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Results for “kinetic pathways”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
NASA NTRS2000

A calcium-dependent protein kinase can inhibit a calmodulin-stimulated Ca2+ pump (ACA2) located in the endoplasmic reticulum of Arabidopsis

The magnitude and duration of a cytosolic Ca(2+) release can potentially be altered by changing the rate of Ca(2+) efflux. In plant cells, Ca(2+) efflux from the cytoplasm is mediated by H(+)/Ca(2+)-antiporters and two types of Ca(2+)-ATPases. ACA2 was recently identified as a calmodulin-regulated Ca(2+)-pump located in the endoplasmic reticulum. Here, we show that phosphorylation of its N-terminal regulatory domain by a Ca(2+)-dependent protein kinase (CDPK isoform CPK1), inhibits both basal activity ( approximately 10%) and calmodulin stimulation ( approximately 75%), as shown by Ca(2+)-transport assays with recombinant enzyme expressed in yeast. A CDPK phosphorylation site was mapped to Ser(45) near a calmodulin binding site, using a fusion protein containing the N-terminal domain as an in vitro substrate for a recombinant CPK1. In a full-length enzyme, an Ala substitution for Ser(45) (S45/A) completely blocked the observed CDPK inhibition of both basal and calmodulin-stimulated activities. An Asp substitution (S45/D) mimicked phosphoinhibition, indicating that a negative charge at this position is sufficient to account for phosphoinhibition. Interestingly, prior binding of calmodulin blocked phosphorylation. This suggests that, once ACA2 binds calmodulin, its activation state becomes resistant to phosphoinhibition. These results support the hypothesis that ACA2 activity is regulated as the balance between the initial kinetics of calmodulin stimulation and CDPK inhibition, providing an example in plants for a potential point of crosstalk between two different Ca(2+)-signaling pathways.

NASA Discipline Plant Biology↗
NASA NTRS1992

AMP deaminase histochemical activity and immunofluorescent isozyme localization in rat skeletal muscle

The cellular distribution of AMP deaminase (AMPda) isozymes was documented for rat soleus and plantaris muscles, utilizing immunofluorescence microscopy and immunoprecipitation methods. AMPda is a ubiquitous enzyme existing as three distinct isozymes, A, B and C, which were initially purified from skeletal muscle, liver (and kidney), and heart, respectively. AMPda-A is primarily concentrated subsarcolemmally and intermyofibrillarly within muscle cells, while isozymes B and C are concentrated within non-myofiber elements of muscle tissue. AMPda-B is principally associated with connective tissues surrounding neural elements and the muscle spindle capsule, and AMPda-C is predominantly associated with circulatory elements, such as arterial and venous walls, capillary endothelium, and red blood cells. These specific localizations, combined with documented differences in kinetic properties, suggest multiple functional roles for the AMPda isozymes or temporal segregation of similar AMPda functions. Linkage of the AMPda substrate with adenosine production pathways at the AMP level and the localization of isozyme-C in vascular tissue suggest a regulatory role in the microcirculation.

Non-NASA Center↗
NASA NTRS1999

Sequential and coordinated action of phytochromes A and B during Arabidopsis stem growth revealed by kinetic analysis

Photoreceptor proteins of the phytochrome family mediate light-induced inhibition of stem (hypocotyl) elongation during the development of photoautotrophy in seedlings. Analyses of overt mutant phenotypes have established the importance of phytochromes A and B (phyA and phyB) in this developmental process, but kinetic information that would augment emerging molecular models of phytochrome signal transduction is absent. We have addressed this deficiency by genetically dissecting phytochrome-response kinetics, after having solved the technical issues that previously limited growth studies of small Arabidopsis seedlings. We show here, with resolution on the order of minutes, that phyA initiated hypocotyl growth inhibition upon the onset of continuous red light. This primary contribution of phyA began to decrease after 3 hr of irradiation, the same time at which immunochemically detectable phyA disappeared and an exclusively phyB-dependent phase of inhibition began. The sequential and coordinated actions of phyA and phyB in red light were not observed in far-red light, which inhibited growth persistently through an exclusively phyA-mediated pathway.

