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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 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Coherent Acoustic Interferometry during the Photodriven Oxygen Evolution Reaction Associates Strain Fields with the Reactive Oxygen Intermediate (Ti–OH*)

The oxygen evolution reaction (OER) from water requires the formation of metastable, reactive oxygen intermediates to enable oxygen–oxygen bond formation. Conversely, such reactive intermediates could also structurally modify the catalyst. Here, a descriptor for the overall catalytic activity, the first electron and proton transfer OER intermediate from water, (M–OH*), has been associated with significant distortions of the metal–oxygen bonds upon charge-trapping. Time-resolved spectroscopy of in situ, photodriven OER on transition metal oxide surfaces has characterized M–OH* for the charge trapping and the symmetry of the lattice distortions by optical and vibrational transitions, respectively, but had yet to detect an interfacial strain field arising from a surface coverage M–OH*. Here, we utilize picosecond, coherent acoustic interferometry to detect the uniaxial strain normal to the SrTiO 3 /aqueous interface directly caused by Ti–OH*. The spectral analysis applies a fairly general methodology for detecting a combination of the spatial extent, magnitude, and generation time of the interfacial strain through the coherent oscillations’ phase. For lightly n-doped SrTiO 3 , we identify the strain generation time (1.31 ps), which occurs simultaneously with Ti–OH* formation, and a tensile strain of 0.06% (upper limit 0.6%). In addition to fully characterizing this intermediate across visible, mid-infrared, and now GHz-THz probes on SrTiO 3 , we show that strain fields occur with the creation of some M–OH*, which modifies design strategies for tuning catalytic activity and provides insight into photo-induced degradation so prevalent for OER. To that end, the work put forth here provides a unique methodology to characterize intermediate-induced interfacial strain across OER catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Cooperative Effects Drive Water Oxidation Catalysis in Cobalt Electrocatalysts through the Destabilization of Intermediates

A barrier to understanding the factors driving catalysis in the oxygen evolution reaction (OER) is understanding multiple over- lapping redox transitions in the OER catalysts. The complexity of these transitions obscure the relationship between the coverage of adsorbates and OER kinetics, leading to an experimental challenge in measuring activity descriptors, such as binding energies, as well as adsorbate interactions, which may destabilize intermediates and modulate their binding energies. Herein, we utilize a newly designed optical spectroelectrochemistry system to measure these phenomena in order to contrast the behavior of two electrocatalysts, cobalt oxyhydroxide (CoOOH) and cobalt-iron hexacyanoferrate (cobalt-iron Prussian blue, CoFe-PB). Three distinct optical spectra are observed in each catalyst, corresponding to three separate redox transitions, the last of which we show to be active for the OER using time-resolved spectroscopy and electrochemical mass spectroscopy. By combining predictions from density functional theory with parameters obtained from electroadsorption isotherms, we demonstrate that a destabilization of catalytic intermediates occurs with increasing coverage. In CoOOH, a strong (~0.34 eV/ monolayer) destabilization of a strongly bound catalytic intermediate is observed, leading to a potential offset between the accumulation of the intermediate and measurable O 2 evolution. We contrast these data to CoFe-PB, where catalytic intermediate generation and O 2 evolution onset coincide due to weaker binding and destabilization (~0.19 eV/monolayer). By considering a correlation between activation energy and binding strength, we suggest that such adsorbate driven destabilization may account for a significant fraction of the observed OER catalytic activity in both materials. Finally, we disentangle the effects of adsorbate interactions on state coverages and kinetics to show how adsorbate interactions determine the observed Tafel slopes. Crucially, the case of CoFe-PB shows that, even where interactions are weaker, adsorption remains non-Nernstian, which strongly influences the observed Tafel slope.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Nature of the Reactive Biferric Peroxy Intermediate P′ in the Arylamine Oxygenases and Related Binuclear Fe Enzymes

