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All sourcesNASA NTRSDOE OSTI
NASA NTRS1991

Acridine orange staining reaction as an index of physiological activity in Escherichia coli

The assumption that the acridine orange (AO) color reaction may be used as an index of physiological activity was investigated in laboratory grown Escherichia coli. Spectrofluorometric observations of purified nucleic acids, ribosomes and the microscopic color of bacteriophage-infected cells stained with AO confirmed the theory that single-stranded nucleic acids emit orange to red fluorescence while those that are double-stranded fluoresce green in vivo. Bacteria growing actively in a rich medium could be distinguished from cells in stationary phase by the AO reaction. Cells from log phase appeared red, whereas those in stationary phase were green. However, this differentiation was not seen when the bacteria were grown in a minimal medium or when a variation of the staining method was used. Also, shifting bacteria in stationary phase to starvation conditions rapidly changed their AO staining reaction. Boiling and exposure to lethal concentrations of azide and formalin resulted in stationary-phase cells that appeared red after staining but bacteria killed with chlorine remained green. These findings indicate that the AO staining reaction may be suggestive of physiological activity under defined conditions. However, variables in staining and fixation procedures as well as uncertainties associated with mixed bacterial populations in environmental samples may produce results that are not consistent with the classical interpretation of this reaction. The importance of validating the putative physiological implications of this staining reaction is stressed.

NASA Discipline Number 04-10↗
NASA NTRS1992

Reaction cycle and thermodynamics in bacteriorhodopsin

Light causes the all-trans to 13-cis isomerization of the retinal in bacteriorhodopsin; the thermal relaxation leading back to the initial state drives proton transport first via proton transfer between the retinal Schiff base and D85 and then between the Schiff base and D96. The reaction sequence and thermodynamics of this photocycle are described by measuring time-resolved absorption changes with a gated multichannel analyzer between 100 ns and 100 ms, at six temperatures between 5 degrees C and 30 degrees C. Analysis of the energetics of the chromophore reaction sequence is on the basis of a recently proposed model (Varo & Lanyi, Biochemistry 30, 5016-5022, 1991) which consists of a single cycle and many reversible reactions: BR -hv-->K<==>L<==>M1-->M2<==>N<==>O-->BR. The existence of the M1-->M2 reaction, which functions as the switch in the proton transfer, is confirmed by spectroscopic evidence. The calculated thermodynamic parameters indicate that the exchange of free energy between the protein and the protons is at the switch step. Further, a large entropy decrease at this reaction suggests a protein conformation change which will conserve delta G for driving the completion of the reaction cycle. The results provide insights to mechanism and energy coupling in this system, with possible relevance to the general question of how ion pumps function.

Review↗
NASA NTRS1991

Nucleotides as nucleophiles: reactions of nucleotides with phosphoimidazolide activated guanosine

An earlier study of the reaction of phosphoimidazolide activated nucleosides (ImpN) in aqueous phosphate buffers indicated two modes of reaction of the phosphate monoanion and dianion. The first mode is catalysis of the hydrolysis of the P-N bond in ImpN's which leads to imidazole and nucleoside 5'-monophosphate. The second represents a nucleophilic substitution of the imidazole to yield the nucleoside 5'-diphosphate. This earlier study thus served as a model for the reaction of ImpN with nucleoside monophosphates (pN) because the latter can be regarded as phosphate derivatives. In the present study we investigated the reaction of guanosine 5'-phosphate-2-methylimidazolide, 2-MeImpG, in the presence of pN (N = guanosine, adenosine and uridine) in the range 6.9 less than or equal to pH less than or equal to 7.7. We observed that pN's do act as nucleophiles to form NppG, and as general base to enhance the hydrolysis of the P-N bond in 2-MeImpG, i.e. pN show the same behavior as inorganic phosphate. The kinetic analysis yields the following rate constants for the dianion pN2-: knpN = 0.17 +/- 0.02 M-1 h-1 for nucleophilic attack and khpN = 0.11 +/- 0.07 M-1 h-1 for general base catalysis of the hydrolysis. These rate constants which are independent of the nucleobase compare with kp.2 = 0.415 M-1 h-1 and khp2. = 0.217 M-1 h-1 for the reactions of HPO4(2-). In addition, this study shows that under conditions where pN presumably form stacks, the reaction mechanism remains unchanged although in quantitative terms stacked pN are somewhat less reactive. Attack by the 2'-OH and 3'-OH groups of the ribose moiety in amounts greater than or equal to 1% is not observed; this is attributed to the large difference in nucleophilicity in the neutral pH range between the phosphate group and the ribose hydroxyls. This nucleophilicity rank is not altered by stacking.

