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At least 451 records · Page 25

Dissolution kinetics of a lunar glass simulant at 25 degrees C: the effect of pH and organic acids

The dissolution kinetics of a simulated lunar glass were examined at pH 3, 5, and 7. Additionally, the pH 7 experiments were conducted in the presence of citric and oxalic acid at concentrations of 2 and 20 mM. The organic acids were buffered at pH 7 to examine the effect of each molecule in their dissociated form. At pH 3, 5, and 7, the dissolution of the synthetic lunar glass was observed to proceed via a two-stage process. The first stage involved the parabolic release of Ca, Mg, Al, and Fe, and the linear release of Si. Dissolution was incongruent, creating a leached layer rich in Si and Ti which was verified by transmission electron microscopy (TEM). During the second stage the release of Ca, Mg, Al, and Fe was linear. A coupled diffusion/surface dissolution model was proposed for dissolution of the simulated lunar glass at pH 3, 5, and 7. During the first stage the initial release of mobile cations (i.e., Ca, Mg, Al, Fe) was limited by diffusion through the surface leached layer of the glass (parabolic release), while Si release was controlled by the hydrolysis of the Si-O-Al bonds at the glass surface (linear release). As dissolution continued, the mobile cations diffused from greater depths within the glass surface. A steady-state was then reached where the diffusion rate across the increased path lengths equalled the Si release rate from the surface. In the presence of the organic acids, the dissolution of the synthetic lunar glass proceeded by a one stage process. The release of Ca, Mg, Al, and Fe followed a parabolic relationship, while the release of Si was linear. The relative reactivity of the organic acids used in the experiments was citrate > oxalate. A thinner leached layer rich in Si/Ti, as compared to the pH experiments, was observed using TEM. Rate data suggest that the chemisorption of the organic anion to the surface silanol groups was responsible for enhanced dissolution in the presence of the organic acids. It is proposed that the increased rate of Si release is responsible for the one stage parabolic release of mobile cations and the relatively thin leached layer compared to experiments at pH 3 and 5.

NASA Discipline Life Support Systems↗

Kinetic and mechanistic analysis of nonenzymatic, template-directed oligoribonucleotide ligation

The role of divalent cations in the mechanism of pyrophosphate-activated, template-directed oligoribonucleotide ligation has been investigated. The dependence of the reaction rate on Mg2+ concentration suggests a kinetic scheme in which a Mg2+ ion must bind before ligation can proceed. Mn2+, Ca2+, Sr2+, and Ba2+ can also catalyze the reaction. Although Pb2+ and Zn2+ do not catalyze the reaction in the absence of other divalent ions, they significantly modulate the reaction rate when added in the presence of Mg2+, with Pb2+ stimulating the reaction (up to 65-fold) and Zn2+ inhibiting the reaction. The logarithm of the ligation rate increases linearly, with slope of 0.95, as a function of pH, indicating that the reaction involves a single critical deprotonation step. The ligation rates observed with the different divalent metal ion catalysts (Mn2+ > Mg2+ > Ca2+ > Sr2+ = Ba2+) vary inversely with the pKa values of their bound water molecules. The pH profile and these relative ligation rates suggest a mechanism in which a metal-bound hydroxide ion located near the ligation junction promotes catalysis, most likely by deprotonation of the hydroxl nucleophile. The effects of changing either the leaving group or the attacking hydroxyl, together with the large delta S(++) value for oligonucleotide ligation (about -20 eu), are consistent with an associative transition state.

