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At least 37 records · Page 2

Computational and Experimental Investigation of Li-doped Ionic Liquid Electrolytes: [pyr14][tfsi], [pyr13][fsi], and [EMIM][BF4]

We employ molecular dynamics (MD) simulation and experiment to investigate the structure, thermodynamics, and transport of N-methyl-N-butylpyrrolidinium bis(trifluoromethylsufonyl)imide ([pyr14][TFSI]), N -methyl-N-propylpyrrolidinium bis(fluorosufonyl)imide ([pyr13][FSI]), and 1-ethyl-3-methylimidazolium boron tetrafluoride ([EMIM][BF4]), as a function of Li-salt mole fraction (0.05 xLi+ 0.33) and temperature (298 K T 393 K). Structurally, Li+ is shown to be solvated by three anion neigh- bors in [pyr14][TFSI] and four anion neighbors in both [pyr13][FSI] and [EMIM][BF4], and at all levels of xLi+ we find the presence of lithium aggregates. Pulsed field gradient spin-echo NMR measurements of diffusion and electrochemical impedance spectroscopy measurements of ionic conductivity are made for the neat ionic liquids as well as 0.5 molal solutions of Li-salt in the ionic liquids. Bulk ionic liquid properties (density, diffusion, viscosity, and ionic conductivity) are obtained with MD and show excellent agreement with experiment. While the diffusion exhibits a systematic decrease with increasing xLi+, the contribution of Li+ to ionic conductivity increases until reach- ing a saturation doping level of xLi+ 0.10. Comparatively, the Li+ conductivity of [pyr14][TFSI] is an order of magnitude lower than that of the other liquids, which range between 0.1-0.3 mScm. Our transport results also demonstrate the necessity of long MD simulation runs ( 200 ns) required to converge transport properties at room T. The differences in Li+ transport are reflected in the residence times of Li+ with the anions (Li), which are revealed to be much larger for [pyr14][TFSI] (up to 100 ns at the highest doping levels) than in either [EMIM][BF4] or [pyr13][FSI]. Finally, to comment on the relative kinetics of Li+ transport in each liquid, we find that while the net motion of Li+ with its solvation shell (vehicular) significantly contributes to net diffusion in all liquids, the importance of transport through anion exchange (hopping) increases at high xLi+ and in liquids with large anions.

electrolytes↗

Use of sorption technology for treatment of humidity condensate for potable water

This research focused on the testing of the original potable water processor aboard Space Station Freedom that was to produce potable water from the humidity condensate and additional water generated by carbon dioxide reduction. Humidity condensate was simulated by an influent water model 'Ersatz'. The humidity condensate was treated with multifiltration (MF) beds that consisted of a train of sorption beds (referred to as 'Unibed') designed to remove specific contaminants. For the complete simulated MF system runs tested for 100 bed volumes (BV) (volume processed/total column volume), 0.6 percent of the TOC was removed by the SAC/IRN 77 (Strong Acid Cation exchange resin), 39.6 percent of the total organic carbon (TOC) was removed by the WBA/IRA 68 (Weak Base Anion exchange resin), 13.2 percent of the TOC was removed by activated carbon adsorption (580-26), and the remaining sorbent media acted as polishing units to remove an additional 1.6 percent of the TOC at steady state. At steady state, 45 percent of the influent TOC passed through the MF bed.

Ajjarapu, Sundara R. M.↗

Phosphate binding protein as the biorecognition element in a biosensor for phosphate

