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At least 55 records · Page 3

Fluorescent indicator dyes for calcium ions

The present invention discloses a new class of highly fluorescent indicator dyes that are specific for calcium ions. The new fluorescent indicator dyes combine a stilbene-type fluorophore with a tetracarboxylate parent Ca.sup.2+ chelating compound having the octacoordinate pattern of liganding groups characteristic of EGTA and BAPTA. Preferred forms contain extra heterocyclic bridges to reinforce the ethylenic bond of the stilbene and to reduce hydrophobicity. Compared to their widely used predecessor, quin2, the new dyes offer up to thirty-fold brighter fluorescence, major changes in wavelength (not just intensity) upon Ca.sup.2+ binding, slightly lower affinities for Ca.sup.2+, slightly longer wavelengths of excitation, and considerably improved selectivity for Ca.sup.2+ over other divalent cations. These properties, particularly the wavelength sensitivity to Ca.sup.2+, make the dyes useful indicators for many intracellular applications, especially in single cells, adherent cell layers, or bulk tissues. The present invention also discloses an improved method for synthesizing alpha-acyloxyalkyl bromides wherein the bromides so synthesized are free of contaminating bis(1-bromoalkyl)ether. The improved method is exemplified herein in the synthesis of acetoxymethyl bromide, a compound useful in preparing the acetoxymethyl esters disclosed herein as novel Ca.sup.2+ specific fluorescent indicators.

Tsien, Roger Y.↗

Determination of CA-41, I-129 and OS-187 in the Rochester tandem accelerator and some applications of these isotopes

The measurement of Ca-41 and I-129 utilizing the Rochester Tanden Accelerator Mass Spectrometer (TAMS) is discussed. Ca-41, having a half-life of 100,000 yrs., is of potential use for the dating of ground water as well as of bones in the age range between 50,000 and 1 million yrs. A major problem for the measurement of Ca-41 with TAMS is the fact that calcium does not readily form negative atomic ions. It does, however, form negative molecular ions. The production of CaO ions from compounds such as CaO and CaCO3 and from free Ca molecules sprayed with oxygen gas was studied. A project to utilize I-129 as a tracer for hydrothermal convection in sediment-covered oceanic crust is also briefly described. Finally, plans to use the Os-187/Os-186 ratio for the determination of extraterrestrial material in the Ries crater in Germany are summarized.

Fehn, U.↗

Corrosion Preventive Compounds Lifetime Testing

Lifetime Testing of Corrosion Preventive Compounds (CPCs) was performed to quantify performance in the various environments to which the Space Shuttle Orbiter is exposed during a flight cycle. Three CPCs are approved for use on the Orbiter: RD Calcium Grease, Dinitrol AV-30, and Braycote 601 EF. These CPCs have been rigorously tested to prove that they mitigate corrosion in typical environments, but little information is available on how they perform in the unique combination of the coastal environment at the launch pad, the vacuum of low-earth orbit, and the extreme heat of reentry. Currently, there is no lifetime or reapplication schedule established for these compounds that is based on this combination of environmental conditions. Aluminum 2024 coupons were coated with the three CPCs and exposed to conditions that simulate the environments to which the Orbiter is exposed. Uncoated Aluminum 2024 coupons were exposed to the environmental conditions as a control. Visual inspection and Electro- Impedance Spectroscopy (EIS) were performed on the samples in order to determine the effectiveness of the CPCs. The samples were processed through five mission life cycles or until the visual inspection revealed the initiation of corrosion and EIS indicated severe degradation of the coating.