NASA Discipline Plant Biology↗
NASA NTRS1990

Oxidation kinetics of model compounds of metabolic waste in supercritical water

In this NASA-funded study, the oxidation kinetics of methanol and ammonia in supercritical water have been experimentally determined in an isothermal plug flow reactor. Theoretical studies have also been carried out to characterize key reaction pathways. Methanol oxidation rates were found to be proportional to the first power of methanol concentration and independent of oxygen concentration and were highly activated with an activation energy of approximately 98 kcal/mole over the temperature range 480 to 540 C at 246 bar. The oxidation of ammonia was found to be catalytic with an activation energy of 38 kcal/mole over temperatures ranging from 640 to 700 C. An elementary reaction model for methanol oxidation was applied after correction for the effect of high pressure on the rate constants. The conversion of methanol predicted by the model was in good agreement with experimental data.

Webley, Paul A.↗
NASA NTRS2007

Shifting Surface Currents in the Northern North Atlantic Ocean

Analysis of surface drifter tracks in the North Atlantic Ocean from the time period 1990 to 2006 provides the first evidence that the Gulf Stream waters can have direct pathways to the Nordic Seas. Prior to 2000, the drifters entering the channels leading to the Nordic Seas originated in the western and central subpolar region. Since 2001 several paths from the western subtropics have been present in the drifter tracks leading to the Rockall Trough through which the most saline North Atlantic Waters pass to the Nordic Seas. Eddy kinetic energy from altimetry shows also the increased energy along the same paths as the drifters, These near surface changes have taken effect while the altimetry shows a continual weakening of the subpolar gyre. These findings highlight the changes in the vertical structure of the northern North Atlantic Ocean, its dynamics and exchanges with the higher latitudes, and show how pathways of the thermohaline circulation can open up and maintain or increase its intensity even as the basin-wide circulation spins down.

Hakkinen, Sirpa↗
NASA NTRS2018

Growth of Bio Sensor Materials by Physical Vapor Transport Method

Recently there is a big thrust on bio-inspired sensors and there has been a large rise in the investment and expectations for nanotechnology to meet these goals. For in situ sensor development materials deposition on substrate is essential part of device development. Physical vapor deposition (PVD), chemical vapor deposition (CVD) and molecular organic vapor deposition methods have developed for growth of semiconductor bulk and thin film growth with some modifications have been used for these materials. Oxides and other elements of the VI group such as sulfides and selenides are key components in the skins of many species. Growth of ordered structures containing these elements have been achieved by using PVD method. This paper describes effect of growth parameters during PVD growth on the quality of materials. Growth kinetics and mechanism will be discussed for the vertical and horizontal growth reactors. Since most of the efficient materials systems are multinary and in many cases non-congruent, PVD provides a pathway to grow materials below melting temperature.

Sachs, David↗
NASA NTRS2024

Eddy-Mediated Turbulent Mixing of Oxygen in the Equatorial Pacific

In the tropical Pacific, weak ventilation and intense microbial respiration at depth give rise to a low dissolved oxygen (O 2 ) environment that is thought to be ventilated primarily by the equatorial current system (ECS). The role of mesoscale eddies and vertical mixing as potential pathways of O 2 supply in this region, however, remains poorly known due to sparse observations and coarse model resolution. Using an eddy resolving simulation of ocean circulation and biogeochemistry, we assess the contribution of these processes to the O 2 budget balance and find that vertical mixing of O 2 , which is modulated by the surface wind speed and the vertical shear of the eddying currents, contributes substantially to the replenishment of O 2 in the upper equatorial Pacific thermocline, complementing the advective supply of O 2 by the ECS and meridional circulation at depth. These transport processes vary seasonally in conjunction with the wind: mixing of O 2 into the upper thermocline is strongest during boreal summer and fall when the vertical shear and eddy kinetic energy are intensified. The relationship between eddy activity and the downward mixing of O 2 arises from the modulation of equatorial turbulence by Tropical Instability Waves via their impacts on the vertical shear. This interaction of processes across scales sustains a local pathway of O 2 delivery into the equatorial Pacific interior and highlights the need for adequate observations and models of turbulent mixing and mesoscale processes for understanding and predicting the fate of the tropical Pacific O 2 content in a warmer and more stratified ocean.

