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NASA NTRS1994

Atmospheric chemistry of the reaction ClO + O2 reversible reaction ClO (center dot) O2: Where it stands, what needs to be done, and why?

Possible existence and chemistry of ClO (center dot) O2 was originally proposed to explain the Norrish-Neville effect that O2 suppresses chlorine photosensitized loss of ozone. It was also thought that ClO (center dot) O2 might have some atmospheric chemistry significance. Recently, doubts have been cast on this proposal, because certain laboratory data seem to imply that the equilibrium constant of the title reaction is so small that ClO (center dot) O2 may be too unstable to matter. However, those data create only a superficial illusion to that effect, because on a closer analysis they do not disprove a moderately stable and chemically significant ClO (center dot) O2. Furthermore, our state-of-the-science accurate computational chemistry calculations also suggest that ClO (center dot) O2 may be a weakly bound ClOOO radical with a reactive (2)A ground electronic state. There is therefore a need to design and perform definitive experimental tests of the existence and chemistry of the ClO (center dot) O2 species, which we discuss and which have the potential to mediate the chlorine-catalyzed stratospheric ozone depletion.

Prasad, Sheo S.↗

NASA NTRS2000

Preparation and Characterization of Fluorescent Derivatives of Chicken Egg White Lysozyme

Fluorescence is one of the most versatile and powerful tools for the study of macromolecules. While most proteins are intrinsically fluorescent, working at crystallization concentrations require the use of covalently prepared derivatives added as tracers. This approach requires derivatives that do not markedly affect the crystal packing. We have prepared a number of fluorescent derivatives of chicken egg white lysozyme with probes bound to one of two different sites on the protein molecule. Lucifer yellow, cascade blue, and 5-(2-aminoethyl)aminonapthalene-l-sulfonic acid (EDANS) have been attached to the side chain carboxyl of asp101 using a carbodiimide coupling procedure. asp101 lies within the active site cleft, and it is believed that the probes are at least partially "buried" within that cleft. Lucifer yellow and MANS probes with iodoacetamide reactive groups have been bound to hisl5, located on the "back side" of the molecule relative to the active site. The fluorescently labeled protein is readily purified from the starting material by cation exchange chromatography. All the derivatives fluoresce in both the solution and the crystalline states. Fluorescence characterization has focused on determining the bound probe quantum yields, lifetimes, absorption and emission spectra, and quenching by added solutes in comparison to the free probe. No appreciable changes are found in the lifetimes of any of the probes except for cascade blue, where Tau(sub free) = 3.52 ns vrs Tau(sub bound) = 2.8 ns. Spectral shifts are found in most cases. Particularly strong quenching upon binding is found in the case of the cascade blue derivative, likely due to probe interactions with the active site cleft. While none of the asp101 bound probes are well quenched by commonly employed solutes, such as potassium and sodium iodide, acrylamide, primuline, the chloride salts of manganese, cesium, and cobalt, trifluoroacetamide, trichloroethanol, and thallium iodide, in those cases where quenching is observed the bound probe is less efficiently quenched relative to the free probe. This indicates that the bound probes are less accessible to the bulk solution, an expected finding for attachment within the active site cleft. Attempts have been made to bind other molecules to these sites, with varying success. Interestingly, all three probes contain one or more sulfonate ((Ar-S03)-) groups. We have not been successful in binding analogous probes without sulfate groups such as pyrene, or with derivatized sulfonate groups such as dansyl type probes, analogous to MANS but where the sulfonate group is derivatized, Ar-S02-N2C2H7. None of the probes is rigidly bound to the protein, i.e., they all have a probe motion superimposed on that of the protein.

Sumida, John↗

NASA NTRS1982

Radiative lifetimes and dipole moments of the A 2Sigma/+/, B 2Sigma /+/, and C 2Sigma/+/ states of OH

After describing independent theoretical studies of the eigenfunctions of the X 2Pi and excited A 2Sigma(+), B 2Sigma(+), and C 2Sigma(+) states of OH, results are presented for the transition dipole moments connecting each excited state to the others and to the ground state. The radiative lifetimes derived from calculation of the bound-bound and bound-free vibrational band transition probabilities are compared with measured values, confirming recent measurements of the A 2Sigma(+) and C 2Sigma(+) states but not the lifetimes measured for the B 2Sigma(+) state.

