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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 55 records · Page 3

The 3-(bromoacetamido)-propylamine hydrochloride: A novel sulfhydryl reagent and its future potential in the configurational study of S1-myosin

Configurational study of S1-Myosin is an important step towards understanding force generation in muscle contraction. Previously reported NMR studies were corroborated. A new compound was synthesized, 3-(Bromoacetamido)-propylamine hydrochloride. Its potential as a sulfhydryl reagent provides an indirect but elegant approach towards future structural elucidation of S1-Myosin. The preliminary investigation has shown that this compound, BAAP, reacted with S1 in the absence of MgADP. The modified enzyme had a 2-fold increase in CaATPase activity and no detectable K-EDTA ATPase activity. Reaction of BAAP with S1 in the presence of MgADP resulted in a modified enzyme which retained a Ca-ATPase activity that was about 60 percent of the unmodified S1 and had essentially zero K-EDTA ATPase activity. Sulfhydryl titration indicated that about 1.5 and 3.5 SH groups per S1 molecule were blocked by BAAP in the absence and presence of MgADP, respectively. When coupled to a carboxyl group of EDTA, the resulting reagent could become a useful SH reagent in which chelated paramagnetic or luminescent lanthanide ions can be exploited to probe S1 conformation.

Sharma, Prasanta↗

Hydrothermal liquefaction of sewage sludge – effect of four reagents on relevant parameters related to biocrude and $\mathrm{PFAS}$

Catalytic hydrothermal liquefaction (HTL) can convert wet biomass into crude-like oil and has potential to degrade pollutants during the thermal depolymerization process. To avoid negative environmental impacts from per- and polyfluoroalkyl substances (PFAS) in sewage sludge after its final disposal, we comprehensively evaluated catalytic destruction of PFAS in sludge through HTL. Here the results showed that adding red mud to HTL was beneficial for the biocrude yield and significantly increased the carbon conversion efficiency and energy recovery of the hydrothermal process. HTL at 300 °C for 2 h degraded > 96% of spiked perfluorooctanoic acid (PFOA). The mass of spiked perfluorobutanesulfonic acid (PFBS) and perfluorooctanesulfonic acid (PFOS) and pre-existing perfluorohexanoic acid (PFHxA) and perfluoroheptanoic acid (PFHpA), however, increased in the HTL product streams. The remaining PFAS after HTL mainly stayed in the biocrude phase. Our findings indicated that HTL under the studied condition was not able to degrade all PFAS existed in sewage sludge. Although adding red mud could improve the HTL performance with respect to biocrude, this reagent did not improve the removal of perfluoroalkyl acids (PFAAs). As a matter of fact, the hydrothermal process amended with the selected reagents resulted in increased mass of PFBS, PFHxA, and PFHpA in the HTL products due to degradation of PFAA precursors. Thus, other treatment approaches for PFAS removal from sewage sludge need to be identified to prevent possible contamination of environments receiving PFAS-containing sludge.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Amino acids in the Tagish Lake Meteorite

High-performance liquid chromatography (HPLC) based amino acid analysis of a Tagish Lake meteorite sample recovered 3 months after the meteorite fell to Earth have revealed that the amino acid composition of Tagish Lake is strikingly different from that of the CM and CI carbonaceous chondrites. We found that the Tagish Lake meteorite contains only trace levels of amino acids (total abundance = 880 ppb), which is much lower than the total abundance of amino acids in the CI Orgueil (4100 ppb) and the CM Murchison (16 900 ppb). Because most of the same amino acids found in the Tagish Lake meteorite are also present in the Tagish Lake ice melt water, we conclude that the amino acids detected in the meteorite are terrestrial contamination. We found that the exposure of a sample of Murchison to cold water lead to a substantial reduction over a period of several weeks in the amount of amino acids that are not strongly bound to the meteorite matrix. However, strongly bound amino acids that are extracted by direct HCl hydrolysis are not affected by the leaching process. Thus even if there had been leaching of amino acids from our Tagish Lake meteorite sample during its 3 month residence in Tagish Lake ice and melt water, a Murchison type abundance of endogenous amino acids in the meteorite would have still been readily detectable. The low amino acid content of Tagish Lake indicates that this meteorite originated fiom a different type of parent body than the CM and CI chondrites. The parent body was apparently devoid of the reagents such as aldehyldes/ketones, HCN and ammonia needed for the effective abiotic synthesis of amino acids. Based on reflectance spectral measurements, Tagish Lake has been associated with P- or D-type asteroids. If the Tagish Lake meteorite was indeed derived fiom these types of parent bodies, our understanding of these primitive asteroids needs to be reevaluated with respect to their potential inventory of biologically important organic compounds.