Eddy-Mediated↗
NASA NTRS2018

Stable Isotope Fractionation in Titan Aerosol Formation

Stable isotope ratio measurements are a powerful tool used to understand both ancient and modern planetary processes. Instruments on the Cassini- Huygens spacecraft along with ground-based observations have measured several isotope pairs, including C-13/C-12 and N-15/N-14, in Titan's atmosphere. This includes isotopic measurements of the major atmospheric species, CH4 and N2, along with HCN, HC3N, C2H2. C2H6 and C4H2. However, the isotopic fractionation of Titan's organic aerosol has not conclusively been measured and therefore the effect of aerosol formation as an isotopic fractionation pathway in Titan's atmosphere has not been considered. Laboratory studies have measured the carbon and/or nitrogen isotopic fractionation of Titan aerosol analogs. [18] found that the carbon fractionation of photochemical organic aerosol analogs are more enriched in C-13. This enrichment in the aerosol analogs is opposite of what is predicted for photochemical products by the kinetic isotope effect. Additionally, both [16] and [18] found that the nitrogen fractionation in the organic aerosol analogs are opposite of what is observed in Titan's atmospheric N2 and HCN, with the aerosol analogs being a light nitrogen sink. Here we monitor the gas phase during photochemical aerosol analog production as a function of reaction time. In a recirculation experiment, the isotopic fractionation of carbon within the gas-phase products is measured as the CH4 reservoir is depleted. This allows us to monitor the isotopic fractionation pathway during photochemical aerosol analog formation.

Ugelow, M. S.↗
NASA NTRS1994

Kinetic and mechanistic analysis of dinucleotide and oligonucleotide formation from the 5'-phosphorimidazolide of adenosine on Na(+)-montmorillonite

The rate constants for the condensation reaction of the 5'-phosphorimidazolide of adenosine (ImpA) to form dinucleotides and oligonucleotides have been measured in the presence of Na(+)-volclay (a Na(+)-montmorillonite) in pH 8 aqueous solution at 25 degrees C. The rates of the reaction of ImpA with an excess of adenosine 5'-monophosphoramidate (NH2pA), P1,P2-diadenosine 5',5'-pyrophosphate (A5'ppA), or adenosine 5'-monophosphate (5'-AMP or pA) in the presence of the montmorillonite to form NH2pA3'pA, A5'ppA3'pA, and pA3'pA, respectively, were measured. Only 3',5'-linked products were observed. The magnitude of the rate constants decrease in the order NH2pA3'pA > A5'-ppA3'pA > pA3'pA. The binding of ImpA to montmorillonite was measured, and the adsorption isotherm was determined. The binding of ImpA to montmorillonite and the formation of higher oligonucleotides is not observed in the absence of salts. Mg2+ enhances binding and oligonucleotide formation more than Ca2+ and Na+. The rate constants for the oligonucleotide formation were determined from the reaction products formed from 10 to 40 mM ImpA in the presence of Na(+)-montmorillonite using the computer program SIMFIT. The magnitudes of the rate constants for the formation of oligonucleotides increased in the order 2-mer < 3-mer < 4-mer ... 7-mer. The rate constants for dinucleotide and trinucleotide formation are more than 1000 times larger than those measured in the absence of montmorillonite. The rate constants for the formation of dinucleotide, trinucleotide, and tetranucleotide are 41,2.6, and 3.7 times larger than those for the formation of oligo(G)s with a poly(C) template. The hydrolysis of ImpA was accelerated 35 times in the presence of the montmorillonite. The catalytic ability of montmorillonite to form dinucleotides and oligonucleotides is quantitatively evaluated and possible pathways for oligo(A) formation are proposed.

NASA Discipline Exobiology↗
NASA NTRSDate not supplied

Isotopic Tracers for CO 2 Produced During A Planetary Impact Into Limestone Target Rocks

