The reactivity of sodium alanates with O[2], H[2]O, and CO[2] : an investigation of complex metal hydride contamination in the context of automotive systems.

Safe and efficient hydrogen storage is a significant challenge inhibiting the use of hydrogen as a primary energy carrier. Although energy storage performance properties are critical to the success of solid-state hydrogen storage systems, operator and user safety is of highest importance when designing and implementing consumer products. As researchers are now integrating high energy density solid materials into hydrogen storage systems, quantification of the hazards associated with the operation and handling of these materials becomes imperative. The experimental effort presented in this paper focuses on identifying the hazards associated with producing, storing, and handling sodium alanates, and thus allowing for the development and implementation of hazard mitigation procedures. The chemical changes of sodium alanates associated with exposure to oxygen and water vapor have been characterized by thermal decomposition analysis using simultaneous thermogravimetric modulated beam mass spectrometry (STMBMS) and X-ray diffraction methods. Partial oxidation of sodium alanates, an alkali metal complex hydride, results in destabilization of the remaining hydrogen-containing material. At temperatures below 70 C, reaction of sodium alanate with water generates potentially combustible mixtures of H{sub 2} and O{sub 2}. In addition to identifying the reaction hazards associated with the oxidation of alkali-metal containing complex hydrides, potential treatment methods are identified that chemically stabilize the oxidized material and reduce the hazard associated with handling the contaminated metal hydrides

Compact fuel cell system utilizing a combination of hydrogen storage materials for optimized performance.

An entirely new class of light-weight reversible hydrides was recently discovered (the Ti-doped alanates)[1]. These NaAIH{sub 4}-based materials have demonstrated reversible hydrogen storage capacities of up to 5 wt%, nearly 4 times the gravimetrically density of commercial metal hydrides. For this reason, they have been considered a breakthrough for hydrogen storage in fuel cell vehicles. This project is the first to publish the use of alanates for the generation of electrical power and the first demonstration of a hydride-fueled elevated-temperature PEM Fuel Cell. Because the kinetics of hydrogen uptake and release by the alanate improves with elevated temperatures, novel concepts were tested for the purpose of developing a highly efficient stand-alone power system. A major focus of this work was on the modeling, design, construction and testing of an integrated fuel cell stack and hydrogen storage system that eliminates the need of complicated heat transfer systems and media. After extensive modeling efforts, a proof-of-concept system was built that employs an integrated fuel cell stack and hydride beds that balancing the generation of fuel cell waste heat with the endothermic release of hydrogen from the alanates. Our demonstration unit was capable of greater than one hour of operation on a single charge of hydrogen from the integrated 173 gram alanate bed. In addition, composite hydride materials with synergistic reaction heats were evaluated and tested to enhance the operational performance of the alanates. The composites provide a unique opportunity to utilize the heat produced from hydriding classic metal hydrides to improve both absorption and desorption rates of the alanates. A particular focus of the mixed storage materials work was to balance the thermodynamics and kinetics of the hydrides for start-up conditions. Modeling of the sorption properties proved invaluable in evaluating the optimum composition of hydrides. The modeling efforts were followed by full validation by experimental measurements. This project successfully completed the proof-of-concept goals and generated a powerful set of tools for optimizing the complete power-generation system. It has also created a new direction for hydrogen power generation as well the potential for new R&D based on this work

Composite Materials for Hazard Mitigation of Reactive Metal Hydrides.