Kminek, G.↗

An improved method for analysis of hydroxide and carbonate in alkaline electrolytes containing zinc

A simplified method for titration of carbonate and hydroxide in alkaline battery electrolyte is presented involving a saturated KSCN solution as a complexing agent for zinc. Both hydroxide and carbonate can be determined in one titration, and the complexing reagent is readily prepared. Since the pH at the end point is shifted from 8.3 to 7.9 - 8.0, m-cresol purple or phenol red are used as indicators rather than phenolphthalein. Bromcresol green is recommended for determination of the second end point of a pH of 4.3 to 4.4.

Reid, M. A.↗

An improved method for analysis of hydroxide and carbonate in alkaline electrolytes containing zinc

A simplified method for titration of carbonate and hydroxide in alkaline battery electrolyte is presented involving a saturated KSCN solution as a complexing agent for zinc. Both hydroxide and carbonate can be determined in one titration, and the complexing reagent is readily prepared. Since the pH at the end point is shifted from 8.3 to 7.9-8.0, m-cresol purple or phenol red are used as indicators rather than phenolphthalein. Bromcresol green is recommended for determination of the second end point of a pH of 4.3 to 4.4.

Reid, M. A.↗

Energy Requirements of Hydrogen-Utilizing Microbes: Boundary Condition for Subsurface Life

For planetary bodies with surface conditions that are too harsh to permit continuous occupation by life, the deep subsurface offers a potentially stable and habitable niche. For organisms occupying this niche, the spectrum of possible metabolisms must be limited to those which do not include sunlight as an energy source or oxygen as a chemical reagent - generally, low-energy anaerobic oxidation-reduction processes. The quantity of energy released in such processes is critical, because currently understood mechanisms of biological energy conservation indicate that energy is only 'useful' to an organism when it is available at a certain minimum level - the 'biological energy quantum'. The mere existence of a BEQ implies that a significant fraction of the chemical energy present in the environment cannot be exploited by life; similarly, the absolute magnitude of the BEQ must be a key variable in determining the potential viability and distribution of subsurface microbial communities. Laboratory culture studies suggest that organisms require an energy of about -20 kJ/mol to grow. However, we find that hydrogen-utilizing microorganisms in an energy-limited natural ecosystem are active with energy yields as low as -10 kJ/mol. A lower BEQ would mean a significantly expanded range of energetically viable subsurface habitat for life.

Hoehler, Tori M.↗

Dual ion beam deposition of carbon films with diamondlike properties

A single and dual ion beam system was used to generate amorphous carbon films with diamond like properties. A methane/argon mixture at a molar ratio of 0.28 was ionized in the low pressure discharge chamber of a 30-cm-diameter ion source. A second ion source, 8 cm in diameter was used to direct a beam of 600 eV Argon ions on the substrates (fused silica or silicon) while the deposition from the 30-cm ion source was taking place. Nuclear reaction and combustion analysis indicate H/C ratios for the films to be 1.00. This high value of H/C, it is felt, allowed the films to have good transmittance. The films were impervious to reagents which dissolve graphitic and polymeric carbon structures. Although the measured density of the films was approximately 1.8 gm/cu cm, a value lower than diamond, the films exhibited other properties that were relatively close to diamond. These films were compared with diamondlike films generated by sputtering a graphite target.

