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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 253 records · Page 14
All sourcesNASA NTRSDOE OSTI
NASA NTRS1996

State modeling and pass automation in spacecraft control

The integrated monitoring and control commercial off-the-shelf system (IMACCS), which demonstrates the feasibility of automating spacecraft monitoring and control activities through the use of state modeling, is described together with its use. The use of the system for the control and ground support of the solar, anomalous and magnetic particle explorer (SAMPEX) spacecraft is considered. A key component of IMACCS is the Altair mission control system which implements finite state modeling as an element of its expert system capability. Using the finite state modeling and state transition capabilities of the Altair mission control system, IMACCS features automated monitoring, routine pass support, anomaly resolution and emergency 'lights on again' response. Automatic orbit determination and the production of typical flight dynamics products exists. These functionalities are described.

Klein, J.↗
NASA NTRS1996

AB Initio Characterization of MgCCH, MgCCH(+), and MgC2, and Pathways to their Formation in the Interstellar Medium

A study of Mg-bearing compounds has been performed in order to determine molecular properties which are critical for planning new astronomical searches and laboratory studies. The primary focus of the work is on MgCCH, MgCCH(+), and the isomers of MgC2. Only MgCCH has been identified in laboratory studies. Additional calculations have been carried out on MgH, MgNC, MgCN, and their cations in an effort to evaluate pathways to the formation of MgCCH and MgCCH(+) in the InterStellar Medium (ISM) or in circumstellar envelopes. Correlated ab initio methods and correlation-consistent basis sets have been employed. Properties including structures, rotational constants, dipole moments, and harmonic frequencies are reported. A transition state between linear MgCC and cyclic MgC2 has been characterized and was found to yield a minimal barrier (approx. 0.5 kcal/mole), indicating easy interconversion to the cyclic form. Direct reactions in the ISM between Mg or Mg(+) and HCCH are precluded by energetic considerations, but a number of ion- molecule or neutral-neutral exchange reactions between CCH and various Mg-containing species offer plausible pathways to MgCCH or MgCCH(+). Weakly bound MgH may react with CCH to form MgCCH, but MgH has not been detected. Both MgNC and MgCN have been observed, but reactions with CCH are slightly endothermic by 1-3 kcal/mole. Although MgH(+), MgNC(+), and MgCN(+) have not been detected, their reactions with CCH to form MgCCH(+) are all exothermic. With only a small barrier separating linear MgCC and cyclic MgC2, the dissociative recombination of MgCCH(+) with an electron is expected to yield cyclic MgC2, and regenerate Mg and CCH. New astronomical searches for MgCCH, MgCCH(+), cyclic MgC2, MgNC(+), and MgCN(+) will provide further insight into organo-magnesium astrochemistry.

Woon, David E.↗
NASA NTRS1997

Rate Coefficients for Reactions of Ethynyl Radical (C2H) With HCN and CH3CN: Implications for the Formation of Comples Nitriles on Titan

Rate coefficients for the reactions of C2H + HCN yields products and C2H + CH3CN yields products have been measured over the temperature range 262-360 K. These experiments represent an ongoing effort to accurately measure reaction rate coefficients of the ethynyl radical, C2H, relevant to planetary atmospheres such as those of Jupiter and Saturn and its satellite Titan. Laser photolysis of C2H2 is used to produce C2H, and transient infrared laser absorption is employed to measure the decay of C2H to obtain the subsequent reaction rates in a transverse flow cell. Rate constants for the reaction C2H + HCN yields products are found to increase significantly with increasing temperature and are measured to be (3.9-6.2) x 10(exp 13) cm(exp 3) molecules(exp -1) s(exp -1) over the temperature range of 297-360 K. The rate constants for the reaction C2H + CH3CN yields products are also found to increase substantially with increasing temperature and are measured to be (1.0-2.1) x 10(exp -12) cm(exp 3) molecules(exp -1) s(exp -1) over the temperature range of 262-360 K. For the reaction C2H + HCN yields products, ab initio calculations of transition state structures are used to infer that the major products form via an addition/elimination pathway. The measured rate constants for the reaction of C2H + HCN yields products are significantly smaller than values currently employed in photochemical models of Titan, which will affect the HC3N distribution.