In an attempt to mitigate the hazards associated with storing large quantities of reactive metal hydrides, polymer composite materials were synthesized and tested under simulated usage and accident conditions. The composites were made by polymerizing vinyl monomers using free-radical polymerization chemistry, in the presence of the metal hydride. Composites with vinyl-containing siloxane oligomers were also polymerized with and without added styrene and divinyl benzene. Hydrogen capacity measurements revealed that addition of the polymer to the metal hydride reduced the inherent hydrogen storage capacity of the material. The composites were found to be initially effective at reducing the amount of heat released during oxidation. However, upon cycling the composites, the mitigating behavior was lost. While the polymer composites we investigated have mitigating potential and are physically robust, they undergo a chemical change upon cycling that makes them subsequently ineffective at mitigating heat release upon oxidation of the metal hydride. Acknowledgements The authors would like to thank the following people who participated in this project: Ned Stetson (U.S. Department of Energy) for sponsorship and support of the project. Ken Stewart (Sandia) for building the flow-through calorimeter and cycling test stations. Isidro Ruvalcaba, Jr. (Sandia) for qualitative experiments on the interaction of sodium alanate with water. Terry Johnson (Sandia) for sharing his expertise and knowledge of metal hydrides, and sodium alanate in particular. Marcina Moreno (Sandia) for programmatic assistance. John Khalil (United Technologies Research Corp) for insight into the hazards of reactive metal hydrides and real-world accident scenario experiments. Summary In an attempt to mitigate and/or manage hazards associated with storing bulk quantities of reactive metal hydrides, polymer composite materials (a mixture of a mitigating polymer and a metal hydride) were synthesized and tested under simulated usage and accident conditions. Mitigating the hazards associated with reactive metal hydrides during an accident while finding a way to keep the original capability of the active material intact during normal use has been the focus of this work. These composites were made by polymerizing vinyl monomers using free-radical polymerization chemistry, in the presence of the metal hydride, in this case a prepared sodium alanate (chosen as a representative reactive metal hydride). It was found that the polymerization of styrene and divinyl benzene could be initiated using AIBN in toluene at 70 degC. The resulting composite materials can be either hard or brittle solids depending on the cross-linking density. Thermal decomposition of these styrene-based composite materials is lower than neat polystyrene indicating that the chemical nature of the polymer is affected by the formation of the composite. The char-forming nature of cross-linked polystyrene is low and therefore, not an ideal polymer for hazard mitigation. To obtain composite materials containing a polymer with higher char-forming potential, siloxane-based monomers were investigated. Four vinyl-containing siloxane oligomers were polymerized with and without added styrene and divinyl benzene. Like the styrene materials, these composite materials exhibited thermal decomposition behavior significantly different than the neat polymers. Specifically, the thermal decomposition temperature was shifted approximately 100 degC lower than the neat polymer signifying a major chemical change to the polymer network. Thermal analysis of the cycled samples was performed on the siloxane-based composite materials. It was found that after 30 cycles the siloxane-containing polymer composite material has similar TGA/DSC-MS traces as the virgin composite material indicating that the polymer is physically intact upon cycling. Hydrogen capacity measurements revealed that addition of the polymer to the metal hydride in the form of a composite material reduced the inherent hydrogen storage capacity of the material. This reduction in capacity was observed to be independent of the amount of charge/discharge cycles except for the composites containing siloxane, which showed less of an impact on hydrogen storage capacity as it was cycled further. While the reason for this is not clear, it may be due to a chemically stabilizing effect of the siloxane on the metal hydride. Flow-through calorimetry was used to characterize the mitigating effectiveness of the different composites relative to the neat (no polymer) material. The composites were found to be initially effective at reducing the amount of heat released during oxidation, and the best performing material was the siloxane-containing composite which reduced the heat release to less than 50% of the value of the neat material. However, upon cycling the composites, all mitigating behavior was lost. The combined results of the flow-through calorimetry, hydrogen capacity, and thermogravimetric analysis tests lead to the proposed conclusion that while the polymer composites have mitigating potential and are physically robust under cycling, they undergo a chemical change upon cycling that makes them ineffective at mitigating heat release upon oxidation of the metal hydride

Two Planets Straddling the Habitable Zone of The Nearby K dwarf Gl 414A

We present the discovery of two planets orbiting the nearby (D = 11.9 pc) K7 dwarf Gl 414A. Gl 414A b is a sub-Neptune mass planet with M_b sin i_b = 9.28^(+3.19)_(−2.54) M_⊕ and a semi-major axis of 0.24 ± 0.01 au. Gl 414A c is a sub-Saturn mass planet with M_c sin i_c = 59.48^(+9.98)_(−9.69) M_⊕ and a semi-major axis of 1.43 ± 0.06 au. We jointly analyzed radial velocity data from Keck/HIRES and the Automated Planet Finder at Lick Observatory, as well as photometric data from KELT, to detect the two planets as well as two additional signals related to the rotationally-modulated activity and the long term magnetic activity cycle of the star. The outer planet in this system is a potential candidate for future direct imaging missions

Desalination utilizing clathrate hydrates (LDRD final report).