Non-NASA Center↗

Protein kinetics during and after long-duration spaceflight on MIR

Human spaceflight is associated with a loss of body protein. Bed rest studies suggest that the reduction in the whole body protein synthesis (PS) rate should be approximately 15%. The objectives of this experiment were to test two hypotheses on astronauts and cosmonauts during long-duration (>3 mo) flights on MIR: that 1) the whole body PS rate will be reduced and 2) dietary intake and the PS rate should be increased postflight because protein accretion is occurring. The 15N glycine method was used for measuring whole body PS rate before, during, and after long-duration spaceflight on the Russian space station MIR. Dietary intake was measured together with the protein kinetics. Results show that subjects lost weight during flight (4.64 +/- 1.0 kg, P < 0.05). Energy intake was decreased inflight (2,854 +/- 268 vs. 2,145 +/- 190 kcal/day, n = 6, P < 0.05), as was the PS rate (226 +/- 24 vs. 97 +/- 11 g protein/day, n = 6, P < 0.01). The reduction in PS correlated with the reduction in energy intake (r2 = 0.86, P < 0.01, n = 6). Postflight energy intake and PS returned to, but were not increased over, the preflight levels. We conclude that the reduction in PS found was greater than predicted from ground-based bed rest experiments because of the shortfall in dietary intake. The expected postflight anabolic state with increases in dietary intake and PS did not occur during the first 2 wk after landing.

STS-40 Shuttle Project↗

The kinetics of translocation and cellular quantity of protein kinase C in human leukocytes are modified during spaceflight

Protein kinase C (PKC) is a family of serine/threonine kinases that play an important role in mediating intracellular signal transduction in eukaryotes. U937 cells were exposed to microgravity during a space shuttle flight and stimulated with a radiolabeled phorbol ester ([3H]PDBu) to both specifically label and activate translocation of PKC from the cytosol to the particulate fraction of the cell. Although significant translocation of PKC occurred at all g levels, the kinetics of translocation in flight were significantly different from those on the ground. In addition, the total quantity of [3H]PDBu binding PKC was increased in flight compared to cells at 1 g on the ground, whereas the quantity in hypergravity (1.4 g) was decreased with respect to 1 g. Similarly, in purified human peripheral blood T cells the quantity of PKCdelta varied in inverse proportion to the g level for some experimental treatments. In addition to these novel findings, the results confirm earlier studies which showed that PKC is sensitive to changes in gravitational acceleration. The mechanisms of cellular gravisensitivity are poorly understood but the demonstrated sensitivity of PKC to this stimulus provides us with a useful means of measuring the effect of altered gravity levels on early cell activation events.

short duration↗

Kinetics, Ca2+ dependence, and biophysical properties of integrin-mediated mechanical modulation of transmitter release from frog motor nerve terminals

Neurotransmitter release from frog motor nerve terminals is strongly modulated by change in muscle length. Over the physiological range, there is an approximately 10% increase in spontaneous and evoked release per 1% muscle stretch. Because many muscle fibers do not receive suprathreshold synaptic inputs at rest length, this stretch-induced enhancement of release constitutes a strong peripheral amplifier of the spinal stretch reflex. The stretch modulation of release is inhibited by peptides that block integrin binding of natural ligands. The modulation varies linearly with length, with a delay of no more than approximately 1-2 msec and is maintained constant at the new length. Moreover, the stretch modulation persists in a zero Ca2+ Ringer and, hence, is not dependent on Ca2+ influx through stretch activated channels. Eliminating transmembrane Ca2+ gradients and buffering intraterminal Ca2+ to approximately normal resting levels does not eliminate the modulation, suggesting that it is not the result of release of Ca2+ from internal stores. Finally, changes in temperature have no detectable effect on the kinetics of stretch-induced changes in endplate potential (EPP) amplitude or miniature EPP (mEPP) frequency. We conclude, therefore, that stretch does not act via second messenger pathways or a chemical modification of molecules involved in the release pathway. Instead, there is direct mechanical modulation of release. We postulate that tension on integrins in the presynaptic membrane is transduced mechanically into changes in the position or conformation of one or more molecules involved in neurotransmitter release, altering sensitivity to Ca2+ or the equilibrium for a critical reaction leading to vesicle fusion.