Mirtich, M. J.↗

Dual-ion-beam deposition of carbon films with diamond-like properties

A single and dual ion beam system was used to generate amorphous carbon films with diamond like properties. A methane/argon mixture at a molar ratio of 0.28 was ionized in the low pressure discharge chamber of a 30-cm-diameter ion source. A second ion source, 8 cm in diameter was used to direct a beam of 600 eV Argon ions on the substrates (fused silica or silicon) while the deposition from the 30-cm ion source was taking place. Nuclear reaction and combustion analysis indicate H/C ratios for the films to be 1.00. This high value of H/C, it is felt, allowed the films to have good transmittance. The films were impervious to reagents which dissolve graphitic and polymeric carbon structures. Although the measured density of the films was approximately 1.8 gm/cu cm, a value lower than diamond, the films exhibited other properties that were relatively close to diamond. These films were compared with diamond like films generated by sputtering a graphite target.

Mirtich, M. J.↗

Reprocessable and Recyclable Polymer Network Electrolytes via Incorporation of Dynamic Covalent Bonds

Mechanically durable polymer network electrolytes are desirable for batteries; however, covalent cross-linking adversely affects their large-scale manufacturing, and they are difficult to recycle post-lifespan. In this work, we address the electrolyte reprocessability and recyclability challenges through the use of dynamic covalent bonds for polymer network solid electrolytes. Specifically, the associative dynamic vinylogous urethane motif is incorporated into a poly(ethylene oxide) network electrolyte containing lithium bis(fluorosulfonyl)imide (LiFSI) salt. The resulting dynamic covalent network electrolyte possesses a modest ion conductivity (~10–5 S/cm at room temperature) and good reprocessability. Stress–relaxation studies indicate that the LiFSI salt can catalyze the bond exchange and enhance the network dynamics. Furthermore, the reprocessability associated with bond exchange can be tuned by simply adjusting the formulation of reagent compositions, in which increasing the amount of excess amine or using a shorter chain of PEO prepolymer can further enhance the network dynamics and corresponding reprocessability.

25 ENERGY STORAGE↗

Nanotube Dispersions Made With Charged Surfactant

Dispersions (including monodispersions) of nanotubes in water at relatively high concentrations have been formulated as prototypes of reagents for use in making fibers, films, and membranes based on single-walled carbon nanotubes (SWNTs). Other than water, the ingredients of a dispersion of this type include one or more charged surfactant(s) and carbon nanotubes derived from the HiPco(TradeMark) (or equivalent) process. Among reagents known to be made from HiPco(TradeMark)(or equivalent) SWNTs, these are the most concentrated and are expected to be usable in processing of bulk structures and materials. Test data indicate that small bundles of SWNTs and single SWNTs at concentrations up to 1.1 weight percent have been present in water plus surfactant. This development is expected to contribute to the growth of an industry based on applied carbon nanotechnology. There are expected to be commercial applications in aerospace, avionics, sporting goods, automotive products, biotechnology, and medicine.

Kuper, Cynthia↗

Insights into Chemical Prelithiation of SiO x /Graphite Composite Anodes through Scanning Electron Microscope Imaging

Initial Coulombic efficiency (ICE) is critical for determining the energy density of lithium-ion batteries (LIBs) used for practical applications; however, it is typically disregarded in anode research. We used SiO x and graphite composite anodes for commercial lithium-ion batteries in our preliminary research to achieve a balance between ICE, capacity, and cycling life. ICE reached 88%; however, it needs further improvement for commercial applications. Prelithiation is a process that involves the introduction of extra lithium ions into LIBs during their manufacturing to enhance the overall performance of the LIBs. We applied a chemical prelithiation method on our SiO x /graphite composite anodes, which comprised 95 wt % of the active material mass loading on the electrode. The ICE increased from 88% to 98% using an aryllithium reagent impregnation method within 2 min of prelithiation. The anode’s specific capacity density, rate, and cycle performance also significantly improved. Scanning electron microscopy (SEM) imaging enhanced by an osmium tetroxide staining method indicated that the P-anode contained a stable solid electrolyte interface (SEI) layer after the prelithiation process and cycling electrochemical test. The P-anode’s stable charge differential peak over 500 cycles also showcases a robust artificial SEI layer that was generated by the prelithiation procedure. Here, this prelithiation process has significant potential for adoption in the LIB industry’s current electrode manufacturing process.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Some aspects of using ultrasounds to improve sulfurous mineral flotation technology