Binuclear nonheme iron enzymes activate O 2 to perform a wide range of chemical transformations. The process of O 2 activation typically involves a biferric peroxy-level intermediate P. It has been previously found that this intermediate undergoes further activation, either protonation or rearrangement to form P′ or further oxidation to form high-valent intermediates Q or X. Here, this study defines the structure of the P′ intermediate in the N-oxygenases CmlI (and AurF based on previous data) using nuclear resonance vibrational spectroscopy (NRVS) in conjugation with density functional theory (DFT) calculations. These results, combined with variable temperature variable field (VTVH) magnetic circular dichroism (MCD) spectroscopy on the 1-electron cryoreduced P′, define the structure of the P′ intermediate as a μ-1,2-hydroxoperoxo biferric site with a second hydroxide bridge. Reaction coordinate calculations demonstrate that single electron transfer (SET) is facilitated by protonation of the peroxo, activating its reductive cleavage, and that the additional hydroxide bridge does not impact this reaction. VTVH MCD studies further reveal that the hydroxide bridge is absent in the biferrous site, suggesting that during the O 2 reaction with the biferrous site, a water molecule forms the hydroxide bridge in providing the proton that activates the peroxide in P′ for reactivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Carbon Dioxide Dimer Radical Anion as Surface Intermediate of Photoinduced CO 2 Reduction at Aqueous Cu and CdSe Nanoparticle Catalysts by Rapid-Scan FT-IR Spectroscopy

Monitoring of visible light sensitized reduction of CO 2 at Cu nanoparticles in aqueous solution by rapid-scan ATR FT-IR spectroscopy on the time scale of seconds allowed structural identification of a one-electron intermediate and demonstrated its kinetic relevancy for the first time. Isotopic labeling ( 12 C: 1632, 1358, 1346 cm -1 ; 13 C: 1588, 1326, 1316 cm -1 ) revealed a species of carbon dioxide dimer radical anion structure, most likely bound to the catalyst surface through carbon. Intermediacy of Cu—C(═O)OCO 2 - surface species is in agreement with a recently proposed mechanism for electrocatalytic CO 2 reduction at Cu metal nanoparticles based on Tafel slope analysis. Spontaneous decrease of the intermediate after termination of the photosensitization pulse (Sn porphyrin excited at 405 nm) was accompanied by the growth of HCO 3 - . CO was produced as well, but sensitive detection required photolysis for tens of minutes. A direct kinetic link between a C 2 O 4 - surface intermediate and the CO product was also demonstrated for photocatalyzed CO 2 reduction at aqueous CdSe nanoparticles, where first order growth of a Cd—C(═O)OCO 2 - species was accompanied by rise of CO (monitored by a fast Ni complex trap) and HCO 3 - showing a distinct induction period. The detection of the one-electron surface intermediate and confirmation of its catalytic relevancy was enabled by the delivery of electrons one-by-one by the photosensitization method. The observation of carbon dioxide dimer radical anion points to approaches for rate enhancements of heterogeneous CO 2 reduction by creating catalytic environments that favor formation of this intermediate.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

An Unexpected Species Determined by X-ray Crystallography that May Represent an Intermediate in the Reaction Catalyzed by Quinolinate Synthase

Quinolinic acid is a common intermediate in the biosynthesis of nicotinamide adenine dinucleotide and its derivatives in all organisms that synthesize the molecule de novo. In most prokaryotes, it is formed from the condensation of dihydroxyacetone phosphate (DHAP) and iminoaspartate (IA) by the action of quinolinate synthase (NadA). NadA contains a [4Fe–4S] cluster cofactor with a unique noncysteinyl-ligated iron ion (Fe a ), which is proposed to bind the hydroxyl group of an intermediate in its reaction to facilitate a dehydration step. However, direct evidence for this role in catalysis has yet to be provided, and the exact chemical mechanism that underlies this transformation remains elusive. Herein, we present a structure of NadA from Pyrococcus horikoshii (PhNadA) in complex with IA and show that a carboxylate group of the molecule is ligated to Fe a of the iron–sulfur cluster, occupying the site to which DHAP has been proposed to bind during catalysis. When crystals of PhNadA in complex with IA are soaked briefly in DHAP before freezing, electron density for a new molecule is observed, which we suggest is related to an intermediate in the reaction. Similar, but slightly different, “intermediates” are observed when crystals of a PhNadA Glu198Gln variant are incubated with DHAP, oxaloacetate, and ammonium chloride, conditions under which IA is formed chemically. Furthermore, continuous-wave and pulse electron paramagnetic resonance techniques are used to verify the binding mode of substrates and proposed intermediates in frozen solution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Rapid unimolecular reaction of stabilized Criegee intermediates and implications for atmospheric chemistry