Langhoff, S. R.↗

NASA NTRS1970

Method of statistical filtering

Minimal formula for bounding the cross correlation between a random forcing function and the state error when this correlation is unknown is used in optimal linear filter theory applications. Use of the bound results in overestimation of the estimation-error covariance.

Battin, R. H.↗

NASA NTRS2018

A Common Probe Design for Multiple Planetary Destinations

Atmospheric probes have been successfully flown to planets and moons in the solar system to conduct in-situ measurements. They include the Pioneer Venus multi-probes, the Galileo Jupiter probe, and Huygens probe. Probe mission concepts to five destinations, including Venus, Jupiter, Saturn, Uranus, and Neptune, have all utilized similar-shaped aeroshells and concept of operations, namely a 45 deg sphere cone shape with high density heatshield material and parachute system for extracting the descent vehicle from the aeroshell. Each concept designed its probe to meet specific mission requirements and to optimize mass, volume, and cost. At the 2017 IPPW, NASA Headquarters postulated that a common aero-shell design could be used successfully for multiple destinations and missions. This "common probe" design could even be assembled with multiple copies, properly stored, and made available for future NASA missions, potentially realizing savings in cost and schedule and reducing the risk of losing technologies and skills difficult to sustain over decades. Thus the NASA Planetary Science Division funded a study to investigate whether a common probe design could meet most, if not all, mission needs to the five planetary destinations with extreme entry environments. The Common Probe study involved four NASA Centers and addressed these issues, including constraints and inefficiencies that occur in specifying a common design.Study methodology: First, a notional payload of instruments for each destination was defined based on priority measurements from the Planetary Science Decadal Survey. Steep and shallow entry flight path angles (EFPA) were defined for each planet based on qualification and operational g-load limits for current, state-of-the-art instruments. Interplanetary trajectories were then identified for a bounding range of EFPA. Next, 3-DoF simulations for entry trajectories were run using the entry state vectors from the interplanetary trajectories. Aeroheating correlations were used to generate stagnation point convective and radiative heat flux profiles for several aeroshell shapes and entry masses. High fidelity thermal response models for various TPS materials were used to size stagnation point thicknesses, with margins based on previous studies. Backshell TPS masses were assumed based on scaled heat fluxes from the heatshield and also from previous mission concepts.

Hwang, Helen H.↗

NASA NTRS1977

The influence of autoionization accompanied by excitation on dielectronic recombination and ionization equilibrium

In the process of dielectronic recombination, the doubly excited state formed by radiationless capture may autoionize preferentially into an excited state of the recombining ion. This additional autoionization process has not been discussed in previous treatments of dielectronic recombination. The dielectronic recombination rates for certain nonhydrogenic Fe ions, although still larger than the direct radiative recombination rates, are found to be substantially reduced by the inclusion of the additional autoionization rate in the branching ratio for the stabilizing radiative transition. Consequently, the temperatures of maximum equilibrium abundance are significantly lower than those predicted by recent calculations. Finally, the radiative energy loss rate coefficients are calculated for radiation processes involving electron Fe-ion collisions in high-temperature plasmas. Electron impact excitation of resonance line radiation is the dominant radiative cooling mechanism in steady-state plasmas at temperatures where ions with bound electrons are abundant. However, it is found that the radiation emitted during dielectronic recombination can be more important than direct recombination radiation and bremsstrahlung.

Jacobs, V. L.↗

NASA NTRS1984

Stress intensity factors in a reinforced thick-walled cylinder

An elastic thick-walled cylinder containing a radial crack is considered. It is assumed that the cylinder is reinforced by an elastic membrane on its inner surface. The model is intended to simulate pressure vessels with cladding. The formulation of the problem is reduced to a singular integral equation. Various special cases including that of a crack terminating at the cylinder-reinforcement interface are investigated and numerical examples are given. Results indicate that in the case of the crack touching the interface the crack surface displacement derivative is finite and consequently the stress state around the corresponding crack tip is bounded; and generally, for realistic values of the stiffness parameter, the effect of the reinforcement is not very significant.