Hoobler, Ray J.↗
NASA NTRS1999

Computational Study of Field Initiated Surface Reactions for Synthesis of Diamond and Silicon

This project involves using quantum chemistry to simulate surface chemical reactions in the presence of an electric field for nanofabrication of diamond and silicon. A field delivered by a scanning tunneling microscope (STM) to a nanometer scale region of a surface affects chemical reaction potential energy surfaces (PES) to direct atomic scale surface modification to fabricate sub-nanometer structures. Our original hypothesis is that the applied voltage polarizes the charge distribution of the valence electrons and that these distorted molecular orbitals can be manipulated with the STM so as to change the relative stabilities of the electronic configurations over the reaction coordinates and thus the topology of the PES and reaction kinetics. Our objective is to investigate the effect of applied bias on surface reactions and the extent to which STM delivered fields can be used to direct surface chemical reactions on an atomic scale on diamond and silicon. To analyze the fundamentals of field induced chemistry and to investigate the application of this technique for the fabrication of nanostructures, we have employed methods capable of accurately describing molecular electronic structure. The methods we employ are density functional theory (DFT) quantum chemical (QC) methods. To determine the effect of applied bias on surface reactions we have calculated the QC PESs in various applied external fields for various reaction steps for depositing or etching diamond and silicon. We have chosen reactions which are thought to play a role in etching and the chemical vapor deposition growth of Si and diamond. The PESs of the elementary reaction steps involved are then calculated under the applied fields, which we vary in magnitude and configuration. We pay special attention to the change in the reaction barriers, and transition state locations, and search for low energy reaction channels which were inaccessible without the applied bias.

Musgrave, Charles Bruce↗
NASA NTRS1997

Can Chlorine Anion Catalyze the Reaction fo HOCl with HCl?

The reaction of HOCl + HCl -> Cl2 + H20 in the presence of Cl has been studied using ab initio methods. This reaction has been shown to have a high activation barrier of 46.5 kcal/mol. The chlorine anion, Cl- is found to catalyze the reaction, viz. two mechanisms. The first involves Cl- interacting through the concerted four-center transition state of the neutral reaction. The other mechanism involves the formation of a HCl-HOCl-Cl- intermediate which dissociates into Cl2 + Cl- + H20. The steps are found to have no barriers. The overall exothermicity is 15.5 kcal/mol.

Richardson, S. L.↗
NASA NTRS2002

Tensile Strength of Carbon Nanotubes Under Realistic Temperature and Strain Rate

Strain rate and temperature dependence of the tensile strength of single-wall carbon nanotubes has been investigated with molecular dynamics simulations. The tensile failure or yield strain is found to be strongly dependent on the temperature and strain rate. A transition state theory based predictive model is developed for the tensile failure of nanotubes. Based on the parameters fitted from high-strain rate and temperature dependent molecular dynamics simulations, the model predicts that a defect free micrometer long single-wall nanotube at 300 K, stretched with a strain rate of 1%/hour, fails at about 9 plus or minus 1% tensile strain. This is in good agreement with recent experimental findings.

Wei, Chen-Yu↗
NASA NTRS2001

Reactions of SiCl2 and SiHCl with H and Cl Atoms

Calculations have been carried out for the reaction of SiCl2 and SiHCl with H and Cl atoms. In each case, the stationary point geometries and harmonic frequencies were characterized using CASSCF/derivative methods and the cc-pVDZ basis set. Accurate energetics were obtained by combining the CCSD(T) results using the a-cc-pVTZ basis set with an extrapolation to the basis set limit using the a-cc-pVDZ, a-cc-pVTZ, and a-cc-pVQZ basis sets at the MP2 level. The geometries, energetics, and harmonic frequencies were used to obtain rate constants using conventional transition state theory or a Gorin-like model. In each case we find direct abstraction pathways compete with an addition elimination pathway. In the case of SiClH + H the two direct pathways are H abstraction which is barrierless and Cl abstraction with a barrier of 13.5 kcal/mol, while the addition elimination process has a barrier of 26.9 kcal/mol. In the case of SiCl2 + H the direct pathway is Cl abstraction with a barrier of 16.4 kcal/mol, while the addition elimination pathway has a barrier of 29.6 kcal/mol. In the case of SiClH + Cl the direct pathway is H abstraction which is barrierless and the addition elimination pathway has a barrier of 2.0 kcal/mol.