The results are discussed which were obtained with a new method of desorption of collector reagents connected with improving the selectivity of the flotation of copper and lead concentrate through the action of ultrasounds. Analysis of the results obtained by treating copper and lead concentrate in an ultraacoustic field indicates an increase in the copper content of the copper concentrate, of the lead content in the lead concentrate and, at the same time, a reduction in the lead of the copper concentrate.

Mihu, V. P.↗

Nanoparticle O–H Bond Dissociation Free Energies from Equilibrium Measurements of Cerium Oxide Colloids

A novel equilibrium strategy for measuring the hydrogen atom affinity of colloidal metal oxide nanoparticles is presented. Reactions between oleate-capped cerium oxide nanoparticle colloids (nanoceria) and organic proton-coupled electron transfer (PCET) reagents are used as a model system. Nanoceria redox changes, or hydrogen loadings, and overall reaction stoichiometries were followed by both 1 H NMR and X-ray absorption near-edge spectroscopies. Furthermore, these investigations revealed that, in many cases, reactions between nanoceria and PCET reagents reach equilibrium states with good mass balance. Each equilibrium state is a direct measure of the bond strength, or bond dissociation free energy (BDFE), between nanoceria and hydrogen. Further studies, including those with larger nanoceria, indicated that the relevant bond is a surface O–H. Thus, we have measured surface O–H BDFEs for nanoceria—the first experimental BDFEs for any nanoscale metal oxide. Remarkably, the measured CeO–H BDFEs span 13 kcal mol –1 (0.56 eV) with changes in the average redox state of the nanoceria colloid. Possible chemical models for this strong dependence are discussed. We propose that the tunability of ceria BDFEs may be important in explaining its effectiveness in catalysis. More generally, metal oxide BDFEs have been used as predictors of catalyst efficacy that, traditionally, have only been accessible by computational methods. These results provide important experimental benchmarks for metal oxide BDFEs and demonstrate that the concepts of molecular bond strength thermochemistry can be applied to nanoscale materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Foliar elemental distribution in Blepharidium guatemalense assessed by synchrotron X-ray fluorescence spectroscopy and colorimetric optical microscopy

The hyperaccumulation phenomenon holds significant potential for Ni agromining in ultramafic areas; however, data on tropical hyperaccumulator species, particularly regarding metal distribution and tolerance mechanisms, remain scarce. Here, this study characterized the foliar elemental distribution of Blepharidium guatemalense, analyzed its metal localization at both tissue and cellular levels, and quantified its Ni accumulation when grown in Brazilian ultramafic soil. Plants were grown in pots for 90 days, and Ni concentrations in the aerial biomass and bio-ore were determined. Synchrotron-based micro-X-ray fluorescence (S-µXRF) was used to assess metal distribution in tissues, supplemented by microscopic examination with dimethylglyoxime (DMG) to visualize Ni accumulation in specific cell types. B. guatemalense reached 19,000 mg kg −1 Ni in leaves. Processing leaf biomass produced ash containing 24 wt% Ni, indicating promising metal-recovery potential for the species. S-µXRF revealed that Ni was predominantly localized in the central and secondary veins of the leaves, suggesting efficient vascular transport. Microscopic analysis using the colorimetric reagent DMG further showed that Ni accumulation occurs near the epidermis and phloem, suggesting that B. guatemalense employs specific physiological mechanisms for Ni translocation, potentially supporting both defense and growth functions. These results establish B. guatemalense as a promising candidate for large-scale Ni agromining in tropical regions.