Tang, R.↗

NASA NTRS1985

The enigma of the Uranian satellites' orbital eccentricities

The eccentricity decay times for the Uranian satellites are calculated using recent observations (Brown et al., 1982) of the diameters and orbital elements of the satellites and assuming reasonable dissipation functions and rigidities for icy satellites. For the outer two satellites, Titania and Oberon, the decay times are found to be very long, whereas the inner three satellites, Miranda, Ariel, and Umbriel, have decay times on the order of 10 to the 7th to 10 to the 8th years and have a near-commensurability in their mean motions that cannot force their eccentricities. There are several possible solutions for the lack of resonant forcing: (1) the reported eccentricities are incorrect, and are very nearly zero, (2) the reported mean motions are incorrect, and an exact commensurability exists, (3) the physical properties assumed for the satellites are grossly in error, and (4) the system is evolving rapidly, perhaps from a previous state of higher eccentricity. A new lower bound of about 17,000 on the dissipation function of Uranus is calculated from the mass of Ariel and its proximity to Uranus.

Squyres, S. W.↗

NASA NTRS1986

Transpression as the main deformational event in an Archaean greenstone belt, northeastern Minnesota

Deformed and metamorphosed sedimentary and volcanic rocks of the Vermilion district constitute an Archean greenstone belt trending east-west between higher grade rocks of the Vermilion Granitic Complex to the north and the Giants Range batholith to the south. Metamorphic grade is low throughout, being lowest in the center of the belt (chlorite zone of the greenschist facies). All the measured strain, a cleavage or schistosity, and a mineral lineation in this belt are attributed to the main phase of deformation D sub 2 that followed an earlier nappe-forming event D sub 1, which left little evidence of penetrative fabric. Previous work assumed that the D sub 2 deformation resulted from north-south compression across the district. It is now believed that a significant component of this deformation resulted from dextral shear across the whole region. Thus the Vermilion fault, a late-state largely strike-slip structure that bounds the Vermilion district to the north, may simply be the latest, most brittle expression of a shear regime that was much more widespread in space and time. Features that are indicative of shear include ductile shear zones with sigmoidal foliation patterns, highly schistose zones with the development of shear bands, feldspar clasts or pyrite cubes with asymmetric pressure shadows, and the fact that the asymmetry of the F sub 2 folds is predominantly Z for at least 15 km south of the Vermilion fault.

Hudleston, P. J.↗

NASA NTRS1986

Optimal landing of a helicopter in autorotation

The landing of a helicopter in autorotation is formulated as a nonlinear optimal control problem. A unique feature in the present formulation is the addition of path inequality constraints on both the control and the state vectors. The control variable inequality constraint is a reflection of the limitation on the rotor thrust coefficient. The state-variable inequality constraint is an upper bound on the vertical sink-rate of the helicopter during descent. Optimal trajectories are calculated for entry conditions well within the height-velocity (H-V) restriction curve, with the helicopter initially in hover or in forward flight. The optimal solutions exhibited control techniques similar to those used by helicopter pilots in actual autorotational landings. The study indicates that, subject to pilot acceptability, a substantial reduction could be made in the H-V restriction zone using optimal control techniques.

Lee, A. Y.↗

NASA NTRS1986

Stability regions for multiloop LQ-regulated systems with state estimators

This note investigates the closed-loop stability of linear, time-invariant systems controlled by linear-quadratic-Gaussian (LQG) type controllers, when the actuators have nonlinearities. The nonlinearities N(sigma) are assumed to violate the standard LQ robustness condition either for values of sigma away from sigma = 0, or in a neighborhood of sigma = 0. The cases with an exponentially stable state estimator, and an estimator with ultimately bounded estimation error are considered, and expressions are obtained for the regions of attraction and ultimate boundedness.

