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At least 1,603 records · Page 89

A convenient way of activating carbon quantum dots and the efficient isolation

Highlights: • Chemical tuning with N-hydroxysuccinimide on carbon quantum dots (CQDs) was realized. • N-hydroxysuccinimide-modified CQDs were isolated eifficiently from the mixtures. • The modified CQDs could be bonded with BSA for the fluorescent labeling. - Abstract: Photoluminescence of carbon quantum dots (CQDs) attracts extensive interests. Chemical modifications in a proper way on CQDs are vital for their applications. However, isolating the modified CQDs efficiently from the mixture is still a challenge. Conventional dialysis isolation did not effect at all since the unremarkable changes in size of the modified CQDs. Herein active N-hydroxysuccinimide (NHS) ester was introduced chemically onto the CQDs in very mild conditions, which was demonstrated by IR and X-ray photoelectron spectra. Such activated CQDs could be extracted by ethyl acetate from the mixture efficiently and conveniently which was confirmed by photoluminescence spectra. Experimental results also demonstrated the low cytotoxicity and the high stability against photo-bleaching of the CQDs-NHS. The high reactivity of NHS moiety was demonstrated by the reaction with bovine serum albumin, which revealed in an experiment of sodium dodecyl sulfate polyacrylamide gel electropheresis and the fluorescence imaging.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Stimulated backscatter of laser light from BigFoot hohlraums on the National Ignition Facility

The high implosion velocity, high adiabat BigFoot design [Casey et al. , Phys. Plasmas 25 , 056308 (2018)] has produced the highest neutron yield to date in an ignition hohlraum on the National Ignition Facility. It has used up to 500 TW of peak power and nearly 2 MJ of laser energy in pulses up to 8 ns in duration, with the goal of fielding controlled implosions with high coupled energy, which can suppress deleterious hydrodynamic instabilities. However, when the laser pulse exceeds 6 ns with the laser energy greater than 1.6 MJ, stimulated Brillouin scattering (SBS) reaches levels that may damage optical components in the laser. Pending development of techniques to reduce SBS, limitation of laser power, and energy to avoid damage prevents the full exploitation of this approach to ignition. In this manuscript, we present three-dimensional simulations that match the experimentally measured SBS energy, in particular, reproducing quantitatively the time in the pulse when maximum backscatter occurs, and its magnitude across ~10 BigFoot experiments. The demonstrated robustness of the modeling, which combines LASNEX and pF3D simulations, motivates us to explore and recommend several feasible SBS mitigation strategies: modified laser pointing, different laser frequencies for each cone of beams, increased laser bandwidth on all or some of the cones, and materials with a mixture of light and heavy atoms lining the inside of the hohlraum walls.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Anaerobic Biohydrogenation of Isoprene by Acetobacterium wieringae Strain Y

Isoprene is a ubiquitously distributed, biogenic, and climate-active organic compound. Microbial isoprene degradation in oxic environments is fairly well understood; however, studies exploring anaerobic isoprene metabolism remain scarce, with no isolates for study available. Here, we obtained an acetogenic isolate, designated Acetobacterium wieringae strain Y, which hydrogenated isoprene to a mixture of methyl-1-butenes at an overall rate of 288.8 ± 20.9 μM day -1 with concomitant acetate production at a rate of 478.4 ± 5.6 μM day -1 . Physiological characterization demonstrated that isoprene was not utilized in a respiratory process; rather, isoprene promoted acetogenesis kinetically. Bioinformatic analysis and proteomics experiments revealed the expression of candidate ene-reductases responsible for isoprene biohydrogenation. Notably, the addition of isoprene to strain Y cultures stimulated the expression of proteins associated with the Wood-Ljungdahl pathway, indicating unresolved impacts of isoprene on carbon cycling and microbial ecology in anoxic environments (e.g., promoting CO 2 plus H 2 reductive acetogenesis while inhibiting methanogenesis). Our new findings advance understanding of microbial transformation of isoprene under anoxic conditions and suggest that anoxic environments are isoprene sinks.

59 BASIC BIOLOGICAL SCIENCES↗

Effect of large amounts of dihydroxyacetone in the diet of rats.

Experiments in which dihydroxyacetone (DHA) was used as nutrient for growing rats have not fulfilled the expectation that DHA could be used as a significant portion of the diet. Any attempt to treat major cerebral damage by prolonged administration of DHA is strongly contraindicated. For this reason, regenerated formose mixtures containing appreciable amounts of DHA will not be suitable as a significant portion of the diet for the crews of long-duration space missions.

