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Demonstrated viability and utilization of: a) Fluidized powder bed. b) WCl6 CVD process. c) Coated spherical particles with tungsten. The highly corrosive nature of the WCl6 solid reagent limits material of construction. Indications that identifying optimized process variables with require substantial effort and will likely vary with changes in fuel requirements.
Single-arm dual-mode optical waveguide interferometer utilizes interference between two modes of different order. Sensing effect results from the change in propagation conditions of the modes caused by the environment. The waveguide is made as an open asymmetric structure containing a dye-doped polymer film onto a quartz substrate. It is more sensitive to the change of environment than its conventional polarimetric analog using orthogonal modes (TE and TM) of the same order. The sensor still preserves the option of operating in polarimetric regime using a variety of mode combinations such as TE(sub 0)/TM(sub 0) (conventional) TE(sub 0)/TM(sub 1), TE(sub 1)/TM(sub 0), or TE(sub 1)/TM(sub 1) but can also work in nonpolarimetric regime using combinations TE(sub 0)/TE(sub 1) or TM(sub 0)/TM(sub 1). Utilization of different mode combinations simultaneously makes the device more versatile. Application of the sensor to gas sensing is based on doping polymer film with an organic indicator dye targeting a particular gaseous reagent. Change of the optical absorption spectrum of the dye caused by the gaseous pollutant results in change of the reactive index of the dye-doped polymer film that can be detected by the sensor. As indicator dyes we utilize Bromocresol Purple doped into polymer poly(methyl) methacrylate that is sensitive to small concentrations of ammonia. The indicator dye demonstrated an irreversible increase in optical absorption near the peak at 350 nm being exposed to 5% ammonia in pure nitrogen at 600 Torr. The dye also showed reversible growth of the absorption peak near 600 nm after exposure to a vapor of standard medical ammonia spirit (65% alcohol). We have built a breadboard prototype of the sensor with He-Ne laser as a light source and with a single mode fiber input and a multimode fiber output. The prototype showed a sensitivity to temperature change of the order of 2 C per 2pi phase shift. The sensitivity of the sensor to the presence of dTy ammonia is not less than 300 ppm per 2pi phase shift. The proposed sensor can be used as a robust stand-alone instrument for continuous environment pollution monitoring.
NASA is interested in green monopropellants to replace hydrazine in reaction control systems (RCSs). Some current NASA programs require reduced vapor pressure and low toxicity monopropellant (green) and superior performance (specific impulse and density) formulations. Earlier vapor phase studies of a candidate green monopropellant at the NASA White Sands Test Facility (WSTF) showed the presence of a volatile species that warranted further investigation. The purpose of this study was to further characterize the volatile species and to evaluate it. The evaluation was with respect to whether the volatile species was an impurity or how it is formed, and to use that information to examine whether its presence as an impurity can be eliminated during formulation. The evaluation also considered whether formation of the volatile impurity could be prevented while not compromising the propellant. To reduce variables associated with evaluation of the propellant formulation as a whole, a precursor to one of the individual components in the propellant formulation was subjected to a NASA Standard 6001B Flammability, Off-gassing, and Compatibility Requirements and Test Procedures "Determination of Off-gassed Products (Test 7)". Testing took place in the NASA WSTF Molecular Desorption and Analysis Laboratory. One gram of the precursor was placed in a flask within a specimen container. After thermal conditioning for 72 +/- 1 h at 50 +/- 3 deg C (122 +/- 5 deg F), the atmosphere inside the specimen container was analyzed for off-gassed compounds by cryotrap gas chromatography-mass spectrometry (GC-MS) and fixed sample loop GC-flame ionization detection (GC-FID). The specimen container used was glass to minimize potential catalytic surfaces. The identification of compounds was difficult due to the complexity of the vapor phase concentrations and overlapping chromatographic peaks and mass spectra. However, eleven compounds were specifically identified and five compounds or classes of compounds were reported as unidentified. Quantitation of most of the compounds, including unidentified compounds, was as methane. Quantitating compounds or classes of compounds that were detected but for which specific calibration is not established as methane is in accordance with the Test 7 standard protocol. The thermal decomposition temperature of the precursor was significantly higher than the test temperature. Based on thermal decomposition temperature and on an examination of the structure and chemistry of the identified volatile species, the presence of the volatile species appears to be chemically reasonable with respect to the propellant formulation and is at this time attributed to impurities. Further examination of the overall propellant formulation process (including the individual components' synthesis processes) and process quality control (including purity of reagents and possible decomposition reactions) is indicated.