Terrestrial meteorite impacts have been directly linked with multiple mass extinction events throughout Earth’s history. Among these impacts, those that land in sedimentary target rocks are thought to generate large quantities of CO 2 via decarbonation. This injection of CO 2 into the atmosphere has the potential to alter the climate and threaten terrestrial habitability. The magnitude of this change depends upon the net amount of CO 2 released, which is controlled by how much CO 2 is produced by the impact, how much CO 2 is removed by back-reactions after the impact, and other post-impact CO 2 sinks. To interrogate the behavior of CO 2 release into the impact atmosphere, we present carbon (δ 13 C), oxygen (δ 18 O), and clumped (Δ 47 ) isotope results from carbonate clasts preserved within the impact breccia of the Steen River Impact Structure (SRIS) in Alberta, Canada. These clasts exhibit a ~65‰ range in δ 13 C and a ~5‰ variation in δ 18 O. However, while δ 13 C and δ 18 O are positively correlated, Δ 47 unexpectedly has a negative relationship with δ 13 C and δ 18 O. Based on prior assumptions, there would either be (1) no relationship with carbonate Δ 47 and the bulk ratios because Δ 47 would be reset at extreme impact temperatures, or (2) Δ 47 would have a positive correlation with the bulk ratios, reflecting gradual Δ 47 ‘resetting.’ To reconcile the SRIS result with these expectations, we conducted a series of in vacuo heating experiments at temperatures above calcite decomposition. As predicted by Rayleigh fractionation, these heating experiments generated depletions in δ 13 C and δ 18 O that increased with reaction time. Mimicking the SRIS results, these experiments also produced concomitant increases in Δ 47 . Using an adaptation of a mechanistic model for decomposition fractionation (Hayles & Killingsworth, 2022) we hypothesize that these exotic isotope trends are caused by Rayleigh fractionation and a Δ 47 kinetic isotope effect that results from the disproportionation of O to CaO and CO 2 during thermal decomposition. This high Δ 47 CO 2 subsequently exchanges with the residual CaCO 3 . This work highlights a potential pathway for identifying and quantifying CO 2 generation by impacts and builds on the relatively limited literature characterizing the behavior of carbonate clumped isotopes at very high geologic temperatures.

Multi-isotope systems↗
NASA NTRSDate not supplied

Zircon (U-Th)/He Impact Crater Thermochronometry and the Effects of Shock Microstructures on Helium Diffusion Kinetics

Accurate and precise age determination of impact cratering events remains challenging and often contentious; less than half of all known craters are regarded as accurately and precisely dated. Zircon (U-Th)/He (ZHe) dating of impactites can be employed to date medium to large impact structures as ZHe ages can be fully reset in minutes at T >1000°C, a plausible scenario in the central melt pool. In contrast, complete resetting of ZHe at 200-300°C, encountered near the crater margins or due to post-impact hydrothermal overprinting, may take >103-6 years. To test the reliability of ZHe impact dating, we have quantified the effects of shock-induced microstructures on helium diffusion kinetics in well-characterized variably shocked zircon. We investigated samples from two impact structures, the Chicxulub multi-ring crater and Ries complex crater, to compare diffusion kinetics from structures with different size, age, and hydrothermal system longevity. Shock microstructures were characterized by backscattered-electron imaging prior to determining the He diffusion kinetics by prograde and retrograde fractional-release experiments via light-bulb furnace with incremental step-heating (10°C) from 300°C to 600°C. Next, we examine the internal interconnectivity and sizes of the diffusion domains by EBSD. While we found that zircon with few shock microstructures exhibited no marked deviation from helium diffusion kinetics of undamaged zircon, zircon grains with planar microstructures and granular textures are characterized by a dramatic decrease in helium retentivity due to the reduction in the effective domain size and the introduction of interconnected fast diffusion pathways. A subset of grains were ZHe dated and showed that less deformed grains yielded a weighted mean age within error of the accepted impact ages, while the grains with planar microstructures or granular textures gave systematically younger ages. These new diffusion data and ZHe ages demonstrate that highly shocked grains are unsuitable for ZHe impact crater dating. Therefore, detailed characterization of impact-induced microstructures is critical for determining accurate ZHe impact ages and offers the possibility of investigating post-impact hydrothermal circulation.