Shapira, J.↗

Development of an experiment for determining the autoignition characteristics of aircraft-type fuels

An experimental test apparatus was developed to determine the autoignition characteristics of aircraft-type fuels in premixing prevaporizing passages at elevated temperatures and pressures. The experiment was designed to permit independent variation and evaluation of the experimental variables of pressure, temperature, flow rate, and fuel-air ratio. A comprehensive review of the autoignition literature is presented. Performance verification tests consisting of measurements of the ignition delay times for several lean fuel-air mixture ratios were conducted using Jet-A fuel at inlet air temperatures in the range 600 K to 900 K and pressures in the range 9 atm to 30 atm.

Spadaccini, L. J.↗

Experimental and analytical analyses of the mechanisms governing the dispersion of flammable clouds formed by liquid hydrogen spills

This paper presents the initial findings of hydrogen vapor cloud dispersion experiments conducted by NASA. The experiments were performed to obtain basic information regarding the physical phenomena governing the dispersion of flammable clouds formed as the result of spills of large quantities of liquid hydrogen. The experiments consisted of ground spills of up to 5.7 cu m of liquid hydrogen with spill durations of approx. 35 s. Instrumented towers, located downwind of the spill site, gathered data on the temperature, hydrogen concentration and turbulence levels as the hydrogen vapor cloud drifted downwind. Preliminary results of the experiments indicate that, for rapid spills, thermal and momentum-induced turbulences cause the cloud to disperse to safe concentration levels and become positively buoyant long before mixing due to normal atmospheric turbulence becomes a major factor. An adiabatic mixing model has been developed to deduce hydrogen-air mixture ratios for temperature measurements obtained within the cloud formed by liquid hydrogen spills.

Witcofski, R. D.↗

Preparation and evaluation of advanced catalysts for phosphoric acid fuel cells

The platinum electrocatalysts were characterized for their crystallite sizes and the degree of dispersion on the carbon supports. One application of these electrocatalysts was for anodic oxidation of hydrogen in hot phosphoric acid fuel cells, coupled with the influence of low concentrations of carbon monoxide in the fuel gas stream. In a similar way, these platinum on carbon electrocatalysts were evaluated for oxygen reduction in hot phosphoric acid. Binary noble metal alloys were prepared for anodic oxidation of hydrogen and noble metal-refractory metal mixtures were prepared for oxygen reduction. An exemplar alloy of platinum and palladium (50/50 atom %) was discovered for anodic oxidation of hydrogen in the presence of carbon monoxide, and patent disclosures were submitted. For the cathode, platinum-vanadium alloys were prepared showing improved performance over pure platinum. Preliminary experiments on electrocatalyst utilization in electrode structures showed low utilization of the noble metal when the electrocatalyst loading exceeded one weight percent on the carbon.

Stonehart, P.↗

Life support systems research at the Johnson Space Center

The bioregenerative life support systems research at Johnson Space Center focuses on the use of lunar regolith as a plant growth medium. Current dissolution experiments are being conducted to ascertain the response of lunar regolith to various solvents and weathering environments. The transformation of lunar minerals into minerals such as zeolites which would be more conducive to plant growth is also investigated. A study is currently underway to examine the ability of zeolite/apatite mixtures to provide N, P, and K through dissolution and ion exchange. The development and characterization of simulated lunar regolith for preliminary experimentation are also discussed. The life support systems technology used on the Mercury, Gemini, Apollo, and Shuttle missions is reviewed and current research on regenerative life support systems technology for potential use in Space Station Freedom is discussed.

Henninger, D. L.↗

The Other Chemistry of the Jovian Icy Satellites - Low Energy and Sulfurous

Spectra of Jupiter's icy satellites reveal surfaces dominated by H2O-ice with minor amounts of SO2 and other materials. The co-existence of H2O and SO2 in surfaces exposed to jovian magnetospheric radiation suggests that sulfuric acid (H2SO4) also could be present. This was noted by Carlson et al. (1999), who supported this suggestion with assignments of near-IR bands in Europa spectra to hydrated H2SO4. Laboratory experiments since have demonstrated radiolytically-driven syntheses in S- and SO2-containing H2O-Ices (Carlson et al., 2002; Moore et al., 2006). In the Cosmic Ice Laboratory, we recently have investigated the thermal chemistry of SO2 trapped in H2O-ice. IR spectra of H2O + SO2 mixtures recorded at 10 to 230 K were used to follow low-temperature reactions in the absence of radiation effects. No SO2 reactions were found at 10 K, but warming to more-relevant Europa temperatures produced both HSO3(-) and S2O5(2-). Added NH3 shifted the product composition toward SO3(2-) and away from the other ions. We find that H2O and SO2 react to produce sulfur oxyanions, such as bisulfite, that as much as 30% of the SO2 can be consumed through this reaction, and that the products remain in the ice when the temperature is lowered, indicating that these reactions are irreversible. Our results suggest that thermally-induced reactions can alter the chemistry at and below the surfaces of the icy satellites in the jovian system.