Walch, Stephen P.↗
NASA NTRS2002

Understanding the Long-Term Spectral Variability of Cygnus X-1 from BATSE and ASM Observations

We present a spectral analysis of observations of Cygnus X-1 by the RXTE/ASM (1.5-12 keV) and CGRO/BATSE (20-300 keV), including about 1200 days of simultaneous data. We find a number of correlations between intensities and hardnesses in different energy bands from 1.5 keV to 300 keV. In the hard (low) spectral state, there is a negative correlation between the ASM 1.5-12 keV flux and the hardness at any energy. In the soft (high) spectral state, the ASM flux is positively correlated with the ASM hardness (as previously reported) but uncorrelated with the BATSE hardness. In both spectral states, the BATSE hardness correlates with the flux above 100 keV, while it shows no correlation with the flux in the 20-100 keV range. At the same time, there is clear correlation between the BATSE fluxes below and above 100 keV. In the hard state, most of the variability can be explained by softening the overall spectrum with a pivot at approximately 50 keV. The observations show that there has to be another, independent variability pattern of lower amplitude where the spectral shape does not change when the luminosity changes. In the soft state, the variability is mostly caused by a variable hard (Comptonized) spectral component of a constant shape superimposed on a constant soft blackbody component. These variability patterns are in agreement with the dependence of the rms variability on the photon energy in the two states. We interpret the observed correlations in terms of theoretical Comptonization models. In the hard state, the variability appears to be driven mostly by changing flux in seed photons Comptonized in a hot thermal plasma cloud with an approximately constant power supply. In the soft state, the variability is consistent with flares of hybrid, thermal/nonthermal, plasma with variable power above a stable cold disk. Also, based on broadband pointed observations simultaneous with those of the ASM and BATSE, we find the intrinsic bolometric luminosity increases by a factor of approximately 3-4 from the hard state to the soft one, which supports models of the state transition based on a change of the accretion rate.

Zdziarski, Andrzej A.↗
NASA NTRS2002

Aspects of Supercritical Turbulence: Direct Numerical Simulation of O2/H2 and C7H16/N2 Temporal Mixing Layers

Results from Direct Numerical Simulations of temporal, supercritical mixing layers for two species systems are analyzed to elucidate species-specific turbulence aspects. The two species systems, O2/H2 and C7HG16/N2, have different thermodynamic characteristics; thus, although the simulations are performed at similar reduced pressure (ratio of the pressure to the critical pressure), the former system is dose to mixture ideality and has a relatively high solubility with respect to the latter, which exhibits strong departures from mixture ideality Due to the specified, smaller initial density stratification, the C7H16/N2 layers display higher growth and increased global molecular mixing as well as larger turbulence levels. However, smaller density gradients at the transitional state for the O2/H2 system indicate that on a local basis, the layer exhibits an enhanced mixing, this being attributed to the increased solubility and to mixture ideality. These thermodynamic features are shown to affect the irreversible entropy production (i.e. the dissipation), which is larger for the O2/H2 layer and is primarily concentrated in high density-gradient magnitude regions that are distortions of the initial density stratification boundary. In contrast, the regions of largest dissipation in the C7H16/N2 layer are located in high density-gradient magnitude regions resulting from the mixing of the two fluids.

Bellan, J.↗
NASA NTRS2002

Tensile Yielding of Multi-Wall Carbon Nanotube

The tensile yielding of multiwall carbon nanotubes (MWCNTs) has been studied using Molecular Dynamics simulations and a Transition State Theory based model. We find a strong dependence of the yielding on the strain rate. A critical strain rate has been predicted above/below which yielding strain of a MWCNT is larger/smaller than that of the corresponding single-wall carbon nanotubes. At experimentally feasible strain rate of 1% /hour and T = 300K, the yield strain of a MWCNT is estimated to be about 3-4 % higher than that of an equivalent SWCNT (Single Wall Carbon Nanotube), in good agreement with recent experimental observations.