Hale, Stephanie M.↗

Corrosion Preventive Compounds Lifetime Testing

Lifetime Testing of Corrosion Preventive Compounds (CPCs) was performed to quantify performance in the various environments to which the Space Shuttle Orbiter is exposed during a flight cycle. Three CPCs are approved for use on the Orbiter: HD Calcium Grease, Dinitrol AV-30, and Braycote 601 EF. These CPCs have been rigorously tested to prove that they mitigate corrosion in typical environments, but little information is available on how they perform in the unique combination of the coastal environment at the launch pad, the vacuum of low-earth orbit, and the extreme heat of reentry. Currently, there is no lifetime or reapplication schedule established for these compounds that is based on this combination of environmental conditions. Aluminum 2024 coupons were coated with the three CPCs and exposed to conditions that simulate the environments to which the Orbiter is exposed. Uncoated Aluminum 2024 coupons were exposed to the environmental conditions as a control. Visual inspection and Electro- Impedance Spectroscopy (EIS) were performed on the samples in order to determine the effectiveness of the CPCs. The samples were processed through five mission life cycles or until the visual inspection revealed the initiation of corrosion and EIS indicated severe degradation of the coating.

Hale, Stephanie M.↗

In Situ Electrosynthesis of Polymethyl Methacrylate Within Ceramic Launch Pad Materials

Electrokinetic deposition of methylmethacrylate is used to mitigate corrosion in reinforced concrete. The methylmethacrylate (MMA) monomer deposits in the pores in the concrete where it is converted into its polymer, polymethylmethacrylate, thus creating a barrier that also enhances the mechanical properties of the concrete. Previous to the MMA treatment an Electrokinetic deposition is used to transport calcium, sodium and potassium hydroxide particles through the capillary pores of concrete directly to the concrete reinforcement. The intent is to use these compounds as a sacrificial electrode layer during the electrokinetic deposition of methylmethacrylate monomer. Cylindrical reinforced concrete specimens were subjected to electrokinetic treatment and the specimens were tested to characterize porosity reduction and tensile splitting strength showing an increase in the tensile strength. In addition, nine specimens treated electro-kinetically and in long-term atmospheric exposure testing at NASA's Kennedy Space Center, seaside atmospheric exposure test site were tested to determine their corrosion rate.

Acevedo, Raul↗

Development of Reliable Life Support Systems

The life support systems on the International Space Station (ISS) are the culmination of an extensive effort encompassing development, design, and test to provide the highest possible confidence in their operation on ISS. Many years of development testing are initially performed to identify the optimum technology and the optimum operational approach. The success of this development program depends on the accuracy of the system interfaces. The critical interfaces include the specific operational environment, the composition of the waste stream to be processed and the quality of the product. Once the development program is complete, a detailed system schematic is built based on the specific design requirements, followed by component procurement, assembly, and acceptance testing. A successful acceptance test again depends on accurately simulating the anticipated environment on ISS. The ISS Water Recovery System (WRS) provides an excellent example of where this process worked, as well as lessons learned that can be applied to the success of future missions. More importantly, ISS has provided a test bed to identify these design issues. Mechanical design issues have included an unreliable harmonic drive train in the Urine Processor's fluids pump, and seals in the Water Processor's Catalytic Reactor with insufficient life at the operational temperature. Systems issues have included elevated calcium in crew urine (due to microgravity effect) that resulted in precipitation at the desired water recovery rate, and the presence of an organosilicon compound (dimethylsilanediol) in the condensate that is not well removed by the water treatment process. Modifications to the WRS to address these issues are either complete (and now being evaluated on ISS) or are currently in work to insure the WRS has the required reliability before embarking on a mission to Mars.