Hudson, Reggie L.↗

Elastomer Filled With Single-Wall Carbon Nanotubes

Experiments have shown that composites of a silicone elastomer with single-wall carbon nanotubes (SWNTs) are significantly stronger and stiffer than is the unfilled elastomer. The large strengthening and stiffening effect observed in these experiments stands in contrast to the much smaller strengthening effect observed in related prior efforts to reinforce epoxies with SWNTs and to reinforce a variety of polymers with multiple-wall carbon nanotubes (MWNTs). The relative largeness of the effect in the case of the silicone-elastomer/SWNT composites appears to be attributable to (1) a better match between the ductility of the fibers and the elasticity of the matrix and (2) the greater tensile strengths of SWNTs, relative to MWNTs. For the experiments, several composites were formulated by mixing various proportions of SWNTs and other filling materials into uncured RTV-560, which is a silicone adhesive commonly used in aerospace applications. Specimens of a standard "dog-bone" size and shape for tensile testing were made by casting the uncured elastomer/filler mixtures into molds, curing the elastomer, then pressing the specimens from a "cookie-cutter" die. The results of tensile tests of the specimens showed that small percentages of SWNT filler led to large increases in stiffness and tensile strength, and that these increases were greater than those afforded by other fillers. For example, the incorporation of SWNTs in a proportion of 1 percent increased the tensile strength by 44 percent and the modulus of elasticity (see figure) by 75 percent. However, the relative magnitudes of the increases decreased with increasing nanotube percentages because more nanotubes made the elastomer/nanotube composites more brittle. At an SWNT content of 10 percent, the tensile strength and modulus of elasticity were 125 percent and 562 percent, respectively, greater than the corresponding values for the unfilled elastomer.

Files, Bradley S.↗

Liquid-based gating mechanism with tunable multiphase selectivity and antifouling behaviour

Living organisms make extensive use of micro- and nanometre-sized pores as gatekeepers for controlling the movement of fluids, vapours and solids between complex environments. The ability of such pores to coordinate multiphase transport, in a highly selective and subtly triggered fashion and without clogging, has inspired interest in synthetic gated pores for applications ranging from fluid processing to 3D printing and lab-on-chip systems(1-10). But although specific gating and transport behaviours have been realized by precisely tailoring pore surface chemistries and pore geometries(6,11-17), a single system capable of controlling complex, selective multiphase transport has remained a distant prospect, and fouling is nearly inevitable(11,12). Here we introduce a gating mechanism that uses a capillary-stabilized liquid as a reversible, reconfigurable gate that fills and seals pores in the closed state, and creates a non-fouling, liquid-lined pore in the open state. Theoretical modelling and experiments demonstrate that for each transport substance, the gating threshold-the pressure needed to open the pores-can be rationally tuned over a wide pressure range. This enables us to realize in one system differential response profiles for a variety of liquids and gases, even letting liquids flow through the pore while preventing gas from escaping. These capabilities allow us to dynamically modulate gas-liquid sorting in a microfluidic flow and to separate a three-phase air-water-oil mixture, with the liquid lining ensuring sustained antifouling behaviour. Because the liquid gating strategy enables efficient long-term operation and can be applied to a variety of pore structures and membrane materials, and to micro- as well as macroscale fluid systems, we expect it to prove useful in a wide range of applications.