NASA Discipline Exobiology↗
NASA NTRS2007

Quantum Chemical Evaluation of the Astrochemical Significance of Reactions between S Atom and Acetylene or Ethylene

Addition-elimination reactions of S atom in its P-3 ground state with acetylene (C2H2) and ethylene (C2H4) were characterized with both molecular orbital and density functional theory calculations employing correlation consistent basis sets in order to assess the likelihood either reaction might play a general role in astrochemistry or a specific role in the formation of S2 (X (sup 3 SIGMA (sub g) (sup -)) via a mechanism proposed by Saxena and Misra (Mon. Not. R. Astron. Soc. 1995, 272, 89). The acetylene and ethylene reactions proceed through C2H2S ((sup 3)A")) and C2H4S ((sup 3)A")) intermediates, respectively, to yield HCCS ((sup 2)II)) and C2H3S ((sup 2)A')). Substantial barriers were found in the exit channels for every combination of method and basis set considered in this work, which effectively precludes hydrogen elimination pathways for both S + C2H2 and S + C2H4 in the ultracold interstellar medium where only very modest barriers can be surmounted and processes without barriers tend to predominate. However, if one or both intermediates is formed and stabilized efficiently under cometary or dense interstellar cloud conditions, they could serve as temporary reservoirs for S atom and participate in reactions such as S + C2H2S (right arrow) S2 = C2H2 or S + C2H4S (right arrow) S2 + C2H4. For formation and stabilization to be efficient, the reaction must possess a barrier height small enough to be surmountable at low temperatures yet large enough to prevent redissociation to reactants. Barrier heights computed with B3LYP and large basis sets are very low, but more rigorous QCISD(T) and RCCSD(T) results indicate that the barrier heights are closer to 3-4 kcal/mol. The calculations therefore indicate that S + C2H2 or S + C2H4 could contribute to the formation of S2 in comets and may serve as a means to gauge coma temperature. The energetics of the ethylene reaction are more favorable.

Woon, David E.↗
NASA NTRS2008

Sensitivity of Polar Stratospheric Ozone Loss to Uncertainties in Chemical Reaction Kinetics

Several recent observational and laboratory studies of processes involved in polar stratospheric ozone loss have prompted a reexamination of aspects of our understanding for this key indicator of global change. To a large extent, our confidence in understanding and projecting changes in polar and global ozone is based on our ability to simulate these processes in numerical models of chemistry and transport. The fidelity of the models is assessed in comparison with a wide range of observations. These models depend on laboratory-measured kinetic reaction rates and photolysis cross sections to simulate molecular interactions. A typical stratospheric chemistry mechanism has on the order of 50- 100 species undergoing over a hundred intermolecular reactions and several tens of photolysis reactions. The rates of all of these reactions are subject to uncertainty, some substantial. Given the complexity of the models, however, it is difficult to quantify uncertainties in many aspects of system. In this study we use a simple box-model scenario for Antarctic ozone to estimate the uncertainty in loss attributable to known reaction kinetic uncertainties. Following the method of earlier work, rates and uncertainties from the latest laboratory evaluations are applied in random combinations. We determine the key reactions and rates contributing the largest potential errors and compare the results to observations to evaluate which combinations are consistent with atmospheric data. Implications for our theoretical and practical understanding of polar ozone loss will be assessed.