Abstract Elucidating atmospheric oxidation mechanisms is necessary for estimating the lifetimes of atmospheric species and understanding secondary organic aerosol formation and atmospheric oxidation capacity. We report an unexpectedly fast mechanistic pathway for the unimolecular reactions of large stabilized Criegee intermediates, which involves the formation of bicyclic structures from large Criegee intermediates containing an aldehyde group. The barrier heights of the mechanistic pathways are unexpectedly low – about 2–3 kcal/mol – and are at least 10 kcal/mol lower than those of hydrogen shift processes in large syn Criegee intermediates; and the calculated rate constants show that the mechanistic pathways are 10 5 -10 9 times faster than those of the corresponding hydrogen shift processes. The present findings indicate that analogous low-energy pathways can now also be expected in other large Criegee intermediates and that oxidative capacity of some Criegee intermediates is smaller than would be predicted by existing models.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Single-molecule reaction mapping uncovers diverse behaviours of electrocatalytic surface Pd–H intermediates

Many vital electrocatalytic transformations hinge on reactive surface metal–hydrogen intermediates (M–H*), yet the low concentration and transient nature of such intermediates present formidable challenges to in-depth investigation. Here we use single-molecule super-resolution reaction imaging to directly probe surface palladium–hydrogen (Pd–H*) intermediates on individual palladium nanocubes during electrocatalytic hydrogen evolution. Our approach visualizes hydrogen spillover from palladium to the surrounding substrate surface over hundreds of nanometres away and dissects substantial inter- and intraparticle heterogeneity. Through Gaussian-broadening kinetic analysis, we reveal that ensemble-averaged measurements systematically overestimate the stability of Pd–H*. Moreover, we resolve three subpopulations of palladium nanocubes with distinct reactivity features, uncovering critical correlations between intermediate stability, hydrogenation reactivity and transition-state properties. Finally, our findings highlight the necessity of single-particle resolution for capturing the intrinsic complexity of electrocatalysts; our approach is also broadly applicable to interrogate surface-reactive intermediates across a wide array of electrocatalytic pathways.

electrocatalysis↗
DOE OSTI2016

Retention of intermediate polarization states in ferroelectric materials enabling memories for multi-bit data storage

A homogeneous ferroelectric single crystal exhibits only two remanent polarization states that are stable over time, whereas intermediate, or unsaturated, polarization states are thermodynamically instable. Commonly used ferroelectric materials however, are inhomogeneous polycrystalline thin films or ceramics. To investigate the stability of intermediate polarization states, formed upon incomplete, or partial, switching, we have systematically studied their retention in capacitors comprising two classic ferroelectric materials, viz. random copolymer of vinylidene fluoride with trifluoroethylene, P(VDF-TrFE), and Pb(Zr,Ti)O{sub 3}. Each experiment started from a discharged and electrically depolarized ferroelectric capacitor. Voltage pulses were applied to set the given polarization states. The retention was measured as a function of time at various temperatures. The intermediate polarization states are stable over time, up to the Curie temperature. We argue that the remarkable stability originates from the coexistence of effectively independent domains, with different values of polarization and coercive field. A domain growth model is derived quantitatively describing deterministic switching between the intermediate polarization states. We show that by using well-defined voltage pulses, the polarization can be set to any arbitrary value, allowing arithmetic programming. The feasibility of arithmetic programming along with the inherent stability of intermediate polarization states makes ferroelectric materials ideal candidates for multibit data storage.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2019

Time-resolved x-ray crystallography capture of a slow reaction tetrahydrofolate intermediate

Time-resolved crystallography is a powerful technique to elucidate molecular mechanisms at both spatial (angstroms) and temporal (picoseconds to seconds) resolutions. We recently discovered an unusually slow reaction at room temperature that occurs on the order of days: the in crystalline reverse oxidative decay of the chemically labile (6S)-5,6,7,8-tetrahydrofolate in complex with its producing enzyme Escherichia coli dihydrofolate reductase. Here, we report the critical analysis of a representative dataset at an intermediate reaction time point. A quinonoid-like intermediate state lying between tetrahydrofolate and dihydrofolate features a near coplanar geometry of the bicyclic pterin moiety, and a tetrahedral sp 3 C6 geometry is proposed based on the apparent mFo-DFc omit electron densities of the ligand. The presence of this intermediate is strongly supported by Bayesian difference refinement. Isomorphous Fo-Fo difference map and multi-state refinement analyses suggest the presence of end-state ligand populations as well, although the putative intermediate state is likely the most populated. A similar quinonoid intermediate previously proposed to transiently exist during the oxidation of tetrahydrofolate was confirmed by polarography and UV-vis spectroscopy to be relatively stable in the oxidation of its close analog tetrahydropterin. We postulate that the constraints on the ligand imposed by the interactions with the protein environment might be the origin of the slow reaction observed by time-resolved crystallography.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2019