Wei, Chenyu↗
NASA NTRS2003

Masked Proportional Routing

Distributed approach for determining a path connecting adjacent network nodes, for probabilistically or deterministically transporting an entity, with entity characteristic mu from a source node to a destination node. Each node i is directly connected to an arbitrary number J(mu) of nodes, labeled or numbered j=jl, j2, .... jJ(mu). In a deterministic version, a J(mu)-component baseline proportion vector p(i;mu) is associated with node i. A J(mu)-component applied proportion vector p*(i;mu) is determined from p(i;mu) to preclude an entity visiting a node more than once. Third and fourth J(mu)-component vectors, with components iteratively determined by Target(i;n(mu);mu),=alpha(mu).Target(i;n(mu)-1;mu)j+beta(mu).p* (i;mu)j and Actual(i;n(mu);+a(mu)j. Actual(i;n(mu)-l;mu)j+beta(mu).Sent(i;j'(mu);n(mu)-1;mu)j, are computed, where n(mu) is an entity sequence index and alpha(mu) and beta(mu) are selected numbers. In one embodiment, at each node i, the node j=j'(mu) with the largest vector component difference, Target(i;n(mu);mu)j'- Actual (i;n(mu);mu)j'. is chosen for the next link for entity transport, except in special gap circumstances, where the same link is optionally used for transporting consecutively arriving entities. The network nodes may be computer-controlled routers that switch collections of packets, frames, cells or other information units. Alternatively, the nodes may be waypoints for movement of physical items in a network or for transformation of a physical item. The nodes may be states of an entity undergoing state transitions, where allowed transitions are specified by the network and/or the destination node.

David H Wolpert↗
NASA NTRS2003

Reactive Resonances in N+N2 Exchange Reaction

Rich reactive resonances are found in a 3D quantum dynamics study of the N + N2 exchange reaction using a recently developed ab initio potential energy surface. This surface is characterized by a feature in the interaction region called Lake Eyring , that is, two symmetric transition states with a shallow minimum between them. An L2 analysis of the quasibound states associated with the shallow minimum confirms that the quasibound states associated with oscillations in all three degrees of freedom in Lake Eyring are responsible for the reactive resonances in the state-to-state reaction probabilities. The quasibound states, mostly the bending motions, give rise to strong reasonance peaks, whereas other motions contribute to the bumps and shoulders in the resonance structure. The initial state reaction probability further proves that the bending motions are the dominating factors of the reaction probability and have longer life times than the stretching motions. This is the first observation of reactive resonances from a "Lake Eyring" feature in a potential energy surface.

Wang, Dunyou↗
NASA NTRS2004

DNA in a Tunnel: A Comfy Spot for Recognition - or -The Structure of BsoBI Complexed with DNA. What can we Learn about Function via Structure Determination and how can this be Applied to Bone or Muscle Biology?

The structure and function of a biologically active molecule are related. To understand its function, it is necessary (but not always sufficient) to know the structure of the molecule. There are many ways of relating the molecular function with the structure. Mutation analysis can identify pertinent amino acids of an enzyme, or alternatively structure comparison of the of two similar molecules with different function may lead to understanding which parts are responsible for a functional aspect, or a series of "structural cartoons" - enzyme structure, enzyme plus substrate, enzyme with transition state analog, and enzyme with product - may give insight in the function of a molecule. As an example we will discuss the structure and function of the restriction enzyme BsoBI from Bacillus stearothemzophilus in complex with its cognate DNA. The enzyme forms a unique complex with DNA in that it completely encircles the DNA. The structure reveals the enzyme-DNA contacts, how the DNA is distorted compared with the canonical forms, and elegantly shows how two distinct DNA sequences can be recognized with the same efficiency. Based on the structure we may also propose a hypothesis how the enzymatic mechanism works. The knowledge gained thru studies such as this one can be used to alter the function by changing the molecular structure. Usually this is done by design of inhibitors specifically active against and fitting into an active site of the enzyme of choice. In the case of BsoBI one of the objectives of the study was to alter the enzyme specificity. In bone biology there are many candidates available for molecular study in order to explain, alter, or (temporarily) suspend activity. For example, the understanding of a pathway that negatively regulates bone formation may be a good target for drug design to stimulate bone formation and have good potential as the basis for new countermeasures against bone loss. In principle the same approach may aid muscle atrophy, radiation damage, immune response changes and other risks identified for long-duration Space travel.