Non-NASA Center↗

Nutritional value of protein hydrolysis products (oligopeptides and free amino acids) as a consequence of absorption and metabolism kinetics

When pigs were submitted to duodenal infusion of solutions containing a large percentage of small peptides (PEP) or free amino acids with the same pattern (AAL) amino acids appear in the portal blood more rapidly and more uniformly after infusion of PEP then after infusion of AAL, with the notable exception of methionine for which the opposite was true. These differences were lowered when a carbohydrate (maltose dextrin) was present in the solution, but nevertheless remained significant for the first hour after the infusion. The long-term (8-hour) uptake of free amino acids into the liver and the peripheral tissues differed in profile according to the nature of the duodenal infusion. Peripheral uptake was appreciably less well balanced after infusion of free amino acids (deficiency of threonine and phenylalanine) than after infusion of small peptides (deficiency of methionine). Accordingly, in the rat, under conditions of discontinuous enteral nutrition the mixture of small peptides was of greater nutritive value than the mixture of free amino acids. It thus appears that the absorption kinetics which results in important variations in the temporal distribution of free amino acids in the tissues may be at the origin of transitory imbalances in tissue amino acid uptake, and as a result of a lower nutritive value.

Intestinal Absorption/drug effects↗

Deriving the intermediate spectra and photocycle kinetics from time-resolved difference spectra of bacteriorhodopsin. The simpler case of the recombinant D96N protein

The bacteriorhodopsin photocycle contains more than five spectrally distinct intermediates, and the complexity of their interconversions has precluded a rigorous solution of the kinetics. A representation of the photocycle of mutated D96N bacteriorhodopsin near neutral pH was given earlier (Varo, G., and J. K. Lanyi. 1991. Biochemistry. 30:5008-5015) as BRhv-->K<==>L<==>M1-->M2--> BR. Here we have reduced a set of time-resolved difference spectra for this simpler system to three base spectra, each assumed to consist of an unknown mixture of the pure K, L, and M difference spectra represented by a 3 x 3 matrix of concentration values between 0 and 1. After generating all allowed sets of spectra for K, L, and M (i.e., M1 + M2) at a 1:50 resolution of the matrix elements, invalid solutions were eliminated progressively in a search based on what is expected, empirically and from the theory of polyene excited states, for rhodopsin spectra. Significantly, the average matrix values changed little after the first and simplest of the search criteria that disallowed negative absorptions and more than one maximum for the M intermediate. We conclude from the statistics that during the search the solutions strongly converged into a narrow region of the multidimensional space of the concentration matrix. The data at three temperatures between 5 and 25 degrees C yielded a single set of spectra for K, L, and M; their fits are consistent with the earlier derived photocycle model for the D96N protein.

NASA Program Exobiology↗

Using Non-Linear Statistical Methods with Laboratory Kinetic Data

This paper will demonstrate the usefulness of standard non-linear statistical analysis on ICR and SIFT kinetic data. The specific systems used in the demonstration are the isotopic and change transfer reactions in the system of H2O+/D2O, H30+/D2O, and other permutations.

non-linear analysis kinetic isotopic permutations ↗

(abstract) Fundamental Mechanisms of Electrode Kinetics and Alkali Metal Atom Transport at the Alkali Beta'-Alumina/Porous Electrode/Alkali Metal Vapor Three Phase Boundary

The mechanisms of electrode kinetics and mass transport of alkali metal oxidation and alkali metal cation reduction at the solid electrolyte/porous electrode boundary as well as alkali metal transport through porous metal electrodes has important applications in optimizing device performance in alkali metal thermal to electric converter (AMTEC) cells which are high temperature, high current density electrochemical cells. Basic studies of these processes also affords the opportunity to investigate a very basic electrochemical reaction over a wide range of conditions; and a variety of mass transport modes at high temperatures via electrochemical techniques. The temperature range of these investigations covers 700K to 1240K; the alkali metal vapor pressures range from about 10(sup -2) to 10(sup 2) Pa; and electrodes studied have included Mo, W, Mo/Na(sub 2)MoO(sub 4), W/Na(sub 2)WO(sub 4), WPt(sub x), and WRh(sub x) (1.0 < x < 6.0 ) with Na at Na-beta'-alumina, and Mo with K at K-beta'-alumina. Both liquid metal/solid electrolyte/alkali metal vapor and alkali metal vapor/solid electrolyte/vapor cells have been used to characterize the reaction and transport processes. We have previously reported evidence of ionic, free molecular flow, and surface transport of sodium in several types of AMTEC electrodes.