Carrier dynamics of intermediate sub-bandgap transitions in ZnTeO

The incorporation of electronic states in the bandgap, with high radiative efficiency, provides a means for optical up/down conversion and for tuning the carrier lifetime of a material. Such intermediate states in highly mismatched alloys have recently received much attention due to their potential for an efficient solar energy conversion. Understanding the carrier dynamics and pathways for the charge transfer of sub-bandgap transitions is critical for understanding energy conversion processes. In this work, time-resolved photoluminescence of ZnTeO is reported, revealing electron relaxation from the conduction band to the intermediate band and the carrier transfer between intermediate states and the conduction band utilizing two time-delayed optical excitations. Furthermore, this work demonstrates the utility of time-resolved techniques for characterizing energy conversion mechanisms in intermediate band materials, and the ability to use intermediate states to intentionally alter carrier lifetimes in materials for applications such as ultrafast scintillation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Intermediate accelerated solutions as generic late-time attractors in a modified Jordan-Brans-Dicke theory

In this paper we investigate the evolution of a Jordan-Brans-Dicke scalar field, Φ, with a power-law potential in the presence of a second scalar field, φ, with an exponential potential, in both the Jordan and the Einstein frames. We present the relation of our model with the induced gravity model with power-law potential and the integrability of this kind of models is discussed when the quintessence field φ is massless, and has a small velocity. The fact that for some fine-tuned values of the parameters we may get some integrable cosmological models, makes our choice of potentials very interesting. We prove that in Jordan-Brans-Dicke theory, the de Sitter solution is not a natural attractor. Instead, we show that the attractor in the Jordan frame corresponds to an ''intermediate accelerated'' solution of the form a(t) ≅ e{sup α{sub 1} t{sup p{sup {sub 1}}}}, as t → ∞ where α{sub 1} > 0 and 0 < p{sub 1} < 1, for a wide range of parameters. Furthermore, when we work in the Einstein frame we get that the attractor is also an ''intermediate accelerated'' solution of the form a(t) ≅ e{sup α{sub 2} tp{sub 2}} as t → ∞ where α{sub 2} > 0 and 0<p{sub 2}<1, for the same conditions on the parameter space as in the Jordan frame. In the special case of a quadratic potential in the Jordan frame, or for a constant potential in the Einstein's frame, the above intermediate solutions are of saddle type. These results were proved using the center manifold theorem, which is not based on linear approximation. Finally, we present a specific elaboration of our extension of the induced gravity model in the Jordan frame, which corresponds to a particular choice of a linear potential of Φ. The dynamical system is then reduced to a two dimensional one, and the late-time attractor is linked with the exact solution found for the induced gravity model. In this example the ''intermediate accelerated'' solution does not exist, and the attractor solution has an asymptotic de Sitter-like evolution law for the scale factor. Apart from some fine-tuned examples such as the linear, and quadratic potential U(Φ) in the Jordan frame, it is true that ''intermediate accelerated'' solutions are generic late-time attractors in a modified Jordan-Brans-Dicke theory.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2015

SU-C-304-06: Determination of Intermediate Correction Factors for Three Dosimeters in Small Composite Photon Fields Used in Robotic Radiosurgery

Purpose: To calculate using Monte-Carlo the intermediate and total correction factors (CFs) for two microchambers and a plastic scintillator for composite fields delivered by the CyberKnife system. Methods: A linac model was created in BEAMnrc by matching percentage depth dose (PDD) curves and output factors (OFs) measured using an A16 microchamber with Monte Carlo calculations performed in egs-chamber to explicitly model detector response. Intermediate CFs were determined for the A16 and A26 microchambers and the W1 plastic scintillator in fourteen different composite fields inside a solid water phantom. Seven of these fields used a 5 mm diameter collimator; the remaining fields employed a 7.5 mm collimator but were otherwise identical to the first seven. Intermediate CFs are reported relative to the respective CF for a 60 mm collimator (800 mm source to detector distance and 100 mm depth in water). Results: For microchambers in composite fields, the intermediate CFs that account for detector density and volume were the largest contributors to total CFs. The total CFs for the A26 were larger than those for the A16, especially for the 5 mm cone (1.227±0.003 to 1.144±0.004 versus 1.142±0.003 to 1.099±0.004), due to the A26’s larger active volume (0.015 cc) relative to the A16 (0.007 cc), despite the A26 using similar wall and electrode material. The W1 total and intermediate CFs are closer to unity, due to its smaller active volume and near water-equivalent composition, however, 3–4% detector volume corrections are required for 5 mm collimator fields. In fields using the 7.5 mm collimator, the correction is nearly eliminated for the W1 except for a non-isocentric field. Conclusion: Large and variable CFs are required for microchambers in small composite fields primarily due to density and volume effects. Corrections are reduced but not eliminated for a plastic scintillator in the same fields.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2017