Kawa, S. Randolph↗
NASA NTRS2013

Inflight Performance of Cassini Reaction Wheel Bearing Drag in 1997-2013

As the first spacecraft to achieve orbit at Saturn in 2004, Cassini has collected science data throughout its four-year prime mission (2004-08), and has since been approved for a first and second extended missions through September 2017. Cassini is a three-axis stabilized spacecraft. It uses reaction wheels to achieve high level of spacecraft pointing stability that is needed during imaging operations of several science instruments. The Cassini flight software makes in-flight estimates of reaction wheel bearing drag torque and made them available to the mission operations team. These telemetry data are being trended for the purpose of monitoring the long-term health of the reaction wheel bearings. Anomalous drag torque signatures observed over the past 15 years are described in this paper. One of these anomalous drag conditions is bearing cage instability that appeared (and disappeared) spontaneously and unpredictably. Cage instability is an uncontrolled vibratory motion of the bearing cage that can produce high-impact forces internal to the bearing that will cause intermittent and erratic torque transients. Characteristics of the observed cage instabilities and other drag torque "spikes" are described in this paper. In day-to-day operations, the reaction wheels' rates must be neither too high nor too low. To protect against operating the wheels in any undesirable conditions (such as prolonged low spin rate operations), a ground software tool named Reaction Wheel Bias Optimization Tool (RBOT) was developed for the management of the wheels. Disciplined and long-term use of this ground software has led to significant reduction in the daily consumption rate of the wheels' low spin rate dwell time. Flight experience on the use of this ground software tool as well as other lessons learned on the management of Cassini reaction wheels is given in this paper.

Cassini/Huygens Mission↗
NASA NTRS2018

Performance of Cassini Reaction Wheel Friction Compensation Scheme During Spin Rate Zero-Crossing and Drag Spikes

Cassini uses reaction wheels to achieve the spacecraft pointing stability that is needed during imaging operations of several science instruments. The Cassini flight software makes inflight estimates of reaction wheel bearing drag torque and the reaction wheel controller uses these estimates to achieve a high level of spacecraft pointing stability. However, the Cassini drag torque estimator was designed to accurately track the bearing drag torque only in the steady state. When the physical drag torque changes abruptly (for example, during a reaction wheel spin rate reversal or when wheel bearings experienced drag spikes), the drag estimator will not be able to track the physical drag closely. This will lead to a degradation in the spacecraft pointing stability performance. For Cassini, this was not a problem because of the significant performance margin in pointing stability. However, for missions that have very challenging pointing stability requirements and that must perform well in the presence of frequent wheel rate reversals, alternative drag-compensating control schemes must be considered. To this end, alternative drag torque compensating control schemes (such as the adaptive model reference control scheme) are briefly reviewed in this paper. Selected design features used in these friction compensation schemes may be incorporated in reaction wheel controller design to improve the robustness of spacecraft pointing stability performance with regard to a wide range of reaction wheel drag torque anomalous behavior.

Lee, Allan Y↗
NASA NTRS2019

Synthesis of Meteoritic Reaction Intermediates

The organic compounds of carbo- naceous chondrites are structurally diverse products of the prolonged abiotic chemistry that occurred before and during the early stages of the solar system [1]. They also represent the types of prebiotic compounds that may have participated in chemical evolutionary processes that gave rise to life [2]. Pyruvic acid is a key component of primary metabolism that has recently been found in carbonaceous chondrites [3]. Its prominence in biology has inspired us to explore its chemistry and possible role in the origin of metabolism. Our laboratory investigations have found that pyruvate (the ionized form of pyruvic acid) can serve as a single-source reactant to generate what we term a pyruvate reaction network (PRN). The core of the PRN is driven by pyruvate aldol polymerization and decay reactions. These decay reactions lead to the production of stable and unstable compounds which include mono, di, and tricarboxylic acids and a variety of keto acids. Finding evidence of this reaction network in meteorites would establish that the chemistry of pyruvate did occur in a prebiotic environment. Many of the known compounds found in pyruvate reaction mixtures were originally detected in meteorite samples by Cooper et al in 2011. However, multiple synthetic origins not tied to pyruvate chemistry might also explain their meteoritic presence. Thus, a search to find compounds unique to the PRN, such as reaction intermediates, would provide stronger evidence to demonstrate its prebiotic relevance. The identity of these intermediates can only be confirmed by acquiring chemical standards, however, as most are not available commercially, they need to be accessed through chemical synthesis.