Hou, X↗

Phototrophic Lactate Utilization by Rhodopseudomonas palustris Is Stimulated by Coutilization with Additional Substrates

The phototrophic purple nonsulfur bacterium Rhodopseudomonas palustris is known for its metabolic versatility and is of interest for various industrial and environmental applications. Despite decades of research on R. palustris growth under diverse conditions, patterns of R. palustris growth and carbon utilization with mixtures of carbon substrates remain largely unknown. R. palustris readily utilizes most short-chain organic acids but cannot readily use lactate as a sole carbon source. Here we investigated the influence of mixed-substrate utilization on phototrophic lactate consumption by R. palustris. We found that lactate was simultaneously utilized with a variety of other organic acids and glycerol in time frames that were insufficient for R. palustris growth on lactate alone. Thus, lactate utilization by R. palustris was expedited by its coutilization with additional substrates. Separately, experiments using carbon pairs that did not contain lactate revealed acetate-mediated inhibition of glycerol utilization in R. palustris. This inhibition was specific to the acetate-glycerol pair, as R. palustris simultaneously utilized acetate or glycerol when either was paired with succinate or lactate. Overall, our results demonstrate that (i) R. palustris commonly employs simultaneous mixed-substrate utilization, (ii) mixed-substrate utilization expands the spectrum of readily utilized organic acids in this species, and (iii) R. palustris has the capacity to exert carbon catabolite control in a substrate-specific manner. IMPORTANCE. Bacterial carbon source utilization is frequently assessed using cultures provided single carbon sources. However, the utilization of carbon mixtures by bacteria (i.e., mixed-substrate utilization) is of both fundamental and practical importance; it is central to bacterial physiology and ecology, and it influences the utility of bacteria as biotechnology. Here we investigated mixed-substrate utilization by the model organism Rhodopseudomonas palustris. Using mixtures of organic acids and glycerol, we show that R. palustris exhibits an expanded range of usable carbon substrates when provided substrates in mixtures. Specifically, coutilization enabled the prompt consumption of lactate, a substrate that is otherwise not readily used by R. palustris. Additionally, we found that R. palustris utilizes acetate and glycerol sequentially, revealing that this species has the capacity to use some substrates in a preferential order. These results provide insights into R. palustris physiology that will aid the use of R. palustris for industrial and commercial applications.

59 BASIC BIOLOGICAL SCIENCES↗

Wide-Angle X-ray Scattering Study on Shear-Induced Crystallization of Propylene-1-Butylene Random Copolymer: Experiment and Diffraction Pattern Simulation

Shear-induced crystallization of a propylene-1-butylene random copolymer with low butylene content (5.7 mol %) was studied using time-resolved wide-angle X-ray scattering (WAXS) techniques. Polymorphism, preferred crystal orientation, crystallization kinetics, and disorder effect were investigated based on WAXS 2D whole pattern analysis. It was found that at 100 C, the crystallite of P-B copolymer was a mixture of 80% {gamma}-form and 20% {alpha}-form of isotactic polypropylene (iPP) crystals. The application of a step shear (shear rate = 100 s{sup -1}, shear duration =3s) induced {gamma}-form crystals with c-axis oriented perpendicular to the shear direction. In contrast, the c-axis of {alpha}-form crystals was normally in parallel to the shear direction. Both crystallization kinetics and crystallinity were greatly enhanced by shear. The disorder effect was found to play an important role in the crystallization behavior of P-B copolymer. In the early stage crystallization, the chosen copolymer contained a large amount of structure defects, where crystals became more ordered upon annealing. The degree of crystal orientation was also found to decrease during crystallization due to the relaxation after shear.

36 MATERIALS SCIENCE↗

Ion Transport in Batteries with Polymer Electrolytes

We discuss polymer electrolytes for use in rechargeable lithium batteries. Polymer electrolytes have the potential to enable batteries with lithium metal anodes. These batteries have significantly higher theoretical energy densities than current lithium-ion batteries. We consider binary mixtures of polymers and salts. We also cover more complex systems such as polymer electrolytes swollen with a solvent (gel polymer electrolytes) and microphase separated polymer electrolytes. By covalently attaching the anions to the chains in a polymer solid, one obtains a single-ion conductor. We mainly focus on experiments wherein the polymer electrolyte is placed between two lithium metal electrodes. These experiments enable the determination of three transport parameters, ionic conductivity, salt diffusion coefficient, and transference number, and the thermodynamic factor. The properties of dry polymer electrolytes are contrasted with those of gel polymer electrolytes. The gel systems exhibit higher conductivity while the dry systems exhibit superior mechanical properties. We discuss interfacial impedance when lithium metal is contacted with polymer electrolytes and the importance of coulombic efficiency.