Joshi, S. M.↗

NASA NTRS1992

Direct model reference adaptive control with application to flexible robots

A modification to a direct command generator tracker-based model reference adaptive control (MRAC) system is suggested in this paper. This modification incorporates a feedforward into the reference model's output as well as the plant's output. Its purpose is to eliminate the bounded model following error present in steady state when previous MRAC systems were used. The algorithm was evaluated using the dynamics for a single-link flexible-joint arm. The results of these simulations show a response with zero steady state model following error. These results encourage further use of MRAC for various types of nonlinear plants.

Steinvorth, Rodrigo↗

NASA NTRS2000

Fluorescence Studies of Protein Crystal Nucleation

We have postulated that, in the case of tetragonal chicken egg white lysozyme, crystal growth occurs by the addition of pre-critical nuclei sized n-mers that form in the bulk solution, and that the n-mer growth units were multiples of the tetrameric 4(sub 3) helical structure. These have the strongest intermolecular bonds in the crystal and are therefore likely to be the first species formed. High resolution AFM studies provide strong supporting evidence for this model, but the data also suggest that the actual species in solution may not be identical in structure to that found in the crystal. We are using fluorescence resonance energy transfer (FRET) to study the initial solution phase self-assembly process, using covalent fluorescent derivatives which crystallize in the characteristic P4(sub 3)2(sub 1)2(sub 1) space group. FRET studies are being carried out between the cascade blue (CB-lys, donor, Ex(sub max) 366 nm, Em 420 nm) and lucifer yellow (LY-lys, acceptor, Ex(sub max) 430 nm, Em 528 nm) asp101 derivatives. The estimated R(sub 0) for this probe pair, the distance where 50% of the donor energy is transferred to the acceptor, is approx. 1.2 nm, compared to 2.2 nm between the side chain carboxyls of adjacent asp101's in the crystalline 4(sub 3) helix. The short donor lifetime of 2.80 ns (chi(sup 2) = 0.644), coupled with the large average distances between the molecules (greater than or equal to 50 nm) in solution, ensure that any energy transfer observed is not due to random diffusive interactions. Lifetime data show that CB-lys has a single lifetime when it is the only species in solution. Similarly, LY-lys also exhibits a single lifetime of 4.63 ns (chi(sup 2) = 0.42) when alone in solution. Addition of LY-lys to CB-lys results in the appearance of a third lifetime component of 0.348ns for the CB-lys. The fractional intensities of the different species present can be used to estimate the distribution of monomer and n-mers in solution. The self-association process is a function of the protein concentration relative to the saturation concentration, and observing it in dilute solution (conc. less than or equal to 10(exp -5)M) requires that the experiments be performed under low solubility conditions, i.e., low temperatures and high salt concentrations. Data from preliminary steady state FRET studies with N-terminal bound pyrene acetic acid (PAA-lys, donor, Ex 340 nm, Em 376 nm) and asp101 LY-lys as an acceptor showed a consistent trend of decreasing donor fluorescence intensity with increasing total protein concentration. The FRET data have been obtained at pH 4.6, 0.1M NaAc buffer, at 5 and 7% NaCl, 4 C. The corresponding C(sub sat) values are 0.471 and 0.362 mg/ml (approx. 3.3 and approx. 2.5 x 10(exp -5)M respectively). The donor fluorescence decrease is more pronounced at7% NaCl, consistent with the expected increased intermolecular interactions at higher salt concentrations as reflected in the lower solubility. Results from these and other ongoing studies will be discussed in conjunction with an emerging model for how tetragonal lysozyme crystals nucleate and the relevance of that model to other proteins.