Zircon↗
NASA NTRS1997

Physiological Response of Plants Grown on Porous Ceramic Tubes

This research involves the manipulation of the root-zone water potential for the purposes of discriminating the rate limiting step in the inorganic nutrient uptake mechanism utilized by higher plants. This reaction sequence includes the pathways controlled by the root-zone conditions such as water tension and gradient concentrations. Furthermore, plant based control mechanisms dictated by various protein productions are differentiated as well. For the nutrients limited by the environmental availability, the kinetics were modeled using convection and diffusion equations. Alternatively, for the nutrients dependent upon enzyme manipulations, the uptakes are modeled using Michaelis-Menten kinetics. In order to differentiate between these various mechanistic steps, an experimental apparatus known as the Porous Ceramic Tube - Nutrient Delivery System (PCT-NDS) was used. Manipulation of the applied suction pressure circulating a nutrient solution through this system imposes a change in the matric component of the water potential. This compensates for the different osmotic components of water potential dictated by nutrient concentration. By maintaining this control over the root-zone conditions, the rate limiting steps in the uptake of the essential nutrients into tomato plants (Lycopersicon esculentum cv. Cherry Elite) were differentiated. Results showed that the uptake of some nutrients were mass transfer limited while others were limited by the enzyme kinetics. Each of these were adequately modeled with calculations and discussions of the parameter estimations provided.

Tsao, David↗
NASA NTRS2003

The ARG1-LIKE2 gene of Arabidopsis functions in a gravity signal transduction pathway that is genetically distinct from the PGM pathway

The arl2 mutants of Arabidopsis display altered root and hypocotyl gravitropism, whereas their inflorescence stems are fully gravitropic. Interestingly, mutant roots respond like the wild type to phytohormones and an inhibitor of polar auxin transport. Also, their cap columella cells accumulate starch similarly to wild-type cells, and mutant hypocotyls display strong phototropic responses to lateral light stimulation. The ARL2 gene encodes a DnaJ-like protein similar to ARG1, another protein previously implicated in gravity signal transduction in Arabidopsis seedlings. ARL2 is expressed at low levels in all organs of seedlings and plants. arl2-1 arg1-2 double mutant roots display kinetics of gravitropism similar to those of single mutants. However, double mutants carrying both arl2-1 and pgm-1 (a mutation in the starch-biosynthetic gene PHOSPHOGLUCOMUTASE) at the homozygous state display a more pronounced root gravitropic defect than the single mutants. On the other hand, seedlings with a null mutation in ARL1, a paralog of ARG1 and ARL2, behave similarly to the wild type in gravitropism and other related assays. Taken together, the results suggest that ARG1 and ARL2 function in the same gravity signal transduction pathway in the hypocotyl and root of Arabidopsis seedlings, distinct from the pathway involving PGM.

NASA Discipline Plant Biology↗
NASA NTRS1986

Variations in the HCN/HNC abundance ratio in the Orion molecular cloud

Observations of the rare isotopes of HCN and HNC have been used to determine the relative abundance of these two chemical isomers along the central ridge of the Orion molecular cloud. The abundance ratio HCN/HNC decreases by more than an order of magnitude from the relatively warm plateau and hot core sources toward the KL nebula to the colder, more quiescent clouds to the north and south. Even in the cooler regions, however, the ratio is an order of magnitude larger than that found in previous investigations of cold dark clouds. The kinetic temperature in the regions studied is determined from new observations of methylacetylene (CH3CCH), together with other recent estimates of the gas temperature near KL. The results suggest that the warmer portions of the cloud are dominated by different chemical pathways that those in the general instellar cloud material.

Goldsmith, Paul F.↗
NASA NTRS2015

Prototype Biology-Based Radiation Risk Module Project

Biological effects of space radiation and risk mitigation are strategic knowledge gaps for the Evolvable Mars Campaign. The current epidemiology-based NASA Space Cancer Risk (NSCR) model contains large uncertainties (HAT #6.5a) due to lack of information on the radiobiology of galactic cosmic rays (GCR) and lack of human data. The use of experimental models that most accurately replicate the response of human tissues is critical for precision in risk projections. Our proposed study will compare DNA damage, histological, and cell kinetic parameters after irradiation in normal 2D human cells versus 3D tissue models, and it will use a multi-scale computational model (CHASTE) to investigate various biological processes that may contribute to carcinogenesis, including radiation-induced cellular signaling pathways. This cross-disciplinary work, with biological validation of an evolvable mathematical computational model, will help reduce uncertainties within NSCR and aid risk mitigation for radiation-induced carcinogenesis.