This work explores the potential use of a member of the periplasmic family of binding proteins, the phosphate binding protein (PBP), as the biorecognition element in a sensing scheme for the detection of inorganic phosphate (Pi). The selectivity of this protein originates from its natural role which, in Escherichia coli, is to serve as the initial receptor for the highly specific translocation of Pi to the cytoplasm. The single polypeptide chain of PBP is folded into two similar domains connected by three short peptide linkages that serve as a hinge. The Pi binding site is located deep within the cleft between the two domains. In the presence of the ligand, the two globular domains engulf the former in a hinge-like manner. The resultant conformational change constitutes the basis of the sensor development. A mutant of PBP (MPBP), where an alanine was replaced by a cysteine residue, was prepared by site-directed mutagenesis using the polymerase chain reaction (PCR). The mutant was expressed, from plasmid pSD501, in the periplasmic space of E. coli and purified in a single chromatographic step on a perfusion anion-exchange column. Site-specific labeling was achieved by attaching the fluorophore, N-[2-(1-maleimidyl)ethyl]-7-(diethylamino)coumarin-3-carboxamide (MDCC), to the protein through the sulfhydryl group of the cysteine moiety. Steady-state fluorescence studies of the MPBP-MDCC conjugate showed a change in the intensity of the signal upon addition of Pi. Calibration curves for Pi were constructed by relating the intensity of the fluorescence signal with the amount of analyte present in the sample. The sensing system was first developed and optimized on a spectrofluorometer using ml volumes of sample. It was then adapted to be used on a microtiter plate arrangement with microliter sample volumes. The system's versatility was finally proven by developing a fiber optic fluorescence-based sensor for monitoring Pi. In all three cases the detection limits for the analyte were in the sub-microMolar range. It was also demonstrated that the sensing system was selective for phosphate over other structurally-similar anions, paving the way for the design and development of a new family of biosensors utilizing the specific binding properties of periplasmic proteins. c2003 Elsevier B.V. All rights reserved.

NASA Program Fundamental Space Biology↗

Development of anion-selective membranes

Methods were studied of preparing anion-exchange membranes that would have low resistance, high selectivity, and physical and chemical stability when used in acidic media in a redox energy storage system. Of the twelve systems selected for study, only the system that was based on crosslinked poly-4-vinylpyridinium chloride produced physically strong membranes when equilibrated in l M HCl. The resistivity of the best membrane was 12 ohm-cm, and the transference number for chloride ions was 0.81.

Lacey, R. E.↗

Water system microbial check valve development

A residual iodine microbial check valve (RIMCV) assembly was developed and tested. The assembly is designed to be used in the space shuttle potable water system. The RIMCV is based on an anion exchange resin that is supersaturated with an iodine solution. This system causes a residual to be present in the effluent water which provides continuing bactericidal action. A flight prototype design was finalized and five units were manufactured and delivered.

Colombo, G. V.↗

Advanced microbial check valve development

A flight certified assembly identified as a Microbial Check Valve (MCV) was developed and tested. The MCV is a canister packed with an iodinated anionic exchange resin. The device is used to destroy organisms in a water stream as the water passes through the device. The device is equally effective for fluid flow in either direction and its primary method of organism removal is killing rather than filtering. The MCV was successfully developed for the space shuttle to: disinfect fuel cell water; and prevent back contamination of the stored potable water supply. One version of the device consists of a high residual iodinated resin bed that imparts approximately 2 ppm of iodine to the fuel cell water as it flows to the potable water tanks. A second version of the device consists of a low residual iodinated resin bed. One of these low residual beds is located at each use port in the potable water system for the dual purpose of removing some iodine from the potable water as it is dispensed and also to prevent back contamination of the potable supply.

Colombo, G. V.↗

Template-directed synthesis and selective adsorption of oligoadenylates in hydroxyapatite

Polyuridylic acid is adsorbed completely from aqueous solution by hydroxyapatite under conditions that permit template-directed synthesis of oligoadenylates in free solution. The yield of oligoadenylates is enhanced to almost the same extent by poly(U) in the presence or the absence of hydroxyapatite. Under very similar conditions small quantities of hydroxyapatite adsorb higher-molecular-weight oligoadenylates selectively from a mixture of oligomers. On the basis of these results a mechanism for prebiotic oligonucleotide formation is proposed in which selective adsorption on hydroxyapatite or some other immobilized anion-exchanging material plays a major role. Monomers are released from the surface for reactivation, while oligomers are retained in a protected environment by adsorption to the apatite surface.