Rios, Andro C.↗
NASA NTRS1994

Evolution of heliobacteria: implications for photosynthetic reaction center complexes

The evolutionary position of the heliobacteria, a group of green photosynthetic bacteria with a photosynthetic apparatus functionally resembling Photosystem I of plants and cyanobacteria, has been investigated with respect to the evolutionary relationship to Gram-positive bacteria and cyanobacteria. On the basis of 16S rRNA sequence analysis, the heliobacteria appear to be most closely related to Gram-positive bacteria, but also an evolutionary link to cyanobacteria is evident. Interestingly, a 46-residue domain including the putative sixth membrane-spanning region of the heliobacterial reaction center protein show rather strong similarity (33% identity and 72% similarity) to a region including the sixth membrane-spanning region of the CP47 protein, a chlorophyll-binding core antenna polypeptide of Photosystem II. The N-terminal half of the heliobacterial reaction center polypeptide shows a moderate sequence similarity (22% identity over 232 residues) with the CP47 protein, which is significantly more than the similarity with the Photosystem I core polypeptides in this region. An evolutionary model for photosynthetic reaction center complexes is discussed, in which an ancestral homodimeric reaction center protein (possibly resembling the heliobacterial reaction center protein) with 11 membrane-spanning regions per polypeptide has diverged to give rise to the core of Photosystem I, Photosystem II, and of the photosynthetic apparatus in green, purple, and heliobacteria.

NASA Program Exobiology↗
NASA NTRSDate not supplied

Correlated Electromagnetic Levitation Actuator: A Reaction Sphere Based Attitude Control System

To address problems experienced by current reaction wheels and control moment gyroscopebased attitude control systems (ACS), researchers at NASA’s Marshall Space Flight Center have begun developing a reaction sphere actuator based on correlated electromagnetic levitation that will be immune to destructive bearing friction, momentum saturation, and gimbal lock. The Correlated Electromagnetic Levitation Actuator (CELA) advances the state of the art of reaction sphere ACSs by employing the concept of correlated magnetics. It is a frictionless, direct-drive reaction sphere that harnesses a unique technology with an array of applications across multiple disciplines. Correlated electromagnets function in a manner that is analogous to a matched filter; the convolution of two signals is peaked at the index representing the greatest match. For CELA, the signals are the patterns of magnetic flux density as a function of position. The magnitude of the convolution equates to an attractive or repulsive force, and these forces can be azimuthal or radial. The development of CELA is based in four distinct disciplines: Advanced Manufacturing, Prototype Development, Electromagnetic Modeling, and Controls. We are developing novel manufacturing techniques required to build arrays of permanent and electromagnet dipoles on curved surfaces. To print the permanent magnetic array, we have developed a probe with pyramidal magnets that will reside on a robotic arm to induce localized magnetic fields on a surface. The probe also includes the ability to erase dipole patterns from a permanent magnet by heating the surface to its Curie temperature. A number of test articles and prototypes have been developed using additive manufacturing methods. These prototypes have included hemispherical motors to test the drive algorithm, and a levitation test bed that demonstrates a magnetic bearing method based on attractive magnetic forces and ratiometric Hall effect sensors. We developed an array of electromagnetic dipoles on a printed circuit board (PCB) with individual H-bridges controlling each coil. This device created various flux density patterns and we measured their magnetic fields using a custom Hall effect 3-D probe and a LabVIEW virtual instrument. These data will serve as a benchmark for characterizing the accuracy of future models. Current work is focused on modeling the magnetic fields of our prototype arrays using COMSOL Finite Element Analysis and verifying the model against our test data. Accurate modeling will allow us to quickly test new patterns of electromagnets and their macro behavior. Eventually, the magnetic field models will be implemented in our controls simulations to facilitate precise control of the reaction sphere. Initial model results agree with field measurements to within 1 G (5% of measured flux density). Currently, we are testing different material properties of the electromagnets and their magnetic fields and thermal effects. These results will be used to refine the design of the electromagnetic dipoles. Our control efforts have centered on developing commutation, levitation, and field pattern shaping hardware in the form of breadboards and PCBs with software running on a local microcontroller. In addition, our partners developed MATLAB Simulink models to demonstrate a PID controller thatmitigates disturbance forces resulting from the interaction of drive and levitation magnetics. Finally, we have designed a three-axis test stand that will be used in future work to demonstrate CELA’s orientation control capability.

controls↗
NASA NTRSDate not supplied

Correlated Electromagnetic Levitation Actuator: A Reaction Sphere-Based Attitude Control System