Advances are reported in several aspects of clathrate hydrate desalination fundamentals necessary to develop an economical means to produce municipal quantities of potable water from seawater or brackish feedstock. These aspects include the following, (1) advances in defining the most promising systems design based on new types of hydrate guest molecules, (2) selection of optimal multi-phase reactors and separation arrangements, and, (3) applicability of an inert heat exchange fluid to moderate hydrate growth, control the morphology of the solid hydrate material formed, and facilitate separation of hydrate solids from concentrated brine. The rate of R141b hydrate formation was determined and found to depend only on the degree of supercooling. The rate of R141b hydrate formation in the presence of a heat exchange fluid depended on the degree of supercooling according to the same rate equation as pure R141b with secondary dependence on salinity. Experiments demonstrated that a perfluorocarbon heat exchange fluid assisted separation of R141b hydrates from brine. Preliminary experiments using the guest species, difluoromethane, showed that hydrate formation rates were substantial at temperatures up to at least 12 C and demonstrated partial separation of water from brine. We present a detailed molecular picture of the structure and dynamics of R141b guest molecules within water cages, obtained from ab initio calculations, molecular dynamics simulations, and Raman spectroscopy. Density functional theory calculations were used to provide an energetic and molecular orbital description of R141b stability in both large and small cages in a structure II hydrate. Additionally, the hydrate of an isomer, 1,2-dichloro-1-fluoroethane, does not form at ambient conditions because of extensive overlap of electron density between guest and host. Classical molecular dynamics simulations and laboratory trials support the results for the isomer hydrate. Molecular dynamics simulations show that R141b hydrate is stable at temperatures up to 265K, while the isomer hydrate is only stable up to 150K. Despite hydrogen bonding between guest and host, R141b molecules rotated freely within the water cage. The Raman spectrum of R141b in both the pure and hydrate phases was also compared with vibrational analysis from both computational methods. In particular, the frequency of the C-Cl stretch mode (585 cm{sup -1}) undergoes a shift to higher frequency in the hydrate phase. Raman spectra also indicate that this peak undergoes splitting and intensity variation as the temperature is decreased from 4 C to -4 C

Comparative genomics of Cluster O mycobacteriophages

Mycobacteriophages - viruses of mycobacterial hosts - are genetically diverse but morphologically are all classified in the Caudovirales with double-stranded DNA and tails. We describe here a group of five closely related mycobacteriophages - Corndog, Catdawg, Dylan, Firecracker, and YungJamal - designated as Cluster O with long flexible tails but with unusual prolate capsids. Proteomic analysis of phage Corndog particles, Catdawg particles, and Corndog-infected cells confirms expression of half of the predicted gene products and indicates a non-canonical mechanism for translation of the Corndog tape measure protein. Bioinformatic analysis identifies 8-9 strongly predicted SigA promoters and all five Cluster O genomes contain more than 30 copies of a 17 bp repeat sequence with dyad symmetry located throughout the genomes. Comparison of the Cluster O phages provides insights into phage genome evolution including the processes of gene flux by horizontal genetic exchange

Neuregulin-1 Regulates Cell Adhesion via an ErbB2/Phosphoinositide-3 Kinase/Akt-Dependent Pathway: Potential Implications for Schizophrenia and Cancer

Neuregulin-1 (NRG1) is a putative schizophrenia susceptibility gene involved extensively in central nervous system development as well as cancer invasion and metastasis. Using a B lymphoblast cell model, we previously demonstrated impairment in NRG1alpha-mediated migration in cells derived from patients with schizophrenia as well as effects of risk alleles in NRG1 and catechol-O-methyltransferase (COMT), a second gene implicated both in schizophrenia susceptibility and in cancer.Here, we examine cell adhesion, an essential component process of cell motility, using an integrin-mediated cell adhesion assay based on an interaction between ICAM-1 and the CD11a/CD18 integrin heterodimer expressed on lymphoblasts. In our assay, NRG1alpha induces lymphoblasts to assume varying levels of adhesion characterized by time-dependent fluctuations in the firmness of attachment. The maximum range of variation in adhesion over sixty minutes correlates strongly with NRG1alpha-induced migration (r(2) = 0.61). NRG1alpha-induced adhesion variation is blocked by erbB2, PI3K, and Akt inhibitors, but not by PLC, ROCK, MLCK, or MEK inhibitors, implicating the erbB2/PI3K/Akt1 signaling pathway in NRG1-stimulated, integrin-mediated cell adhesion. In cell lines from 20 patients with schizophrenia and 20 normal controls, cells from patients show a significant deficiency in the range of NRG1alpha-induced adhesion (p = 0.0002). In contrast, the response of patient-derived cells to phorbol myristate acetate is unimpaired. The COMT Val108/158Met genotype demonstrates a strong trend towards predicting the range of the NRG1alpha-induced adhesion response with risk homozygotes having decreased variation in cell adhesion even in normal subjects (p = 0.063).Our findings suggest that a mechanism of the NRG1 genetic association with schizophrenia may involve the molecular biology of cell adhesion