Pusey, Marc↗

NASA NTRS2009

Conical-Domain Model for Estimating GPS Ionospheric Delays

The conical-domain model is a computational model, now undergoing development, for estimating ionospheric delays of Global Positioning System (GPS) signals. Relative to the standard ionospheric delay model described below, the conical-domain model offers improved accuracy. In the absence of selective availability, the ionosphere is the largest source of error for single-frequency users of GPS. Because ionospheric signal delays contribute to errors in GPS position and time measurements, satellite-based augmentation systems (SBASs) have been designed to estimate these delays and broadcast corrections. Several national and international SBASs are currently in various stages of development to enhance the integrity and accuracy of GPS measurements for airline navigation. In the Wide Area Augmentation System (WAAS) of the United States, slant ionospheric delay errors and confidence bounds are derived from estimates of vertical ionospheric delay modeled on a grid at regularly spaced intervals of latitude and longitude. The estimate of vertical delay at each ionospheric grid point (IGP) is calculated from a planar fit of neighboring slant delay measurements, projected to vertical using a standard, thin-shell model of the ionosphere. Interpolation on the WAAS grid enables estimation of the vertical delay at the ionospheric pierce point (IPP) corresponding to any arbitrary measurement of a user. (The IPP of a given user s measurement is the point where the GPS signal ray path intersects a reference ionospheric height.) The product of the interpolated value and the user s thin-shell obliquity factor provides an estimate of the user s ionospheric slant delay. Two types of error that restrict the accuracy of the thin-shell model are absent in the conical domain model: (1) error due to the implicit assumption that the electron density is independent of the azimuthal angle at the IPP and (2) error arising from the slant-to-vertical conversion. At low latitudes or at mid-latitudes under disturbed conditions, the accuracy of SBAS systems based upon the thin-shell model suffers due to the presence of complex ionospheric structure, high delay values, and large electron density gradients. Interpolation on the vertical delay grid serves as an additional source of delay error. The conical-domain model permits direct computation of the user s slant delay estimate without the intervening use of a vertical delay grid. The key is to restrict each fit of GPS measurements to a spatial domain encompassing signals from only one satellite. The conical domain model is so named because each fit involves a group of GPS receivers that all receive signals from the same GPS satellite (see figure); the receiver and satellite positions define a cone, the satellite position being the vertex. A user within a given cone evaluates the delay to the satellite directly, using (1) the IPP coordinates of the line of sight to the satellite and (2) broadcast fit parameters associated with the cone. The conical-domain model partly resembles the thin-shell model in that both models reduce an inherently four-dimensional problem to two dimensions. However, unlike the thin-shell model, the conical domain model does not involve any potentially erroneous simplifying assumptions about the structure of the ionosphere. In the conical domain model, the initially four-dimensional problem becomes truly two-dimensional in the sense that once a satellite location has been specified, any signal path emanating from a satellite can be identified by only two coordinates; for example, the IPP coordinates. As a consequence, a user s slant-delay estimate converges to the correct value in the limit that the receivers converge to the user s location (or, equivalently, in the limit that the measurement IPPs converge to the user s IPP).

Sparks, Lawrence↗

NASA NTRS2013

Powered Descent Guidance with General Thrust-Pointing Constraints

The Powered Descent Guidance (PDG) algorithm and software for generating Mars pinpoint or precision landing guidance profiles has been enhanced to incorporate thrust-pointing constraints. Pointing constraints would typically be needed for onboard sensor and navigation systems that have specific field-of-view requirements to generate valid ground proximity and terrain-relative state measurements. The original PDG algorithm was designed to enforce both control and state constraints, including maximum and minimum thrust bounds, avoidance of the ground or descent within a glide slope cone, and maximum speed limits. The thrust-bound and thrust-pointing constraints within PDG are non-convex, which in general requires nonlinear optimization methods to generate solutions. The short duration of Mars powered descent requires guaranteed PDG convergence to a solution within a finite time; however, nonlinear optimization methods have no guarantees of convergence to the global optimal or convergence within finite computation time. A lossless convexification developed for the original PDG algorithm relaxed the non-convex thrust bound constraints. This relaxation was theoretically proven to provide valid and optimal solutions for the original, non-convex problem within a convex framework. As with the thrust bound constraint, a relaxation of the thrust-pointing constraint also provides a lossless convexification that ensures the enhanced relaxed PDG algorithm remains convex and retains validity for the original nonconvex problem. The enhanced PDG algorithm provides guidance profiles for pinpoint and precision landing that minimize fuel usage, minimize landing error to the target, and ensure satisfaction of all position and control constraints, including thrust bounds and now thrust-pointing constraints.