To address problems experienced by current reaction wheels and control moment gyroscopebased attitude control systems (ACS), researchers at National Aeronautics and Space Administration’s (NASA’s) Marshall Space Flight Center (MSFC) have begun developing a reaction sphere actuator based on correlated electromagnetic levitation that will be immune to destructive bearing friction, momentum saturation, and gimbal lock. The Correlated Electromagnetic Levitation Actuator (CELA) advances the state of the art of reaction sphere ACSs by employing the concept of correlated magnetics. It is a frictionless, direct-drive reaction sphere that harnesses a unique technology with an array of applications across multiple disciplines. Correlated electromagnets function in a manner that is analogous to a matched filter; the convolution of two signals is peaked at the index representing the greatest match. For CELA, the signals are the patterns of magnetic flux density as a function of position. The magnitude of the convolution equates to an attractive or repulsive force, and these forces can be azimuthal or radial. The development of CELA is based in four distinct disciplines: Advanced Manufacturing, Prototype Development, Electromagnetic Modeling, and Controls. We are developing novel manufacturing techniques required to build arrays of permanent and electromagnet dipoles on curved surfaces. To print the permanent magnetic array, we have developed a probe with pyramidal magnets that will reside on a robotic arm to induce localized magnetic fields on a surface. We have also used high temperature ovens to erase dipole patterns from a permanent magnet by heating the surface to its Curie temperature. A number of test articles and prototypes have been developed using additive manufacturing methods. These prototypes have included hemispherical motors to test the drive algorithm, and a levitation test bed that demonstrates a magnetic bearing method based on attractive magnetic forces and ratiometric Hall effect sensors. We developed an array of electromagnetic dipoles on a printed circuit board (PCB) with individual H-bridges controlling each coil. This device created various flux density patterns and we measured their magnetic fields using a custom Hall effect 3-D probe and a LabVIEW virtual instrument. These data will serve as a benchmark for characterizing the accuracy of future models. Current work is focused on modeling the magnetic fields of our prototype arrays using COMSOL finite element analysis (FEA) and verifying the model against our test data. Accurate modeling will allow us to quickly test new patterns of electromagnets and their macro behavior. Eventually, the magnetic field models will be implemented in our controls simulations to facilitate precise control of the reaction sphere. Initial model results agree with field measurements to within 1 G (5% of measured flux density). Currently, we are testing different material properties of the electromagnets and their magnetic fields and thermal effects. These results will be used to refine the design of the electromagnetic dipoles. Our control efforts have centered on developing commutation, levitation, and field pattern shaping hardware in the form of breadboards and PCBs with software running on a local microcontroller. In addition, our partners developed MATLAB Simulink models to demonstrate a PID controller that mitigates disturbance forces resulting from the interaction of drive and levitation magnetics. Finally, we have designed a three-axis test stand that will be used in future work to demonstrate CELA’s orientation control capability.

reaction sphere↗
NASA NTRS1973

Rate of reaction between molecular hydrogen and molecular oxygen

The shock tube data of Jachimowski and Houghton were rigorously analyzed to obtain rate constants for the candidate initiation reactions H2 + O2 yields H + HO2, H2 + O2 yields H2O + O, and H2 + O2 yields OH + OH. Reaction (01) is probably not the initiation process because the activation energy obtained is less than the endothermicity and because the derived rates greatly exceed values inferred in the literature from the reverse of reaction (01). Reactions (02) and (03) remain as possibilities, with reaction (02) slightly favored on the basis of steric and statistical considerations. The solution of the differential equations is presented in detail to show how the kinetics of other ignition systems may be solved.

Brokaw, R. S.↗
NASA NTRS1975

Reaction of sulfur dioxide with modified 440C, studied by Auger electron spectroscopy and depth profiling

Auger electron spectroscopy and sputtering were used to study the interaction of SO2 with modified 440C, which is a nominally 77-wt%-Fe, 14-wt%-Cr, and 4-wt%-Mo bearing steel with C, S, Si, Ni, V, P, and Mn making up the balance. The sample was polycrystalline. Three temperatures were used: room temperature, 500 C, and 600 C. The reaction time was varied from 30 minutes to 2 hours. A surface cleaned of oxides was the starting point for each reaction. For reactions at 500 C, the major constituents Cr, O, Fe, and S were present in the surface film. At 600 C, the principal constituents of the film were Cr, O, and S with no Fe present. Therefore, a transition in film composition occurred between 500 and 600 C. Oxides were the primary constituents of the films at both temperatures. Room-temperature reactions indicated that SO2 adsorbed dissociatively, with approximately equal quantities of S and O on the surface. For the same reaction time (1 hr) and pressure, a strong temperature dependence of film thickness was observed. The film formed at 600 C was approximately seven times thicker than that formed at 500 C.