Yu, Xiaopeng↗

Basic properties of eutectic chloride salts NaCl-KCl-ZnCl 2 and NaCl-KCl-MgCl 2 as HTFs and thermal storage media measured using simultaneous DSC-TGA

Concentrated solar power (CSP) technologies tend to work at high temperatures for better energy efficiency, which need high temperature heat transfer fluids (HTF) and thermal storage. A good HTF should have low melting point and be thermally stable at high temperatures. A thermal storage medium needs a high heat capacity in order to store more energy in per unit of mass or volume. The objective of this work is to study the basic thermophysical properties of several eutectic molten salts for HTF and thermal storage media, which can work at upper limit temperatures of 850 °C. The eutectic salts are mixtures by NaCl-KCl-ZnCl 2 , and by NaCl-KCl-MgCl 2 , respectively. The heat capacity, melting point, and heat of fusion of the eutectic salts at different temperatures were measured using Differential Scanning Calorimetry (DSC) and Thermal Gravimetric Analysis (TGA) simultaneously. Details of the measurements and obtained experience of operating the equipment are provided in the work. For each of the eutectic salts multiple samples were tested to check repeatability and to minimize random errors. Finally, in theoretical analysis, mixing rules from literature was used to estimate the heat capacity of the new HTFs, which showed good agreement with experimental data.

14 SOLAR ENERGY↗

Diastereomerically Differentiated Excited State Behavior in Ruthenium(II) Hexafluoroacetylacetonate Complexes of Diphenyl Thioindigo Diimine

Mono- and diruthenium hexafluoroacetylacetonate (hfac) complexes of the thioindigo- N , N '-diphenyldiimine chelating ligand 3 have been prepared. The thioindigo diimine ligand binds to ruthenium in a bidentate fashion in the mononuclear compound 2 and serves as a bidentate chelating bridging ligand in the diruthenium complexes 1a and 1b . Compound 2 was isolated as a racemic mixture while the diruthenium complexes were isolated as the meso (ΔΛ) 1a and rac (ΔΔ and ΛΛ) 1b diastereomers. In-depth structural characterization of the compounds was performed, including X-ray crystallography, 1 H, 13 C, and 19 F nuclear magnetic resonance (NMR) spectroscopy, and 2D NMR correlation experiments. Electrochemical properties were evaluated utilizing cyclic voltammetry. Ground state optical properties of the complexes were examined using UV–visible spectroscopy and spectroelectrochemistry. The excited state dynamics of the series were explored by ultrafast transient absorption spectroscopy. Variable temperature NMR experiments demonstrated that the rac diruthenium compound 1b undergoes conformational exchange with a rate constant of 8700 s –1 at 298 K, a behavior that is not observed in the meso diastereomer 1a . The series of complexes possess metal-to-ligand charge transfer (MLCT) absorption bands in the near-infrared (λ max 689–783 nm). The compounds do not display photoluminescence in room temperature solution-phase experiments or in experiments at 77 K. Transient absorption spectroscopy measurements revealed excited states with picosecond lifetimes for 1a , 1b , and 2 , and spectroelectrochemical experiments confirmed assignment of the transient species as arising from MLCT transitions. Surprisingly, the transient absorption measurements revealed disparate time constants for the excited state decay of diastereomers 1a and 1b .

14 SOLAR ENERGY↗

Demonstration of a Long Pulse X-ray Source at the National Ignition Facility

A long duration high fluence x-ray source has been developed at the National Ignition Facility (NIF). The target was a 14.4 mm tall, 4.1 mm diameter, epoxy walled, gas filled pipe. Approximately 1.34 MJ from the NIF laser was used to heat the mixture of (55:45) Kr:Xe at 1.2 atm (~5.59 mg/cm 3 ) to emit in a fairly isotropic radiant intensity of 400–600 GW/sr from the E photon = 3–7 keV spectral range for a duration of ≈ 14 ns. Lastly, the HYDRA simulated radiant intensities were in reasonable agreement with experiments but deviated at late times.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Radiation burnthrough measurements to infer opacity at conditions close to the solar radiative zone–convective zone boundary

Recent measurements at the Sandia National Laboratory of the x-ray transmission of iron plasma have inferred opacities much higher than predicted by theory, which casts doubt on modeling of iron x-ray radiative opacity at conditions close to the solar convective zone-radiative zone boundary. An increased radiative opacity of the solar mixture, in particular iron, is a possible explanation for the disagreement in the position of the solar convection zone-radiative zone boundary as measured by helioseismology and predicted by modeling using the most recent photosphere analysis of the elemental composition. In this report we present data from radiation burnthrough experiments, which do not support a large increase in the opacity of iron at conditions close to the base of the solar convection zone and provide a constraint on the possible values of both the mean opacity and the opacity in the x-ray range of the Sandia experiments. The data agree with opacity values from current state-of-the-art opacity modeling using the CASSANDRA opacity code.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