vanderWoerd, Mark↗
NASA NTRS1994

New calculations on the ion-molecule processes C2H2(+) + H2 --> C2H3(+) + H and C2H2(+) + H2 --> C2H4+

New high-level quantum chemical calculations have been undertaken to understand the rates and mechanisms of the reactive and associative channels for the reactants C2H2(+) + H2. The reactive channel, which produces C2H3(+) + H, has been shown to be slightly endothermic, confirming earlier calculations at a somewhat lower level and in agreement with some recent experimental work. The associative channel, leading to C2H4+, has been shown to proceed via a transition state with negative energy relative to the reactants, so that association is predicted to be efficient. This result is in conflict with an earlier theoretical study but in agreement with low-temperature experimental measurements.

NASA Discipline Exobiology↗
NASA NTRS1996

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↗
NASA NTRS1991

Catalysis of hydrolysis and nucleophilic substitution at the P-N bond of phosphoimidazolide-activated nucleotides in phosphate buffers

Phosphoimidazolide-activated derivatives of guanosine and cytidine 5'-monophosphates, henceforth called ImpN's, exhibit enhanced rates of degradation in the presence of aqueous inorganic phosphate in the range 4.0 < or = pH < or = 8.6. This degradation is been attributed to (i) nucleophilic substitution of the imidazolide and (ii) catalysis of the P-N bond hydrolysis by phosphate. The first reaction results in the formation of nucleoside 5'-diphosphate and the second in nucleoside 5'-monophosphate. Analysis of the observed rates as well as the product ratios as a function of pH and phosphate concentration allow distinction between various mechanistic possibilities. The results show that both H2PO4- and HPO4(2-) participate in both hydrolysis and nucleophilic substitution. Statistically corrected biomolecular rate constants indicate that the dianion is 4 times more effective as a general base than the monoanion, and 8 times more effective as nucleophile. The low Bronsted value beta = 0.15 calculated for these phosphate species, presumed to act as general bases in facilitating water attack, is consistent with the fact that catalysis of the hydrolysis of the P-N bond in ImpN's has not been detected before. The beta nuc = 0.35 calculated for water, H2PO4-, HPO4(2-), and hydroxide acting as nucleophiles indicates a more associative transition state for nucleotidyl (O2POR- with R = nucleoside) transfers than that observed for phosphoryl (PO3(2-)) transfers (beta nuc = 0.25). With respect to the stability/reactivity of ImpN's under prebiotic conditions, our study shows that these materials would not suffer additional degradation due to inorganic phosphate, assuming the concentrations of phosphate, Pi, on prebiotic Earth were similar to those in the present oceans ([Pi] approximately 2.25 micromoles).

NASA Discipline Number 52-20↗
NASA NTRS1992

Design of potent substrate-analogue inhibitors of canine renin

Through a systematic study of structure-activity relationships, we designed potent renin inhibitors for use in dog models. In assays against dog plasma renin at neutral pH, we found that, as in previous studies of rat renin inhibitors, the structure at the P2 position appears to be important for potency. The substitution of Val for His at this position increases potency by one order of magnitude. At the P3 position, potency appears to depend on a hydrophobic side chain that does not necessarily have to be aromatic. Our results also support the approach of optimizing potency in a renin inhibitor by introducing a moiety that promotes aqueous solubility (an amino group) at the C-terminus of the substrate analogue. In the design of potent dog plasma renin inhibitors, the influence of the transition-state residue 4(S)-amino-3(S)-hydroxy-5-cyclohexylpentanoic acid (ACHPA)-commonly used as a substitute for the scissile-bond dipeptide to boost potency-is not obvious, and appears to be sequence dependent. The canine renin inhibitor Ac-paF-Pro-Phe-Val-statine-Leu-Phe-paF-NH2 (compound 15; IC50 of 1.7 nM against dog plasma renin at pH 7.4; statine, 4(S)-amino-3(S)-hydroxy-6-methylheptanoic acid; paF, para-aminophenylalanine) had a potent hypotensive effect when infused intravenously into conscious, sodium-depleted, normotensive dogs. Also, compound 15 concurrently inhibited plasma renin activity and had a profound diuretic effect.

Non-NASA Center↗