Procedures for the safe destruction of liquid pentaborane(9), B5H9, by solvolysis were investigated. The objective of the study was to establish the optimum conditions for a pilot plant operation that would use water, or alcohol, or water-alcohol mixtures as the solvolysis reagent Small amounts of B5H9 sprayed from a syringe will not necessarily enflame, nor will a small pool on a spot plate. Therefore, a procedure was developed to reproducibly demonstrate the flammability of B5H9 In these tests every sample of neat B5H9 ignited and burned with a very sooty flame till the sample was consumed. The spontaneous self-ignition of B5H9 was quenched by the addition of small concentrations of the ethers THF (tetrahydrofuran) or DME (1,2-dimethoxy ethane). It was found that 10% (volume) of either provided total quenching with a large margin of safety. When these stabilized solutions were exposed to air, they decomposed and evaporated leaving a residue that was identified by NMR analysis as boric acid. Most of the laboratory solvolysis experiments used the 90% B5H9, 10% THF solution. This mixture was safer to handle and its solvolysis reactivity was virtually identical to that of 100% B5H9. Reaction rates were analyzed by measurement of hydrogen evolved during the solvolysis reactions. In terms of the minimum overall complete reaction time, the data indicate that 50150 alcohol/water is the optimum solvolysis reagent. This reaction produced a mixture of boric acid, B(OH)3, and triethoxyborane, B(OEt)3 [Et = C2H5], and mixed exchange derivatives thereof.
Procedures for the safe destruction of liquid pentaborane(9), B5H9, by solvolysis were investigated. The objective of the study was to establish the optimum conditions for a pilot plant operation that would use water, or alcohol, or water-alcohol mixtures as the solvolysis reagent. Small amounts of B5H9 sprayed from a syringe will not necessarily enflame, nor will a small pool on a spot plate. Therefore, a procedure was developed to reproducibly demonstrate the flammability of B5H9. In these tests every sample of neat B5H9 ignited and burned with a very sooty flame till the sample was consumed. The spontaneous self-ignition of B5H9 was quenched by the addition of small concentrations of ethers THF (tetrahydrofuran) or DME (1,2-dimethoxy ethane). It was found that ten percent (volume) of either provided total quenching with a large margin of safety. When these stabilized solutions were exposed to air, they decomposed and evaporated leaving a residue that was identified by nuclear magnetic resonance (NMR) analysis as boric acid. Most of the laboratory solvolysis experiments used the 90 percent B5H9, 10 percent THF solution. This mixture was safer to handle and its solvolysis reactivity was virtually identical to that of 100 percent B5H9. Reaction rates were analyzed by measurement of hydrogen evolved during the solvolysis reactions. In terms of the minimum overall complete reaction time, the data indicate that 50/50 alcohol/water is the optimum solvolysis reagent. This reaction produced a mixture of boric acid, B(OH)3, and triethoxyborane, B(OEt)3[Et = C2H5], and mixed exchange derivatives thereof.
A variety of plasma and ion beam techniques was employed to generate diamondlike carbon films. These methods included the use of RF sputtering, dc glow discharge, vacuum arc, plasma gun, ion beam sputtering, and both single and dual ion beam deposition. Since films were generated using a wide variety of techniques, the physico-chemical properties of these films varied considerably. In general, these films had characteristics that were desirable in a number of applications. For example, the films generated using both single and dual ion beam systems were evaluated for applications including power electronics as insulated gates and protective coatings on transmitting windows. These films were impervious to reagents which dissolve graphitic and polymeric carbon structures. Nuclear reaction and combustion analysis indicated hydrogen to carbon ratios to be 1.00, which allowed the films to have good transmittance not only in the infrared, but also in the visible. Other evaluated properties of these films include band gap, resistivity, adherence, density, microhardness, and intrinsic stress. The results of these studies and those of the other techniques for depositing diamondlike carbon films are presented.