Ferrante, J.↗
NASA NTRS1975

A photoionization study of the formation of CO2/+/ by reaction of excited O2/+/ ions with CO

The production of CO2(+) by the ion-molecule reaction O2(+) + CO yields CO2(+) + O has been investigated using a photoionization mass spectrometer. The photoionization efficiency for production of CO2(+) by this reaction was measured from threshold at 924 A (13.42 eV) to 650 A (19.07 eV). The appearance potential corresponds to reaction of ground vibronic O2(+) ions formed in the nu-prime = 6 level. The high-vibrational-level ions of the ground ionic state are most likely produced by autoionization of O2. At wavelengths shorter than 760 A, there is a large increase in the reaction cross section associated with formation of ions in the metastable state. The peak reaction cross section occurs at 720 A.

Ajello, J. M.↗
NASA NTRS1977

Three model space experiments on chemical reactions

Three investigations conducted aboard Skylab IV and Apollo-Soyuz involved phenomena that are of interest to the biochemistry community. The formaldehyde clock reaction and the equilibrium shift reaction experiments conducted aboard Apollo Soyuz demonstrate the effect of low-g foams or air/liquid dispersions on reaction rate and chemical equilibrium. The electrodeposition reaction experiment conducted aboard Skylab IV demonstrate the effect of a low-g environment on an electrochemical displacement reaction. The implications of the three space experiments for various applications are considered.

Grodzka, P.↗
NASA NTRS1978

Candidate interstellar molecules formed from ion-molecule reactions of NO

Molecular orbital calculations using the MINDO/3 method were performed on a series of small molecules to explore reactions of NO which could lead to formation of interstellar molecules. Specifically, equilibrium geometries, isomeric energies, heats of reactions, and reaction pathways were calculated for plausible ion-molecule reactions involving NO and NO(+). The results of these calculations suggest that HNO(+) and HON(+) could be present in observable abundance in interstellar clouds. These species can be formed by the reaction of NO with H3(+) but not by NO(+) with H2. Moreover, they are stable to dissociation and do not react with H2 to re-form NO or to form isomers of HNOH(+).

Loew, G. H.↗
NASA NTRS1978

Unified connected theory of few-body reaction mechanisms in N-body scattering theory

A unified treatment of different reaction mechanisms in nonrelativistic N-body scattering is presented. The theory is based on connected kernel integral equations that are expected to become compact for reasonable constraints on the potentials. The operators T/sub +-//sup ab/(A) are approximate transition operators that describe the scattering proceeding through an arbitrary reaction mechanism A. These operators are uniquely determined by a connected kernel equation and satisfy an optical theorem consistent with the choice of reaction mechanism. Connected kernel equations relating T/sub +-//sup ab/(A) to the full T/sub +-//sup ab/ allow correction of the approximate solutions for any ignored process to any order. This theory gives a unified treatment of all few-body reaction mechanisms with the same dynamic simplicity of a model calculation, but can include complicated reaction mechanisms involving overlapping configurations where it is difficult to formulate models.

Polyzou, W. N.↗
NASA NTRS1978

A kinetics investigation of several reactions involving chlorine containing compounds

The technique of flash photolysis-resonance fluorescence was utilized to study nine reactions of stratospheric importance. The tropospheric degradation reactions of seven halogenated hydrocarbons were studied to assess their possible influx into the stratosphere. There are reactions of either Cl, OH, or O(3P) species with hydrogenated species, O3 or chlorinated compounds. Apart from the kinetic measurements, the quantum yield for the production of O(1D) from O3 in the crucial wavelength region of 293 to 316.5 nm was studied by utilizing a narrow wavelength laser as the photolysis source. The product formation was monitored by measuring the fluorescence of NO2 formed through O(1D) reaction with N2O followed by NO reaction with O3 to give NO2.

Davis, D. D.↗