronomic tones by minimally-trained caregivers for coordinating both compressions and breaths improves 2CPR performance. Meeting the breath guideline is important to minimize air entering the stomach, thus decreasing the likelihood of gastric aspiration. These results suggest that manifesting a metronome for the ISS may augment the performance of 2CPR on orbit and thus may increase the level of care.
Hurst, Victor, IV↗
Novel Aprotic Heterocyclic Anion-based Ionic Liquids for Carbon Dioxide Capture
Ionic liquids (ILs), or organic salts with melting points at or below room temperature are an incredibly versatile class of materials with many possible applications for NASA’s exploration needs. In particular, appropriately designed ILs can have a high affinity for absorbing carbon dioxide, making them excellent candidates for use as liquid sorbents in cabin air revitalization systems. Unfortunately, many of these ILs have high viscosity, which is only exacerbated by carbon dioxide uptake. High viscosity limits the rate of carbon dioxide uptake. A new class of IL sorbent containing aprotic heterocyclic anions (AHA) has been shown to offer excellent carbon dioxide uptake without a corresponding increase in viscosity. However, there is a paucity of sorption data for these AHA ILs at low partial pressures of carbon dioxide. This paper reports on the characterization of sorption behavior for AHA ILs previously reported in the literature at low concentrations of carbon dioxide and the synthesis and characterization of new, water miscible AHA ILs. Characterization of the new ILs includes measurement of density, viscosity, thermal stability, carbon dioxide capacity, carbon dioxide absorption kinetics, and water-IL vapor liquid equilibrium. Overall, these news ILs are promising alternatives to many of the commonly used IL sorbents.
Eric Townsend Fox↗
Visualizing a Vulnerability: Its Connections to Hardware and Software
All Hazards Analysis (AHA) is a framework developed by Idaho National Laboratory that provides capabilities to collect, store, analyze, and visualize critical infrastructure information. A core function of AHA is its ability to simulate faults or outages in networks of infrastructure originating from a plethora of causes, ranging from natural disasters to cyberattacks. AHA utilizes Hardware and Software Bills of Material (HBOM and SBOM, respectively) along with Known Exploited Vulnerabilities (KEVs) to document the potential attack vectors for each piece of infrastructure. The objective of this contribution to AHA was to create a visualization tool that could capture the small details held in each individual artifact as well as preserve the large-scale connections that link them together to aid threat modeling.
58 GEOSCIENCES↗
In situ visualization of newly synthesized proteins in environmental microbes using amino acid tagging and click chemistry
Summary Here we describe the application of a new click chemistry method for fluorescent tracking of protein synthesis in individual microorganisms within environmental samples. This technique, termed bioorthogonal non‐canonical amino acid tagging ( BONCAT ), is based on the in vivo incorporation of the non‐canonical amino acid L ‐azidohomoalanine ( AHA ), a surrogate for l ‐methionine, followed by fluorescent labelling of AHA ‐containing cellular proteins by azide‐alkyne click chemistry. BONCAT was evaluated with a range of phylogenetically and physiologically diverse archaeal and bacterial pure cultures and enrichments, and used to visualize translationally active cells within complex environmental samples including an oral biofilm, freshwater and anoxic sediment. We also developed combined assays that couple BONCAT with ribosomal RNA (rRNA)‐targeted fluorescence in situ hybridization ( FISH ), enabling a direct link between taxonomic identity and translational activity. Using a methanotrophic enrichment culture incubated under different conditions, we demonstrate the potential of BONCAT‐FISH to study microbial physiology in situ . A direct comparison of anabolic activity using BONCAT and stable isotope labelling by nano‐scale secondary ion mass spectrometry ( 15 NH 3 assimilation) for individual cells within a sediment‐sourced enrichment culture showed concordance between AHA ‐positive cells and 15 N enrichment. BONCAT‐FISH offers a fast, inexpensive and straightforward fluorescence microscopy method for studying the in situ activity of environmental microbes on a single‐cell level.
59 BASIC BIOLOGICAL SCIENCES↗
A Functional All-Hazard Approach to Critical Infrastructure Dependency Analysis
The critical infrastructures protection landscape is a vast and varied pattern of independent, but interconnected infrastructure systems that are essential to the function of our modern society. The U.S. policy on critical infrastructure protection has been continually evolving since the “President’s Commission on Critical Infrastructure Protection” was published in 1997. In response to these policies, federal, state, and local governments, along with research institutions, have invested a substantial amount of time and effort into identifying and analyzing critical infrastructure, their functions, and dependencies/interdependencies to better understand their vulnerabilities. To date, the ability to assess vulnerabilities, resiliency, and priorities for protecting interdependent critical infrastructure systems from an all-hazards perspective remains a difficult problem. In this paper we introduce the All-Hazards Analysis (AHA) methodology, which provides an integrated functional basis across infrastructure systems, through the implementation of a common language and a scalable level of decomposition to effectively evaluate the resilience of interconnected infrastructure systems. AHA models infrastructure systems as directed multidimensional graphs, which enable the evaluation of cross-sector interdependencies prior to, during, and after disruptive events. Finally, and by design, AHA enables the cross linking of data taxonomies to enable more effective data sharing, such as the National Critical Functions (NCF) and Infrastructure Data Taxonomy (IDT).