electrode kinetics thermal to electric conversion ↗

Kinetics and Mechanism of the CIO + CIO Reaction: Pressure and Temperature Dependences of the Bimolecular and Termolecular Channels andThermal Decomposition of Chlorine Peroxide, CIOOCI

The kinetics and mechanism of the CIO + CIO reaction and the thermal decomposition of CIOOCI were studied using the flash photolysis/long path ultraviolet absorption technique. Pressure and temperature dependences were determined for the rate coefficients for the bimolecular and termolecular reaction channels, and for the thermal decompositon of CIOOCI.

Kinetics Thermal Decomposition Biomolecul↗

Design, Fabrication, and Testing of Lumped Element Kinetic inductance Detectors for 3 mm CMB Observations

Kinetic inductance detectors (KIDs) are a promising technology for low-noise, highly-multiplexible mm- and submm-wave detection. KIDs have a number of advantages over other detector technologies, which make them an appealing option in the cosmic microwave background B-mode anisotropy search, including passive frequency domain multiplexing and relatively simple fabrication, but have suffered from challenges associated with noise control. Here we describe design and fabrication of a 20-pixel prototype array of lumped element molybdenum KIDs. We show Q, frequency and temperature measurements from the array under dark conditions. We also present evidence for a double superconducting gap in molybdenum.

cosmic microwave background↗

Partial Overhaul and Initial Parallel Optimization of KINETICS, a Coupled Dynamics and Chemistry Atmosphere Model

KINETICS is a coupled dynamics and chemistry atmosphere model that is data intensive and computationally demanding. The potential performance gain from using a supercomputer motivates the adaptation from a serial version to a parallelized one. Although the initial parallelization had been done, bottlenecks caused by an abundance of communication calls between processors led to an unfavorable drop in performance. Before starting on the parallel optimization process, a partial overhaul was required because a large emphasis was placed on streamlining the code for user convenience and revising the program to accommodate the new supercomputers at Caltech and JPL. After the first round of optimizations, the partial runtime was reduced by a factor of 23; however, performance gains are dependent on the size of the data, the number of processors requested, and the computer used.

KINETICS↗

Closed Loop Terminal Guidance Navigation for a Kinetic Impactor Spacecraft

A kinetic impactor spacecraft is a viable method to deflect an asteroid which poses a threat to the Earth. The technology to perform such a deflection has been demonstrated by the Deep Impact (DI) mission, which successfully collided with comet Tempel 1 in July 2005 using an onboard autonomous navigation system, called AutoNav, for the terminal phase of the mission. In this paper, we evaluate the ability of AutoNav to impact a wide range of scenarios that an deflection mission could encounter, varying parameters such as the approach velocity, phase angle, size of the asteroid, and the determination of spacecraft attitude. Using realistic Monte Carlo simulations, we tabulated the probability of success of the deflection as a function of these parameters, and the highest sensitivity to be due the spacecraft attitude determination mode. In addition, we also specifically analyzed the impact probability for a proposed mission which would send an impactor to the asteroid 1999RQ36. We conclude with some recommendations for future work.

closed loop guidance↗

Superconducting kinetic inductance photon detectors.

We are investigating a novel superconducting detector and readout method that could lead to photon counting, energy resolving focal plane arrays. This concept is intrinsically different from STJ and TES detectors, and in principle could deliver large pixel counts, high sensitivity, and Fano-limited spectral resolution in the ptical/UV/X-ray bands. The readout uses the monotonic relation between the kinetic surface inductance L***subs***, of a superconductor and the density of quasiparticles n, which holds even at temperatures far below T***subc***. This allows a sensitive readout of the number of excess quasiparticles in the detector by monitoring the transmission phase of a resonant circuit. The most intriguing aspect of this concept is that passive frequency multiplexing could be used to read out ~ l0***super4*** detectors with a single HEMT amplifier. Single x-ray events have been observed in prototype detectors.

kinetic↗