Caveolin-1 is a palmitoylated protein involved in assembly of signaling molecules in plasma membrane subdomains termed caveolae and in intracellular cholesterol transport. Three cysteine residues in the C terminus of caveolin-1 are subject to palmitoylation, which is not necessary for caveolar targeting of caveolin-1. Protein palmitoylation is a post-translational and reversible modification that may be regulated and that in turn may regulate conformation, membrane association, protein-protein interactions, and intracellular localization of the target protein. We have undertaken a detailed analysis of [(3)H]palmitate incorporation into caveolin-1 in aortic endothelial cells. The linkage of palmitate to caveolin-1 was hydroxylamine-sensitive and thus presumably a thioester bond. However, contrary to expectations, palmitate incorporation was blocked completely by the protein synthesis inhibitors cycloheximide and puromycin. In parallel experiments to show specificity, palmitoylation of aortic endothelial cell-specific nitric-oxide synthase was unaffected by these reagents. Inhibitors of protein trafficking, brefeldin A and monensin, blocked caveolin-1 palmitoylation, indicating that the modification was not cotranslational but rather required caveolin-1 transport from the endoplasmic reticulum and Golgi to the plasma membrane. In addition, immunophilin chaperones that form complexes with caveolin-1, i.e. FK506-binding protein 52, cyclophilin A, and cyclophilin 40, were not necessary for caveolin-1 palmitoylation because agents that bind immunophilins did not inhibit palmitoylation. Pulse-chase experiments showed that caveolin-1 palmitoylation is essentially irreversible because the release of [(3)H]palmitate was not significant even after 24 h. These results show that [(3)H]palmitate incorporation is limited to newly synthesized caveolin-1, not because incorporation only occurs during synthesis but because the continuous presence of palmitate on caveolin-1 prevents subsequent repalmitoylation.
Free transition metal ions oxidize lipids and lipoproteins in vitro; however, recent evidence suggests that free metal ion-independent mechanisms are more likely in vivo. We have shown previously that human ceruloplasmin (Cp), a serum protein containing seven Cu atoms, induces low density lipoprotein oxidation in vitro and that the activity depends on the presence of a single, chelatable Cu atom. We here use biochemical and molecular approaches to determine the site responsible for Cp prooxidant activity. Experiments with the His-specific reagent diethylpyrocarbonate (DEPC) showed that one or more His residues was specifically required. Quantitative [14C]DEPC binding studies indicated the importance of a single His residue because only one was exposed upon removal of the prooxidant Cu. Plasmin digestion of [14C]DEPC-treated Cp (and N-terminal sequence analysis of the fragments) showed that the critical His was in a 17-kDa region containing four His residues in the second major sequence homology domain of Cp. A full length human Cp cDNA was modified by site-directed mutagenesis to give His-to-Ala substitutions at each of the four positions and was transfected into COS-7 cells, and low density lipoprotein oxidation was measured. The prooxidant site was localized to a region containing His426 because CpH426A almost completely lacked prooxidant activity whereas the other mutants expressed normal activity. These observations support the hypothesis that Cu bound at specific sites on protein surfaces can cause oxidative damage to macromolecules in their environment. Cp may serve as a model protein for understanding mechanisms of oxidant damage by copper-containing (or -binding) proteins such as Cu, Zn superoxide dismutase, and amyloid precursor protein.