Subsequent R + O 2 Chemistry of Intermediates Formed in Low-Temperature R + O 2 Reactions: Potential Importance in Modeling Autoignition Behavior

Comprehensive chemical kinetics models used in the simulation of hydrocarbon and biofuel oxidation rely on accurate prescription of the underlying reaction mechanisms and rate parameters of associated elementary reactions. For practical transportation fuels, such models contain thousands of elementary reactions, which collectively define chain-initiation, -propagation, -branching, and -inhibition pathways. In the low-temperature regime, below approximately 1000 K where R + O 2 reactions dominate, primary oxidation intermediates including cyclic ethers, carbonyls, and conjugate alkenes are formed in abundance via unimolecular decomposition of either chemically activated or thermalized radicals, specifically organic peroxy (ROO) or hydroperoxyalkyl species (QOOH). Experimental results from multiplexed photoionization mass spectrometry (MPIMS) experiments are detailed herein for several intermediates, derived initially from R + O 2 reactions of hydrocarbons and biofuels, and show that intermediate species formed in the initial steps of oxidation undergo similar reactions to those of the parent molecule, including through QOOH-mediated pathways. Products from QOOH decomposition via chain-inhibition and chain-propagation pathways, namely conjugate alkenes, carbonyls, and cyclic ethers, are detected directly. Despite such rich chemistry involving QOOH radicals, most comprehensive chemical kinetics models neglect the complete description of primary oxidation intermediates, and rather consider a restricted number of reaction pathways. It is suggested that exclusion of the details of the oxidation of these intermediate products may affect the interpretation of combustion simulations using such models.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Mechanistic insights to drive catalytic hydrogenation of formamide intermediates to methanol via deaminative hydrogenation

Amine-promoted hydrogenation of CO 2 to methanol typically proceeds via a formamide intermediate when amines are used as additives or if the hydrogenation is performed in carbon capture solvents. The catalysts used for the hydrogenation of the formamide intermediate dictate the selectivity of the products formed: 1) Deoxygenative hydrogenation (C–O bond cleavage) resulting in N-methylation of amine and deactivation of the solvent, 2) Deaminative hydrogenation (C–N bond cleavage) resulting in formation of methanol and regeneration of the solvent. To date, catalytic reductions of CO 2 with amine promoters suffer from poor selectively for methanol which we attribute to the limiting formamide intermediate, though to date, the conditions that favor C–N cleavage have yet to be fully understood. To better understand the reactivity of the formamide intermediates, a range of heterogenous catalysts were used to study the hydrogenation of formamide. Well-known gas phase CO 2 hydrogenation catalysts catalyze the hydrogenation of formamide to N-methyl product via C–O bond cleavage. However, the selectivity can be readily shifted to selective C–N bond cleavage by addition of an additive with sufficient basicity for both homogenous and heterogeneous catalytic systems. The base additive shifts the selectivity by deprotonating a hemiaminal intermediate formed in situ during the formamide hydrogenation. This prevents dehydration process leading to N-methylated product, which is a key capture solvent deactivation pathway that hinders amine use in carbon capture, utilization, and storage (CCUS). The findings from this study provide a roadmap on how to improve the selectivity of known heterogenous catalysts, enabling catalytic reduction of captured CO 2 to methanol.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

REVERBERATION MAPPING WITH INTERMEDIATE-BAND PHOTOMETRY: DETECTION OF BROAD-LINE Hα TIME LAGS FOR QUASARS AT 0.2 < z < 0.4