Carter, Layne↗

Development of Reliable Life Support Systems

The life support systems on the International Space Station (ISS) are the culmination of an extensive effort encompassing development, design, and test to provide the highest possible confidence in their operation on ISS. Many years of development testing are initially performed to identify the optimum technology and the optimum operational approach. The success of this development program depends on the accuracy of the system interfaces. The critical interfaces include the specific operational environment, the composition of the waste stream to be processed and the quality of the product. Once the development program is complete, a detailed system schematic is built based on the specific design requirements, followed by component procurement, assembly, and acceptance testing. A successful acceptance test again depends on accurately simulating the anticipated environment on ISS. The ISS Water Recovery System (WRS) provides an excellent example of where this process worked, as well as lessons learned that can be applied to the success of future missions. More importantly, ISS has provided a test bed to identify these design issues. Mechanical design issues have included an unreliable harmonic drive train in the Urine Processor's fluids pump, and seals in the Water Processor's Catalytic Reactor with insufficient life at the operational temperature. Systems issues have included elevated calcium in crew urine (due to microgravity effect) that resulted in precipitation at the desired water recovery rate, and the presence of an organosilicon compound (dimethylsilanediol) in the condensate that is not well removed by the water treatment process. Modifications to the WRS to address these issues are either complete (and now being evaluated on ISS) or are currently in work to insure the WRS has the required reliability before embarking on a mission to Mars.

Carter, Layne↗

Differential skeletal responses of hindlimb unloaded rats on a vitamin D-deficient diet to 1,25-dihydroxyvitamin D3 and its analog, seocalcitol (EB1089)

Conditions of disuse in bed rest patients, as well as microgravity experienced by astronauts are accompanied by reduced mechanical loading, reduced calcium absorption, and lower serum levels of 1,25(OH)2D3 (1,25-D), the active metabolite of vitamin D, all contributing to bone loss. To determine whether 1,25-D or a less calcemic analog, Seocalcitol or EB1089 (1 alpha,25-dihydroxy-22,24-diene-24,26,27-trihomovitamin D3) can alleviate bone loss in a rat hindlimb unloading model of disuse osteopenia, mature male rats originally on a vitamin D replete diet containing 1.01% calcium were transferred to a vitamin D-deficient diet containing 0.48% calcium and then tail suspended and treated for 28 days with vehicle, 0.05 microg/kg 1,25-D, or 0.05 microg/kg EB1089. The vitamin D-deficient diet caused a substantial decrease in bone mineral density (-8%), which may be compounded by hindlimb unloading (-10%). Exogenous 1,25-D not only prevented the bone loss but also increased the bone mineral density to greater than the baseline level (+7%). EB1089 was less effective in preventing bone loss. Analysis of site and cell-specific effects of 1,25-D and EB1089 revealed that 1,25-D was more active than EB1089 in the intestine, the site of calcium absorption, and in inducing osteoclastogenesis and bone resorption whereas EB1089 was more effective in inducing osteoblast differentiation. These studies suggest that elevating circulating 1,25-D levels presumably increasing calcium absorption can counteract bone loss induced by disuse or microgravity with its associated reductions in circulating 1,25-D and decreased calcium absorption.

Non-NASA Center↗

Interchange for Joint Research Entitled: Miniature Laser Spectrometer for Stable Isotope Measurements

As a first step in successfully measuring carbon isotopes optically we have previously demonstrated the measurement of C-13/C-12 to a precision of 0.1% using a tunable diode laser and CO2 spectral lines in the 2300/cm spectral region. This precision of 0.1% (1 per mil) for carbon isotopes is a value sufficiently precise to provide important isotopic data of interest to astrobiologists. The precision presently attainable in gases is sufficient to permit our instrument to be used in the measurement of isotopic ratios of interest to astrobiologists as well as geologists and planetary scientists. A small stable isotope laser spectrometer with a 10 cm path gas cell was designed and constructed. The cell was integrated with a liquid nitrogen cooled tunable diode laser and indium antimonide detector for evaluation. Using the small gas cell, preliminary measurements of 13C/12C in CO2 were made employing single-beam sequential acquisitions of the required spectral data. The results indicate an accuracy of 0.1% which is sufficiently high to make meaningful measurements of martian samples. In addition, improvements in the spectrometer gas handling system have been made to markedly reduce C-13/C-12 isotopic fractionation during sample gas cell loading which we expect will lead to further improvements in precision and accuracy. An important part of making isotopic ratio measurements in solid samples using diode lasers is the conversion of the elements of interest to molecules that have absorption spectra in the mid-ir spectral range accessible by tunable diode lasers. In this project we have investigated the necessary sample preparation procedures to extract carbon, an element of astrobiological importance, from model soil compounds and to convert it to CO2, a molecule with appropriate optical absorption characteristics for reliable laser spectrometer isotopic ratio measurements of 13C/12C. We have considered calcium carbonate as a model for a component of the martian regolith, and we have formulated a simple heating protocol for extracting carbon in the form of CO2.