02 PETROLEUM↗
Synthesis of hexavalent molybdenum formo- and aceto-hydroxamates and deferoxamine via liquid-liquid metal partitioning
Not Available
Breshears, Andrew T.↗
All Hazards Analysis Core
The All Hazards Knowledge Framework (AHA) is a dynamic analytical framework that enables critical infrastructure knowledge discovery and decision support across the five mission areas – prevention, protection, mitigation, response and recovery. AHA provides the ability to store and model infrastructure systems as a linked multigraphs providing an intuitive and natural representation. This capability provides the foundation to rapidly evaluate and understand the potential consequences of manmade and natural disaster on these systems.
McGillivary, KentE.↗
Evidence for the involvement of carbonic anhydrase and urease in calcium carbonate formation in the gravity-sensing organ of Aplysia californica
To better understand the mechanisms that could modulate the formation of otoconia, calcium carbonate granules in the inner ear of vertebrate species, we examined statoconia formation in the gravity-sensing organ, the statocyst, of the gastropod mollusk Aplysia californica using an in vitro organ culture model. We determined the type of calcium carbonate present in the statoconia and investigated the role of carbonic anhydrase (CA) and urease in regulating statocyst pH as well as the role of protein synthesis and urease in statoconia production and homeostasis in vitro. The type of mineral present in statoconia was found to be aragonitic calcium carbonate. When the CA inhibitor, acetazolamide (AZ), was added to cultures of statocysts, the pH initially (30 min) increased and then decreased. The urease inhibitor, acetohydroxamic acid (AHA), decreased statocyst pH. Simultaneous addition of AZ and AHA caused a decrease in pH. Inhibition of urease activity also reduced total statoconia number, but had no effect on statoconia volume. Inhibition of protein synthesis reduced statoconia production and increased statoconia volume. In a previous study, inhibition of CA was shown to decrease statoconia production. Taken together, these data show that urease and CA play a role in regulating statocyst pH and the formation and maintenance of statoconia. CA produces carbonate ion for calcium carbonate formation and urease neutralizes the acid formed due to CA action, by production of ammonia.
Non-NASA Center↗
Comparison of Bystander Cardiopulmonary Resuscitation (BCPR) Performance in the Absence and Presence of Timing Devices for Coordinating Delivery of Ventilatory Breaths and Cardiac Compressions in a Model of Adult Cardiopulmonary Arrest
Astronaut crew medical officers (CMO) aboard the International Space Station (ISS) receive 40 hours of medical training during the 18 months preceding each mission. Part of this training ilncludes twoperson cardiopulmonary resuscitation (CPR) per training guidelines from the American Heart Association (AHA). Recent studies concluded that the use of metronomic tones improves the coordination of CPR by trained clinicians. Similar data for bystander or "trained lay people" (e.g. CMO) performance of CPR (BCPR) have been limited. The purpose of this study was to evailuate whether use of timing devices, such as audible metronomic tones, would improve BCPR perfomance by trained bystanders. Twenty pairs of bystanders trained in two-person BCPR performled BCPR for 4 minutes on a simulated cardiopulmonary arrest patient using three interventions: 1) BCPR with no timing devices, 2) BCPR plus metronomic tones for coordinating compression rate only, 3) BCPR with a timing device and metronome for coordinating ventilation and compression rates, respectively. Bystanders were evaluated on their ability to meet international and AHA CPR guidelines. Bystanders failed to provide the recommended number of breaths and number of compressions in the absence of a timing device and in the presence of audible metronomic tones for only coordinating compression rate. Bystanders using timing devices to coordinate both components of BCPR provided the reco number of breaths and were closer to providing the recommended number of compressions compared with the other interventions. Survey results indicated that bystanders preferred to use a metronome for delivery of compressions during BCPR. BCPR performance is improved by timing devices that coordinate both compressions and breaths.
Hurst, Victor, IV↗
Overview of reductants utilized in nuclear fuel reprocessing/recycling
The most widely used reductant to partition plutonium from uranium in the Purex process was ferrous sulfamate, other alternates were proposed such as hydrazine-stabilized ferrous nitrate or uranous nitrate, platinum catalyzed hydrogen, and hydrazine, hydroxylamine salts. New candidates to replace hydrazine or hydroxylamine nitrate (HAN) are pursued worldwide. They may improve the performance of the industrial Purex process towards different operations such as de-extraction of plutonium and reduction of the amount of hydrazine which will limit the formation of hydrazoic acid. When looking at future recycling technologies using hydroxamic ligands, neither acetohydroxamic acid (AHA) nor formohydroxamic acid (FHA) seem promising because they hydrolyze to give hydroxylamine and the parent carboxylic acid. Hydroxyethylhydrazine, HOC{sub 2}H{sub 4}N{sub 2}H{sub 3} (HEH) is a promising non-salt-forming reductant of Np and Pu ions because it is selective to neptunium and plutonium ions at room temperature and at relatively low acidity, it could serve as a replacement of HAN or AHA for the development of a novel used nuclear fuel recycling process.
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
User-Centered Software Design in the All Hazards Analysis Application
To design good software, you must always keep the end user in mind. Some benefits of incorporating the user-centered design process include saving users time and effort and helping them to utilize all capabilites of an application. In my work on the All Hazards Analysis (AHA) application, I employed principles of user-centered design to make the application easier for new users to navigate. This poster describes user-centered software design in general and showcases some of my user-centered design work on the AHA application.
58 GEOSCIENCES↗