We present a reverberation mapping (RM) experiment that combines broad- and intermediate-band photometry; it is the first such attempt targeting 13 quasars at 0.2 < z < 0.9. The quasars were selected to have strong Hα or Hβ emission lines that are located in one of three intermediate bands (with FWHM around 200 Å) centered at 8045, 8505, and 9171 Å. The imaging observations were carried out in the intermediate bands and the broad i and z bands using the prime-focus imager 90Prime on the 2.3 m Bok telescope. Because of the large (∼1 deg{sup 2}) field of view (FOV) of 90Prime, we included the 13 quasars within only five telescope pointings or fields. The five fields were repeatedly observed over 20–30 epochs that were unevenly distributed over a duration of 5–6 months. The combination of the broad- and intermediate-band photometry allows us to derive accurate light curves for both optical continuum emission (from the accretion disk) and line emission (from the broad-line region, or BLR). We detect Hα time lags between the continuum and line emission in six quasars. These quasars are at relatively low redshifts 0.2 < z < 0.4. The measured lags are consistent with the current BLR size–luminosity relation for Hβ at z < 0.3. While this experiment appears successful in detecting lags of the bright Hα line, further investigation is required to see if it can also be applied to the fainter Hβ line for quasars at higher redshifts. Finally we demonstrate that, by using a small telescope with a large FOV, intermediate-band photometric RM can be efficiently executed for a large sample of quasars at z > 0.2.

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRS1972

Mechanisms of deterioration of intermediate moisture food systems

A study of shelf stability in intermediate moisture foods was made. Major efforts were made to control lipid oxidation and nonenzymatic browning. In order to determine means of preventing these reactions, model systems were developed having the same water activity content relationship of intermediate moisture foods. Models were based on a cellulose-lipid and protein-lipid system with glycerol added as the humectant. Experiments with both systems indicate that lipid oxidation is promoted significantly in the intermediate moisture range. The effect appeared to be related to increased mobility of either reactants or catalysts, since when the amount of water in the system reached a level where capillary condensation occurred and thus free water was present, the rates of oxidation increased. With added glycerol, which is water soluble and thus increases the amount of mobile phase, the increase in oxidation rate occurs at a lower relative humidity. The rates of oxidation were maximized at 61% RH and decreased again at 75% RH probably due to dilution. No significant non-enzymatic browning occurred in the protein-lipid systems. Prevention of oxidation by the use of metal chelating agents was enhanced in the cellulose system, whereas, with protein present, the lipid soluble chain terminating antioxidants (such as BHA) worked equally as well. Preliminary studies of foods adjusted to the intermediate moisture range bear out the results of oxidation in model systems. It can be concluded that for most fat containing intermediate moisture foods, rancidity will be the reaction most limiting stability.

Labuza, T. P.↗
NASA NTRS1990

Formation, structure, and stability of MHD intermediate shocks

It was recently shown by Wu (1987) that intermediate shocks are admissible and can be formed through nonlinear wave steepening from continuous waves. In this paper, the formation, structure, and stability of intermediate shocks in dissipative MHD are considered in detail. The differences between the conventional theory and the present one are pointed out and clarified. It is shown that all four types of intermediate shocks can be formed from smooth waves. It is also shown that there are free parameters in the structure of the intermediate shocks, and that these parameters are related to the shock stability. In addition, the paper shows that a rotational discontinuity can not exist with finite width, indicates how this is related to the existence of time-dependent intermediate shocks, and shows why the conventional theory is not a good approximation to dissipative MHD solutions whenever there is rotation in magnetic field.

Wu, C. C.↗
NASA NTRS1992

The back photoreaction of the M intermediate in the photocycle of bacteriorhodopsin: mechanism and evidence for two M species

The back photoreaction of the M intermediate in the photocycle of bacteriorhodopsin is investigated both for the native pigment and its D96N mutant. The experimental setup is based on creating the M intermediate by a first pulse, followed by a (blue) laser pulse which drives the back photoreaction of M. Experiments are carried out varying the delay between the two pulses, as well as the temperature over the -25 degrees C-20 degrees C range. It is found that the kinetic patterns of the M back photoreaction change with time after the generation of this intermediate. The data provide independent evidence for the suggestion of a photocycle mechanism based on two distinct M intermediates. They are thus in keeping with the consecutive model of Varo and Lanyi (Biochemistry 30, 5016-5022; 1991), although they cannot exclude other models such as those based on branched or parallel cycles. More generally, we offer a "photochemical" approach to discriminating between intermediate stages in the photocycle which does not depend on spectroscopic and/or kinetic data. While markedly affecting the rate of the M --> N transition in the photocycle, the rate of the thermal step in back photoreaction of M, at both room and low temperatures, is not significantly affected by the D96N mutation. It is proposed that while Asp 96 is the Schiff-base protonating moiety in the M --> N transition, another residue (most probably Asp 85) reprotonates the Schiff base following light absorption by M.

NASA Discipline Exobiology↗