During a recent flight of a Russian satellite (Cosmos #2229), initial experiments examining the effects of space flight on immunologic responses of rhesus monkeys were performed to gain insight into the effect of space flight on resistance to infection. Experiments were performed on tissue samples taken from the monkeys before and immediately after flight. Additional samples were obtained approximately 1 month after flight for a postflight restraint study. Two types of experiments were carried out throughout this study. The first experiment determined the ability of leukocytes to produce interleukin-1 and to express interleukin-2 receptors. The second experiment examined the responsiveness of rhesus bone marrow cells to recombinant human granulocyte-macrophage colony-stimulating factor (GM-CSF). Human reagents that cross-reacted with monkey tissue were utilized for the bulk of the studies. Results from both studies indicated that there were changes in immunologic function attributable to space flight. Interleukin-1 production and the expression of interleukin-2 receptors was decreased after space flight. Bone marrow cells from flight monkeys showed a significant decrease in their response to GM-CSF compared with the response of bone marrow cells from nonflight control monkeys. These results suggest that the rhesus monkey may be a useful surrogate for humans in future studies that examine the effect of space flight on immune response, particularly when conditions do not readily permit human study.
Planetary models suggest that nitrogen was abundant in the early Martian atmosphere as N2 but it was lost by sputtering and photochemical loss to space, impact erosion, and chemical oxidation to nitrates. A nitrogen cycle may exist on Mars where nitrates, produced early in Mars' history, may have been later decomposed back into N2 by the current impact flux. Nitrates are a fundamental source of nitrogen for terrestrial microorganisms, and they have evolved metabolic pathways to perform both oxidation and reduction to drive a complete biological nitrogen cycle. Therefore, the characterization of nitrogen in Martian soils is important to assess habitability of the Martian environment, particularly with respect to the presence of nitrates. The only previous mission that was designed to search for soil nitrates was the Phoenix mission but N-containing species were not detected by TEGA or the MECA WCL. Nitrates have been tentatively identified in Nakhla meteorites, and if nitrogen was oxidized on Mars, this has important implications for the habitability potential of Mars. Here we report the results from the Sample Analysis at Mars (SAM) instrument suite aboard the Curiosity rover during the first year of surface operations in Gale Crater. Samples from the Rocknest aeolian deposit and sedimentary rocks (John Klein) were heated to approx 835degC under helium flow and the evolved gases were analyzed by MS and GC-MS. Two and possibly three peaks may be associated with the release of m/z 30 at temperatures ranging from 180degC to 500degC. M/z 30 has been tentatively identified as NO; other plausible contributions include CH2O and an isotopologue of CO, 12C18O. NO, CH2O, and CO may be reaction products of reagents (MTBSTFA/DMF) carried from Earth for the wet chemical derivatization experiments with SAM and/or derived from indigenous soil nitrogenated organics. Laboratory analyses indicate that it is also possible that <550degC evolved NO is produced via reaction of HCl with nitrates arising from the decomposition of perchlorates. All sources of m/z 30 whether it be martian or terrestrial will be considered and their implications for Mars will be discussed.
The Sample Analysis at Mars (SAM) experiment on the National Aeronautics and Space Administration Curiosity rover seeks evidence of organic compounds on the surface of Mars. Since the beginning of the mission, various organic molecules have been detected and identified. While several have been demonstrated to be indigenous to the Martian soil and rocks analyzed, others appear to have been produced from sources internal to the experiment. The objective of this study is to build an exhaustive molecular database to support the interpretation of SAM results by identifying all the chemical species produced from Tenax® adsorbents, by determining (1) the thermal degradation by‐products of Tenax®, (2) the effect of Tenax® conditioning on the formation of Tenax® by‐products, (3) the impact of MTBSTFA or a mixture of MTBSTFA and DMF on Tenax® decomposition, and (4) the reaction between Tenax® and calcium perchlorate. Our results indicate that the by‐products of the SAM trap are due to the impact of trap heating, the impact of the derivatization reagent (MTBSTFA) and the presence of perchlorate in Martian soil. Some of these by‐products are observed in the SAM gas chromatograph mass spectrometer data from Mars.
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.
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.
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.
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.
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.
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.
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.