Becker, J. F.↗

Combustion system processes leading to corrosive deposits

Degradation of turbine engine hot gas path components by high temperature corrosion can usually be associated with deposits even though other factors may also play a significant role. The origins of the corrosive deposits are traceable to chemical reactions which take place during the combustion process. In the case of hot corrosion/sulfidation, sodium sulfate was established as the deposited corrosive agent even when none of this salt enters the engine directly. The sodium sulfate is formed during the combustion and deposition processes from compounds of sulfur contained in the fuel as low level impurities and sodium compounds, such as sodium chloride, ingested with intake air. In other turbine and power generation situations, corrosive and/or fouling deposits can result from such metals as potassium, iron, calcium, vanadium, magnesium, and silicon.

Stearns, C. A.↗

Combustion system processes leading to corrosive deposits

Degradation of turbine engine hot gas path components by high temperature corrosion can usually be associated with deposits even though other factors may also play a significant role. The origins of the corrosive deposits are traceable to chemical reactions which take place during the combustion process. In the case of hot corrosion/sulfidation, sodium sulfate was established as the deposited corrosive agent even when none of this salt enters the engine directly. The sodium sulfate is formed during the combustion and deposition processes from compounds of sulfur contained in the fuel as low level impurities and sodium compounds, such as sodium chloride, ingested with intake air. In other turbine and power generation situations, corrosive and/or fouling deposits can result from such metals as potassium, iron, calcium, vanadium, magnesium, anad silicon. Previously announced in STAR as N81-23243

Stearns, C. A.↗

Deposition and material response from Mach 0.3 burner rig combustion of SRC 2 fuels

Collectors at 1173K (900 C) were exposed to the combustion products of a Mach 0.3 burner rig fueled with various industrial turbine liquid fuels from solvent refined coals. Four fuels were employed: a naphtha, a light oil, a wash solvent and a mid-heavy distillate blend. The response of four superalloys (IN-100, U 700, IN 792 and M-509) to exposure to the combustion gases from the SRC-2 naphtha and resultant deposits was also determined. The SRC-2 fuel analysis and insights obtained during the combustion experience are discussed. Particular problems encountered were fuel instability and reactions of the fuel with hardware components. The major metallic elements which contributed to the deposits were copper, iron, chromium, calcium, aluminum, nickel, silicon, titanium, zinc, and sodium. The deposits were found to be mainly metal oxides. An equilibrium thermodynamic analysis was employed to predict the chemical composition of the deposits. The agreement between the predicted and observed compounds was excellent. No hot corrosion was observed. This was expected because the deposits contained very little sodium or potassium and consisted mainly of the unreactive oxides. However, the amounts of deposits formed indicated that fouling is a potential problem with the use of these fuels.

Santoro, G. J.↗

Protecting Space Travelers from Kidney Stones: Renal Stone Risk During Space Flight