Gibbs, D.↗

Advances in membrane technology for the NASA redox energy storage system

Anion exchange membranes used in the system serve as a charge transferring medium as well as a reactant separator and are the key enabling component in this storage technology. Each membrane formulation undergoes a series of screening tests for area-resistivity, static (non-flow) diffusion rate determination, and performance in Redox systems. The CDIL series of membranes has, by virtue of its chemical stability and high ion exchange capacity, demonstrated superior properties in the redox environment. Additional resistivity results at several acid and iron solution concentrations, iron diffusion rates, and time dependent iron fouling of the various membrane formulations are presented in comparison to past standard formulations.

Ling, J. S.↗

An electrochemical rebalance cell for Redox systems

An electrochemical rebalance cell for maintaining electrochemical balance, at the system level, of the acidified aqueous iron chloride and chromium chloride reactant solutions in the redox energy storage system was constructed and evaluated. The electrochemical reaction for the cathode is Fe(+3) + e(-) yields Fe(+2), and that for the anode is 1/2H2 yields H(+) + e(-). The iron (carbon felt) electrode and the hydrogen (platinized carbon) electrode are separated by an anion exchange membrane. The performance of the rebalance cell is discussed as well as the assembly of a single rebalance cell and multicell stacks. Various cell configurations were tested and the results are presented and discussed. The rebalance cell was also used to demonstrate its ability, as a preparative tool, for making high purity solutions of soluble reduced metal ionic species. Preparations of titanium, copper, vanadium and chromium ions in acidified solutions were evaluated.

Acevedo, J. C.↗

Phytoxicity study of the products of wet oxidation of a representative biomass (lettuce)

In an attempt to verify the results reported previously concerning the phytotoxicity of wet-oxidation (wet-ox) products, lettuce solids were suspended in water and then heated to 548 K for 3.6 ksec (1 hr) under 4.1x10 to the -7 Pa (400 psig at 294 K) oxygen pressure and 1.52x10 to the 8th (1500 psig at 548 K) total pressure. Such treatment resulted in oxidation of 80% of the initial organic carbon to carbon dioxide. Thirty-three percent of the remaining organic carbon was present in acetic acid. Organic nitrogen in the feed was decreased 90% by the wet-ox treatment. Ammonia and nitrogen gas were the main nitrogen products. Analysis of the liquid product of wet-ox indicated that most of the minerals essential for plant growth were present. However, when tested using a lettuce-root growth-rate assay, the solution was toxic. This toxicity was not due to excessive salt or ammonia or to an improper pH. Analysis of the wet-ox solution revealed the presence of silver and chromium, thus implicating reactor corrosion as the cause of the phytotoxicity. Both cation and anion exchange resins removed the silver and the toxicity of the liquid effluent, indicating silver as the toxic component. Uptake of both silver and chromium by lettuce roots correlated with diminished root growth. Toxicity of the solution from wet-ox was not observed when precautions were taken to minimize contact of the liquid in the reactor with the metal reactor components.

Onisko, B. L.↗

Presynaptic elements involved in the maintenance of the neuromuscular junction

Alterations in the neuromuscular junction were observed in rats preceding loss of muscle mass. In view of the possibility that these alterations involve changes in the secretion of myotrophic agents by presynaptic motor neurons, an investigation was undertaken to characterize a neuronall factor which is thought to be involved in the initiation and maintenance of cholinergic synapses. This factor, which is secreted into the incubation medium by NG108-15 neuroblastoma x glioma hybrid cells, induces the aggregation of nicotinic acetylcholine receptors on primary cultures of rat hindlimb myotubes. Previous attempts to purify this factor failed. Extensive washing of the NG108-15 cells with hepes-buffered salt solution followed by short (4 hour) collection times resulted in the collection of incubation medium containing maximal aggregation activity with as little as 5 ug secreted protein per ml of fresh medium. A three-fold increase in specific activity was obtained after anion exchange chromatography.

Burrows, G. H.↗

Development of a regenerable humidity and CO2 control system for an advanced EMU

A 5-h-regenerable nonventing humidity and CO2 control subsystem (HCCS) technology demonstration unit is being developed for potential use in an Advanced Extravehicular Mobility Unit for Space Station application. The HCCS incorporates a weak-base-anion exchange resin packed in a metal-foam-matrix heat exchanger. This system simultaneously removes CO2 and water vapor, with the resulting exothermic heat of reaction rejected to the heat exchanger. The system has no moving parts, resulting in a highly reliable simple configuration. Regeneration may be accomplished via internal heating and vacuum.