Phage Therapy of Mycobacterium Infections : Compassionate Use of Phages in 20 Patients With Drug-Resistant Mycobacterial Disease

Background Nontuberculous Mycobacterium infections, particularly Mycobacterium abscessus, are increasingly common among patients with cystic fibrosis and chronic bronchiectatic lung diseases. Treatment is challenging due to intrinsic antibiotic resistance. Bacteriophage therapy represents a potentially novel approach. Relatively few active lytic phages are available and there is great variation in phage susceptibilities among M. abscessus isolates, requiring personalized phage identification. Methods Mycobacterium isolates from 200 culture-positive patients with symptomatic disease were screened for phage susceptibilities. One or more lytic phages were identified for 55 isolates. Phages were administered intravenously, by aerosolization, or both to 20 patients on a compassionate use basis and patients were monitored for adverse reactions, clinical and microbiologic responses, the emergence of phage resistance, and phage neutralization in serum, sputum, or bronchoalveolar lavage fluid. Results No adverse reactions attributed to therapy were seen in any patient regardless of the pathogen, phages administered, or the route of delivery. Favorable clinical or microbiological responses were observed in 11 patients. Neutralizing antibodies were identified in serum after initiation of phage delivery intravenously in 8 patients, potentially contributing to lack of treatment response in 4 cases, but were not consistently associated with unfavorable responses in others. Eleven patients were treated with only a single phage, and no phage resistance was observed in any of these. Conclusions Phage treatment of Mycobacterium infections is challenging due to the limited repertoire of therapeutically useful phages, but favorable clinical outcomes in patients lacking any other treatment options support continued development of adjunctive phage therapy for some mycobacterial infections.We describe 20 consecutive cases of bacteriophage treatment of Mycobacterium infections. We observed no adverse reactions, favorable outcomes in at least 50% of patients, no evidence of phage resistance, and neutralizing immune reactions that do not correlate with treatment success.Peer reviewe

Another Shipment of Six Short-Period Giant Planets from TESS

We present the discovery and characterization of six short-period, transiting giant planets from NASA's Transiting Exoplanet Survey Satellite (TESS) -- TOI-1811 (TIC 376524552), TOI-2025 (TIC 394050135), TOI-2145 (TIC 88992642), TOI-2152 (TIC 395393265), TOI-2154 (TIC 428787891), & TOI-2497 (TIC 97568467). All six planets orbit bright host stars (8.9 <G< 11.8, 7.7 <K< 10.1). Using a combination of time-series photometric and spectroscopic follow-up observations from the TESS Follow-up Observing Program (TFOP) Working Group, we have determined that the planets are Jovian-sized (R$_{P}$ = 1.00-1.45 R$_{J}$), have masses ranging from 0.92 to 5.35 M$_{J}$, and orbit F, G, and K stars (4753 $<$ T$_{eff}$ $<$ 7360 K). We detect a significant orbital eccentricity for the three longest-period systems in our sample: TOI-2025 b (P = 8.872 days, $e$ = $0.220\pm0.053$), TOI-2145 b (P = 10.261 days, $e$ = $0.182^{+0.039}_{-0.049}$), and TOI-2497 b (P = 10.656 days, $e$ = $0.196^{+0.059}_{-0.053}$). TOI-2145 b and TOI-2497 b both orbit subgiant host stars (3.8 $<$ $\log$ g $<$4.0), but these planets show no sign of inflation despite very high levels of irradiation. The lack of inflation may be explained by the high mass of the planets; $5.35^{+0.32}_{-0.35}$ M$_{\rm J}$ (TOI-2145 b) and $5.21\pm0.52$ M$_{\rm J}$ (TOI-2497 b). These six new discoveries contribute to the larger community effort to use {\it TESS} to create a magnitude-complete, self-consistent sample of giant planets with well-determined parameters for future detailed studies.Comment: 20 Pages, 6 Figures, 8 Tables, Accepted by MNRA