Carson, John M., III↗

NASA NTRS2019

ASPIRE Aerodynamic Models and Flight Performance

The Advanced Supersonic Parachute Inflation Research Experiments (ASPIRE) project waslaunched to develop the capability for testing supersonic parachutes at Mars-relevant conditions.Three initial parachute tests, targeted as a risk-reduction activity for NASA's upcoming Mars2020 mission, successfully tested two candidate parachute designs and provided valuable data onparachute inflation, forces, and aerodynamic behavior. Design of the flight tests depended onflight mechanics simulations which in turn required aerodynamic models for the payload, andthe parachute. Computational Fluid Dynamics (CFD) was used to generate these models preflightand they are compared against the flight data after the tests. For the payload, thereconstructed aerodynamic behavior is close to the pre-flight predictions, but the uncertaintiesin the reconstructed data are high due to the low dynamic pressures and accelerations duringthe flight period of comparison. For the parachute, the predicted time to inflation agrees wellwith the pre-flight model; the peak aerodynamic force and the steady state drag on the parachuteare within the bounds of the pre-flight models, even as the models over-predict the parachutedrag at supersonic Mach numbers. Notably, the flight data do not show the transonic dragdecrease predicted by the pre-flight model. The ASPIRE flight tests provide previouslyunavailable valuable data on the performance of a large full-scale parachute behind a slenderleading body at Mars-relevant Mach number, dynamic pressure and parachute loads. TheASPIRE results are used to propose a new model for the parachute drag behind slender bodiesto aid future experiments.

Muppidi, Suman↗

NASA NTRS2019

ASPIRE Aerodynamic Models and Flight Performance

The Advanced Supersonic Parachute Inflation Research Experiments (ASPIRE) project waslaunched to develop the capability for testing supersonic parachutes at Mars-relevant conditions.Three initial parachute tests, targeted as a risk-reduction activity for NASA's upcomingMars2020 mission, successfully tested two candidate parachute designs and provided valuabledata on parachute inflation, forces, and aerodynamic behavior. Design of the flight tests dependedon flight mechanics simulations which in turn required aerodynamic models for the payload, andthe parachute. Computational Fluid Dynamics (CFD) was used to generate these models preflightand are compared against the flight data after the tests. For the payload, the reconstructedaerodynamic behavior is close to the pre-flight predictions, but the uncertainties in thereconstructed data are high due to the low dynamic pressures and accelerations during the flightperiod of comparison. For the parachute, the predicted time to inflation agrees well with the preflightmodel; the peak aerodynamic force and the steady state drag on the parachute are withinthe bounds of the pre-flight models, even as the models over-predict the parachute drag atsupersonic Mach numbers. Notably, the flight data does not show the transonic drag decreasepredicted by the pre-flight model. The ASPIRE flight tests provide previously unavailablevaluable data on the performance of a large full-scale parachute behind a slender leading bodyat Mars-relevant Mach number, dynamic pressure and parachute loads. This data is used topropose a new model for the parachute drag behind slender bodies to aid future experiments.

Muppidi, Suman↗

NASA NTRS2005

Real-Time System Verification by Kappa-Induction

We report the first formal verification of a reintegration protocol for a safety-critical, fault-tolerant, real-time distributed embedded system. A reintegration protocol increases system survivability by allowing a node that has suffered a fault to regain state consistent with the operational nodes. The protocol is verified in the Symbolic Analysis Laboratory (SAL), where bounded model checking and decision procedures are used to verify infinite-state systems by k-induction. The protocol and its environment are modeled as synchronizing timeout automata. Because k-induction is exponential with respect to k, we optimize the formal model to reduce the size of k. Also, the reintegrator's event-triggered behavior is conservatively modeled as time-triggered behavior to further reduce the size of k and to make it invariant to the number of nodes modeled. A corollary is that a clique avoidance property is satisfied.

Pike, Lee S.↗