Nalette, Timothy A.↗

Mixed-valence hydroxides as bioorganic host minerals

A range of naturally occurring divalent-trivalent metal cation hydroxides and modified artifical analogs have been synthesized and characterized. Structural and chemical properties of these minerals, determining their capability to selectively concentrate, order and alter molecules of prebiotic interest, include their anion exchange capacity and specificity, photochemical reactivity, production of nascent hydrogen, and catalytic efficiency. Properties relevant to these functions have been investigated and are discussed.

Kuma, K.↗

Evaluation testing of a portable vapor detector for Part-Per-Billion (PPB) level UDMH and N2H4

Trace level detection of hydrazine (N2H4), monomethyl hydrazine (MMH) and unsymmetrical dimethylhydrazine (UDMH) has been receiving increased attention over the past several years. In May 1995 the American Conference of Government Industrial Hygienists (ACGIH) lowered their acceptable threshold limit value (TLV) from 100 parts-per-billion (ppb) to 10 ppb. Several types of ppb-level detectors are being developed by the United States Air Force (USAF) Space and Missile Systems Center (SMSC). A breadboard version of a portable, lightweight hydrazine detection sensor was developed and produced by Giner Corp. for the USAF. This sensor was designed for ppb level UDMH and N2H4 vapor detection in near real-time. This instrument employs electrochemical sensing, utilizing a three electrode cell with an anion-exchange polymer electrolyte membrane as the only electrolyte in the system. The sensing, counter and reference electrodes are bonded to the membrane forming a single component. The only liquid required to maintain the sensor is deionized water which hydrates the membrane. At the request of the USAF SMSC, independent testing and evaluation of the breadboard instrument was performed at NASA's Toxic Vapor Detection Laboratory (TVDL) for response to ppb-level N2H4 and UDMH and MMH. The TVDL, located at Kennedy Space Center (KSC) has the unique ability to generate calibrated sample vapor streams of N2H4, UDMH, and MMH over a range from less than 10 ppb to thousands of parts per million (ppm) with full environmental control of relative humidity (0-90%) and temperature (0-50 C). The TVDL routinely performs these types of tests. Referenced sensors were subjected to extensive testing, including precision, linearity, response/recovery times, zero and span drift, humidity and temperature effects as well as ammonia interference. Results of these tests and general operation characteristics are reported.

Curran, Dan↗

Phosphorus Adsorption and Desorption Properties of Minnesota Basalt Lunar Simulant and Lunar Glass Simulant

Phosphorus (P) adsorption and desorption characteristics of Minnesota Basalt Lunar Simulant (MBLS) and Lunar Glass Simulant (LGS) were evaluated. Results of P interactions with lunar simulants indicated that mineral and glass components adsorbed between 50 and 70% of the applied P and that between 85 and 100% of the applied P was desorbed. The Extended Freundlich equation best described the adsorption data (r(sup 2) = 0.92), whereas the Raven/Hossner equation best described the desorption data ((r(sup 2) = 0.97). Kinetic desorption results indicated that MBLS and LGS released most of their P within 15 h. The expanded Elovich equation fit the data best at shorter times while t/Q(sub DT) equation had a better fit at longer times. These results indicate that P does not strongly adsorb to the two simulants and that any P that was adsorbed was readily desorbed in the presence of anion exchange resin. This work suggests that multiple small applications of P (10-20 mg P/kg) should be added to the simulants to ensure adequate solution P for plant uptake and efficient use of P fertilizer.