Terrier, Douglas↗
NASA NTRS1994

Ammonia on the prebiotic Earth: Iron(II) reduction of nitrite

Theories for the origin of life require the availability of reduced nitrogen. In the non-reducing atmosphere suggested by geochemical evidence, production in the atmosphere and survival of NH3 against photochemical destruction are problematic. Electric discharges and impact shocks would produce NO rather than HCN or NH3. Conversion of NO to nitrous and nitric acid (by way of HNO) and precipitation in acid rain would provide a source of fixed nitrogen to the early ocean. One solution to the NH3 problem may have been the reduction of nitrite/nitrate in the ocean with aqueous ferrous iron, Fe(2+): 6Fe(+2) + 7 H2O + NO2(-) yields 3Fe2O3 + 11 H(+) + NH3. We have measured the kinetics of this reaction as a function of temperature, pH, and concentrations of salts, Fe(+2), and NO2(-). Cations (Na(+), Mg(2+), K(+)) and anions (Cl(-), Br(-), SO4(2-)) increase the rate by factors of 4 to 8. Although a competing pathway yields N2, the efficiency of the conversion of nitrite to ammonia ranges from 25% to 85%. Nitrate reduction was not consistently reproducible; however, when it was observed, its rate was slower by at least 8X than that of nitrite reduction. If the prebiotic atmosphere contained 0.2 to 10 atmospheres CO2 as suggested by Walker (1985), the Fe(+2) concentration and the rate would have been limited by siderite (FeCO3) solubility.

Summers, David P.↗
NASA NTRS2002

Transition from Gaseous Compounds to Aerosols in Titan's Atmosphere

We investigate the chemical transition of simple molecules like C2H2 and HCN into aerosol particles in the context of Titan's atmosphere. Experiments that synthesize analogs (tholins) for these aerosols can help understand and constrain these polymerization mechanisms. Using information available from these experiments, we suggest chemical pathways that can link simple molecules to macromolecules, that will be the precursors to aerosol particles: polymers of acetylene and cyanoacetylene, polycyclic aromatics (PAHs), polymers of HCN and other nitriles, and polynes. Although our goal here is not to build a detailed kinetic model for this transition, we propose parameterizations to estimate the production rates of these macromolecules, their C/N and C/H ratios, and the loss of parent molecules (C2H2, HCN, HC3N and other nitriles, C6H6) from the gas phase to the haze. We use a 1-dimensional photochemical model of Titan's atmosphere to estimate the formation rate of precursors macromolecules. We find a production zone slightly lower than 200 km altitude with a total production rate of 4 x 10(exp -14) g/ sq cm s and a C/N approx. = 4. These results are compared with experimental data, and to microphysical models requirements. The Cassini/Huygens mission will bring a detailed picture of the haze distribution and properties, that will be a great challenge for our understanding of those chemical processes.

Lebonnois, Sebastien↗
NASA NTRS2003

Modeling beta-adrenergic control of cardiac myocyte contractility in silico

The beta-adrenergic signaling pathway regulates cardiac myocyte contractility through a combination of feedforward and feedback mechanisms. We used systems analysis to investigate how the components and topology of this signaling network permit neurohormonal control of excitation-contraction coupling in the rat ventricular myocyte. A kinetic model integrating beta-adrenergic signaling with excitation-contraction coupling was formulated, and each subsystem was validated with independent biochemical and physiological measurements. Model analysis was used to investigate quantitatively the effects of specific molecular perturbations. 3-Fold overexpression of adenylyl cyclase in the model allowed an 85% higher rate of cyclic AMP synthesis than an equivalent overexpression of beta 1-adrenergic receptor, and manipulating the affinity of Gs alpha for adenylyl cyclase was a more potent regulator of cyclic AMP production. The model predicted that less than 40% of adenylyl cyclase molecules may be stimulated under maximal receptor activation, and an experimental protocol is suggested for validating this prediction. The model also predicted that the endogenous heat-stable protein kinase inhibitor may enhance basal cyclic AMP buffering by 68% and increasing the apparent Hill coefficient of protein kinase A activation from 1.0 to 2.0. Finally, phosphorylation of the L-type calcium channel and phospholamban were found sufficient to predict the dominant changes in myocyte contractility, including a 2.6x increase in systolic calcium (inotropy) and a 28% decrease in calcium half-relaxation time (lusitropy). By performing systems analysis, the consequences of molecular perturbations in the beta-adrenergic signaling network may be understood within the context of integrative cellular physiology.

Non-NASA Center↗