Renal stones, popularly known as kidney or bladder stones, are small rock-like objects formed in the kidneys or urinary tract by deposits of calcium and other minerals. The problem arises when the stones block the drainage of the kidney, resulting in urinary obstruction and pain. Passing these stones can be one of the most painful experiences a person will endure so doctors often prescribe pain relievers to ease the experience. Drinking plenty of fluids, which help flush waste out of the body, and eating a well-balanced diet are the first steps to preventing stones. For individuals at risk, this may not be enough, and a doctor may recommend a special diet and medications. Unfortunately, approximately 60 percent of people who have had a renal stone will experience a recurrence. This is particularly true of men, who are four to five times more likely to develop stones than women. Renal stones do not discriminate based on age; even children are at risk. Astronauts are particularly at risk of developing renal stones because they lose bone and muscle mass; calcium, other minerals, and protein normally used for bone and muscle end up in the bloodstream and then in the kidneys. Without plenty of fluid to wash them away, crystals can form and then grow into stones. This factor compounds the risk for astronauts, since they also perceive that they are less thirsty in space and will drink less than normal during the mission. To minimize all of these factors, doctors must instead treat the stone-forming compounds with medication. This study will use potassium citrate to reduce the risk of stone formation. Renal stones are never convenient, but they are a particular concern for astronauts who have limited access to treatment during flight. Researchers are examining how earthbound preventions for renal stone formation work in flight, ensuring missions are not ended prematurely due to this medical condition. During STS-107, earthbound preventions and treatments become astronauts' gain.

Whitson, Peggy↗

Determination of trace elements in triglycine sulfate solutions

Ten elements were divided into 2 groups. The elements in the first group included iron, nickel, chromium, manganese, copper, and gold. The elements in the second group included zinc, cobalt, lead, cadmium, and gold. Five ppm of each element in each group was spiked in a 1 percent triglycine sulfate (TGS) solution. Glycine was removed with 1-naphthyl isocyanate in ether medium. The glycine derivative 1-naphthyl isocyanate glycine was removed by filtration, and the filtrates were analyzed for the different elements. Analysis of these elements was performed by using the 5100 Perkin-Elmer Atomic Absorption Spectrophotometer. The result of these experiments was the observation that there was a decrease in the concentration of chromium and gold, which was interpreted to be due to the chelation of these elements by the derivative 1-naphthyl isocyanate glycine. Further research is needed to determine the concentration of other elements in triglycine sulfate (TGS) solutions. These elements will include lithium, sodium, rubidium, magnesium, calcium, strontium, barium, aluminum, and silicon. These are the most likely elements to be found in the sulfuric acid used in manufacturing the TGS crystal. Moreover, we will extend our research to investigate the structural formula of the violet colored chelated compounds, which had been formed by interaction of the derivative 1-naphthyl isocyanate glycine with the different elements, such as gold, chromium.

Tadros, Shawky H.↗

Evidence for Calcium Carbonate at the Phoenix Landing Site

The Phoenix mission has recently finished its study of the north polar environment of Mars with the aim to help understand both the current climate and to put constraints on past climate. An important part of understanding the past climate is the study of secondary minerals, those formed by reaction with volatile compounds such as H2O and CO2. This work describes observations made by the Thermal and Evolved-Gas Analyzer (TEGA) on the Phoenix Lander related to carbonate minerals. Carbonates are generally considered to be products of aqueous processes. A wet and warmer climate during the early history of Mars coupled with a much denser CO2 atmosphere are ideal conditions for the aqueous alteration of basaltic materials and the subsequent formation of carbonates. Carbonates (Mg- and Ca-rich) are predicted to be thermodynamically stable minerals in the present martian environment, however, there have been only a few indications of carbonates on the surface by a host of orbiting and landed missions to Mars. Carbonates (Mg-rich) have been suggested to be a component (2-5 wt %) of the martian global dust based upon orbital thermal emission spectroscopy. The identifications, based on the presence of a 1480 cm-1 absorption feature, are consistent with Mgcarbonates. A similar feature is observed in brighter, undisturbed soils by Mini-TES on the Gusev plains. Recently, Mg-rich carbonates have been identified in the Nili Fossae region by the CRISM instrument onboard the Mars Reconnaissance Orbiter. Carbonates have also been confirmed as aqueous alteration phases in martian meteorites so it is puzzling why there have not been more discoveries of carbonates by landers, rovers, and orbiters. Carbonates may hold important clues about the history of liquid water and aqueous processes on the surface of Mars.