Sutter, Brad↗

Studies on the "Aerobic" Acetyl-Coenzyme A Synthetase of Saccharomyces Cerevisiae: Purification, Crystallization, and Physical Properties of the Enzyme

A procedure for the purification of a stable acetyl-coenzyme A synthetase (ACS) from aerobic cells of Saccharomyces cerevisiae is presented. The steps include differential centrifugation, solubilization of the bound enzyme from the crude mitochondrial fraction, ammonium sulfate fractionation, crystallization to constant specific activity from ammonium sulfate solutions followed by Bio-Gel A-1.5 m column chromatography. The resulting enzyme preparation is homogeneous as judged by chromatography on Bio-Gel columns, QAE-Sephadex A-50 anion exchange columns, analytical ultracentrifugal studies, and polyacrylamide gel electrophoresis. Sedimentation velocity runs revealed a single symmetric peak with an s(sub (20,w)) value of 10.6. The molecular weight of the native enzyme, as determined by gel filtration and analytical ultracentrifugation, is 250,000 +/- 500. In polyacrylamide gel electrophoresis in the presence of sodium dodecyl sulfate, the molecular weight of the single polypeptide chain is 83,000 +/- 500. The purified enzyme is inhibited by palmityl-coenzyme A with a Hill interaction coefficient, n, of 2.88. These studies indicate that the ACS of aerobic Saccharomyces cerevisiae is composed of three subunits of identical or nearly identical size.

Satyanarayana, T.↗

Indicator Devices for Detection of Trace Gaseous Hydrazines

The relatively recent decrease in the acceptable time-weighted-average for hydrazines from 100 parts-per-billion (ppb) to 10 ppb rendered many trace hydrazine detectors either insensitive or inaccurate. Development of a rapid detection method for hydrazines at the new 10-ppb concentration was necessary so that test area personnel could reliably assess airborne hydrazines concentrations of a potentially contaminated area prior to entry. The reduction of Au(III) to Au(0) by hydrazines is a well characterized reaction and application of the corresponding yellow to purple color change was selected as a potentially useful means for detection of trace hydrazines in air. Tests with small quantities of KAuCl4 deposited on a variety of substrates were conducted using verified sources of 1,1-dimethylhydrazine, methylhydrazine, and hydrazine at approximately 10 ppb in air. Substrates tested were glass fiber filter paper, glass beads, anion exchange resin (AuCl4- form), and diatomaceous earth. The most successful of these substrates were glass fiber filter paper and diatomaceous earth. The KAuC14 impregnated glass fiber filter paper appeared to be somewhat light sensitive so further tests were conducted using the diatomaceous earth substrate. KAuCl4 concentration, substrate particle size, and sampler configuration were evaluated. Based on these tests, the device selected for further evaluation was a 5mm OD by 50mm glass tube containing 0.02-0.03g of 45/60 mesh diatomaceous earth coated with 2 percent KAuCl4. When connected to a sampling pump, response of the device to changes in relative humidity, ambient light, and high levels of other fluids, which might also be found in a propellant test area, was evaluated. False positive responses were not detected for exposures to relative humidity changes from 10 to 80 percent, sunlight for greater than 10 minutes, or percent levels of ammonia, isopropyl alcohol, nitrogen dioxide, and hydrogen. In addition, body emissions did not produce a false positive response in view of potential application for use inside protective clothing. The device was shown to reliably detect less than 10 ppb of the hydrazines tested using a 10 to 20L sample followed by a 2 to 5 minute color development time. Some field tests were conducted in parallel with conventional acidic firebrick sorbent tubes. There was generally very good agreement between the devices and firebrick sorbent tubes when greater than 10 ppb of a hydrazine was present.

Dee, Lou A.↗

Compaction agent clarification of microbial lysates

Recombinant proteins are often purified from microbial lysates containing high concentrations of nucleic acids. Pre-purification steps such as nuclease addition or precipitation with polyethyleneimine or ammonium sulfate are normally required to reduce viscosity and to eliminate competing polyanions before anion exchange chromatography. We report that small polycationic compaction agents such as spermine selectively precipitate nucleic acids during or after Escherichia coli lysis, allowing DNA and RNA to be pelleted with the insoluble cell debris. Analysis by spectrophotometry and protein assay confirmed a significant reduction in the concentration of nucleic acids present, with preservation of protein. Lysate viscosity is greatly reduced, facilitating subsequent processing. We have used 5mM spermine to remove nucleic acids from E. coli lysate in the purification of a hexahistidine-tagged HIV reverse transcriptase.

NASA Discipline Environmental Health↗