36 MATERIALS SCIENCE↗

Lignin Derived Ionic Liquids: Synthesis and Application for Biopolymer Processing (CRADA Final Report)

We have established a scalable and economically viable process to convert lignin into ionic liquids for use in biopolymer processing. We have studied the four main topics: 1) lignin depolymerization to produce vanillin through oxidation, 2) lignin reduction to produce guaiacols, 3) oxidation process scale up, and 4) ionic liquid synthesis and application for biopolymer processing. The main accomplishment is summarized below: A maximal vanillin yield of 4.9% (8.8% total product yield) was achieved under optimal oxidation conditions using design of experiments (DOE); Aminophenol with 94.5% purity was synthesized via reductive amination using vanillin isolated from ion-exchange chromatography; At a higher lignin loading (10%), the vanillin yield in the scale up reaction was lower than the bench scale reaction; The filtration-based downstream separation of the scale-up process was able to recover 76% of vanillin; A maximal lignin reduction product (guaiacols) yield of 6.5% was achieved in the presence of Ru/C, formic acid, and methanol; The lignin reduction product yield and composition were affected by the use of different solvent and catalytic reagents (methanol in combination of Ru/C and formic acid gives the highest product yield); Lignin oxidation and reduction products: vanillin, acetovanillone, guaiacols, and eugenol are successfully used for IL synthesis; XX based ILs showed cellulose solubility with up to xx%; Technoeconomic analysis results indicate the potential of producing affordable ILs from kraft lignin (MSP: $14/kg); Life-cycle assessment results show the potential to reduce GHG emissions by up to 85% relative to existing ILs ([Ch][Lys]) with GHG emission: 1.2 kg CO 2e /kg of IL produced.

09 BIOMASS FUELS↗

BioSentinel: Mission Development of a Radiation Biosensor to Gauge DNA Damage and Repair Beyond Low Earth Orbit on a 6U Nanosatellite.

We are designing and developing a "6U" (10 x 22 x 34 cm; 14 kg) nanosatellite as a secondary payload to fly aboard NASA's Space Launch System (SLS) Exploration Mission (EM) 1, scheduled for launch in late 2017. For the first time in over forty years, direct experimental data from biological studies beyond low Earth orbit (LEO) will be obtained during BioSentinel's 12- to 18- month mission. BioSentinel will measure the damage and repair of DNA in a biological organism and allow us to compare that to information from onboard physical radiation sensors. In order to understand the relative contributions of the space environment's two dominant biological perturbations, reduced gravity and ionizing radiation, results from deep space will be directly compared to data obtained in LEO (on ISS) and on Earth. These data points will be available for validation of existing biological radiation damage and repair models, and for extrapolation to humans, to assist in mitigating risks during future long-term exploration missions beyond LEO. The BioSentinel Payload occupies 4U of the spacecraft and will utilize the monocellular eukaryotic organism Saccharomyces cerevisiae (yeast) to report DNA double-strand-break (DSB) events that result from ambient space radiation. DSB repair exhibits striking conservation of repair proteins from yeast to humans. Yeast was selected because of 1) its similarity to cells in higher organisms, 2) the well-established history of strains engineered to measure DSB repair, 3) its spaceflight heritage, and 4) the wealth of available ground and flight reference data. The S. cerevisiae flight strain will include engineered genetic defects to prevent growth and division until a radiation-induced DSB activates the yeast's DNA repair mechanisms. The triggered culture growth and metabolic activity directly indicate a DSB and its successful repair. The yeast will be carried in the dry state within the 1-atm P/L container in 18 separate fluidics cards with each card having 16 independent culture microwells, with integral microchannels and filters to supply nutrients and reagents, confine the yeast to the wells, and enable optical measurement. The measurement subsystem will monitor each subgroup of culture wells continuously for several weeks, optically tracking DSBtriggered cell growth and metabolism. BioSentinel will also include physical radiation sensors based on the TimePix sensor, as implemented by JSC's RadWorks group, which record individual radiation events including estimates of their linear-energytransfer (LET) values. Radiation-dose and LET data will be compared directly to the rate of DSB-and-repair events measured by the S. cerevisiae biosentinels. The spacecraft bus will operate in a deep space environment with functions that include command and data handling, communications, power generation (via deployable solar panels) and storage, and attitude determination-and-control system with micropropulsion. Development of the BioSentinel spacecraft will mature and prove multiple nanosatellite advances in order to function well beyond LEO: Communications from distances of ≥ 500,000 km; Autonomous attitude control, momentum management, and safe mode of nanosatellites in deep space; Shielding-, hardening-, design-, and software-derived radiation tolerance for electronics; Reliable functionality for 12 - 18 months of key subsystems for biofluidics, memory, communications, power, etc.; Close integration of living biological radiation event monitors with miniature physical radiation spectrometers; Biological measurement of solar particle events beyond Earth orbit In addition to providing the first biological results from beyond LEO in over 4 decades, BioSentinel will provide an adaptable small-satellite instrument platform to perform a range of human-exploration-relevant measurements that characterize the biological consequences of multiple outer space environments. BioSentinel is being developed under NASA's Advanced Exploration Systems program.