Boynton, W. V.↗

Cellular localization of the Ca2+ binding TCH3 protein of Arabidopsis

TCH3 is an Arabidopsis touch (TCH) gene isolated as a result of its strong and rapid upregulation in response to mechanical stimuli, such as touch and wind. TCH3 encodes an unusual calcium ion-binding protein that is closely related to calmodulin but has the potential to bind six calcium ions. Here it is shown that TCH3 shows a restricted pattern of accumulation during Arabidopsis vegetative development. These data provide insight into the endogenous signals that may regulate TCH3 expression and the sites of TCH3 action. TCH3 is abundant in the shoot apical meristem, vascular tissue, the root columella and pericycle cells that give rise to lateral roots. In addition, TCH3 accumulation in cells of developing shoots and roots closely correlates with the process of cellular expansion. Following wind stimulation, TCH3 becomes more abundant in specific regions including the branchpoints of leaf primordia and stipules, pith parenchyma, and the vascular tissue. The consequences of TCH3 upregulation by wind are therefore spatially restricted and TCH3 may function at these sites to modify cell or tissue characteristics following mechanical stimulation. Because TCH3 accumulates specifically in cells and tissues that are thought to be under the influence of auxin, auxin levels may regulate TCH3 expression during development. TCH3 is upregulated in response to low levels of exogenous indole-3-acetic acid (IAA), but not by inactive auxin-related compounds. These results suggest that TCH3 protein may play roles in mediating physiological responses to auxin and mechanical environmental stimuli.

NASA Discipline Plant Biology↗

Possible Detection of Perchlorates by the Sample Analysis at Mars (SAM) Instrument: Comparison with Previous Missions

The first chemical analysis of soluble salts in the soil was carried out by the Phoenix Lander in the Martian Arctic [1]. Surprisingly, chlorine was present as magnesium or calcium perchlorate at 0.4 to 0.6 percent. Additional support for the identification of perchlorate came from the evolved gas analysis which detected the release of molecular oxygen at 350-550C [1]. When Mars-like soils from the Atacama Desert were spiked with magnesium perchlorate (1 percent) and heated using the Viking GC-MS protocol, nearly all the organics were combusted but a small amount was chlorinated, forming chloromethane and dichloromethane [2]. These chlorohydrocarbons were detected by the Viking GC-MS experiments when the Martian soil was analyzed but they were considered to be terrestrial contaminants [3]. Reinterpretation of the Viking results suggests <0.1 percent perchlorate and ppm levels of organic carbon at landing site 1 and 2 [2]. The suggestion of perchlorate in the Viking sites [2] has been challenged on the grounds that the detected compounds (CH3Cl and CH2Cl2) were carried from Earth [4]. Recently the Sample Analysis at Mars (SAM) instrument on board the Mars Science Laboratory (MSL) ran four samples from an aeolian bedform named Rocknest. The samples analyzed were portioned from the fifth scoop at this location. The samples were heated to 835C at 35C/min with a He flow. The SAM QMS detected a major oxygen release (300-500C) [5], coupled with the release of chlorinated hydrocarbons (chloromethane, dichloromethane, trichloromethane, and chloromethylpropene) detected both by SAM QMS and GC-MS derived from known Earth organic contaminants in the instrument [6]. Calcium perchlorate appears to be the best candidate for evolved O2 in the Rocknest samples at this time but other Cl species (e.g., chlorates) are possible and must be evaluated. The potential detection of perchlorates in Rocknest material adds weight to the argument that both Viking Landers measured signatures of perchlorates. Even if the source of the organic carbon detected is still unknown, the chlorine source was likely Martian. Two mechanisms have been hypothesized for the formation of soil perchlorate: (1) Atmospheric oxidation of chlorine; and (2) UV photooxidation of chlorides catalyzed by mineral catalysts [7]. The presence of soil perchlorates in the Martian surface has important implications for the detection of organics [2], carbonates [8] and nitrates [9] by SAM.

Navarro-Gonzalex, Rafael↗