DNA damage↗

BioSentinel: Mission Development of a Radiation Biosensor to Gauge DNA Damage and Repair Beyond Low Earth Orbit on a 6U Nanosatellite

We are designing and developing a 6U (10 x 22 x 34 cm; 14 kg) nanosatellite as a secondary payload to fly aboard NASAs Space Launch System (SLS) Exploration Mission (EM) 1, scheduled for launch in late 2017. For the first time in over forty years, direct experimental data from biological studies beyond low Earth orbit (LEO) will be obtained during BioSentinels 12- to 18-month mission. BioSentinel will measure the damage and repair of DNA in a biological organism and allow us to compare that to information from onboard physical radiation sensors. In order to understand the relative contributions of the space environments two dominant biological perturbations, reduced gravity and ionizing radiation, results from deep space will be directly compared to data obtained in LEO (on ISS) and on Earth. These data points will be available for validation of existing biological radiation damage and repair models, and for extrapolation to humans, to assist in mitigating risks during future long-term exploration missions beyond LEO. The BioSentinel Payload occupies 4U of the spacecraft and will utilize the monocellular eukaryotic organism Saccharomyces cerevisiae (yeast) to report DNA double-strand-break (DSB) events that result from ambient space radiation. DSB repair exhibits striking conservation of repair proteins from yeast to humans. Yeast was selected because of 1) its similarity to cells in higher organisms, 2) the well-established history of strains engineered to measure DSB repair, 3) its spaceflight heritage, and 4) the wealth of available ground and flight reference data. The S. cerevisiae flight strain will include engineered genetic defects to prevent growth and division until a radiation-induced DSB activates the yeasts DNA repair mechanisms. The triggered culture growth and metabolic activity directly indicate a DSB and its successful repair. The yeast will be carried in the dry state within the 1-atm PL container in 18 separate fluidics cards with each card having 16 independent culture microwells, with integral microchannels and filters to supply nutrients and reagents, confine the yeast to the wells, and enable optical measurement. The measurement subsystem will monitor each subgroup of culture wells continuously for several weeks, optically tracking DSB-triggered cell growth and metabolism. BioSentinel will also include physical radiation sensors based on the TimePix sensor, as implemented by JSCs RadWorks group, which record individual radiation events including estimates of their linear-energy-transfer (LET) values. Radiation-dose and LET data will be compared directly to the rate of DSB-and-repair events measured by the S. cerevisiae biosentinels.

Radiation Biosensor↗