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At least 901 records · Page 50

Stiff neural ordinary differential equations

Neural Ordinary Differential Equations (ODEs) are a promising approach to learn dynamical models from time-series data in science and engineering applications. This work aims at learning neural ODEs for stiff systems, which are usually raised from chemical kinetic modeling in chemical and biological systems. We first show the challenges of learning neural ODEs in the classical stiff ODE systems of Robertson’s problem and propose techniques to mitigate the challenges associated with scale separations in stiff systems. We then present successful demonstrations in stiff systems of Robertson’s problem and an air pollution problem. The demonstrations show that the usage of deep networks with rectified activations, proper scaling of the network outputs as well as loss functions, and stabilized gradient calculations are the key techniques enabling the learning of stiff neural ODEs. The success of learning stiff neural ODEs opens up possibilities of using neural ODEs in applications with widely varying time-scales, such as chemical dynamics in energy conversion, environmental engineering, and life sciences.

97 MATHEMATICS AND COMPUTING↗

Measurement techniques for analysis of fission fragment excited gases

Spectroscopic analysis of fission fragment excited He, Ar, Xe, N2, Ne, Ar-N2, and Ne-N2 have been conducted. Boltzmann plot analysis of He, Ar and Xe have indicated a nonequilibrium, recombining plasma, and population inversions have been found in these gases. The observed radiating species in helium have been adequately described by a simple kinetic model. A more extensive model for argon, nitrogen and Ar-N2 mixtures was developed which adequately describes the energy flow in the system and compares favorably with experimental measurements. The kinetic processes involved in these systems are discussed.

Schneider, R. T.↗

Investigation of the hydrochlorination of SiCl4

The hyrochlorination of SiC14 and m.g. silicon metal to produce SiHC13, was investigated. Reaction kinetic measurements were carried out to collect additional rate data at 525 C and 550 C. A theoretical study was carried out to provide a kinetic model and a rate equation for the hydrochlorination reaction. Results of this preliminary study show that the rate of formation of SiHC13 follows a pseudo first order kinetics. The rate constants were measured at three temperatures, 550 C, 500 C and 450 C, respectively. The activation energy was determined from the Arrhenius plot to give a value of 13.2 Kcal/mole. The design of a quartz reactor to measure reaction rates and equilibrium conversion of SiHC13 at reaction temperature up to 650 C was completed.

Mui, J. Y. P.↗

Departures of the electron energy distribution from a Maxwellian in hydrogen. I - Formulation and solution of the electron kinetic equation. II - Consequences

The problem of calculating the steady-state free-electron energy distribution in a hydrogen gas is considered in order to study departures of that distribution from a Maxwellian at sufficiently low degrees of ionization. A model kinetic equation is formulated and solved analytically for the one-particle electron distribution function in a steady-state partially ionized hydrogen gas, and it is shown that the formal solution can be accurately approximated by using the WKB method. The solutions obtained indicate that the high-energy tail of the distribution is susceptible to distortion by imbalanced inelastic collisions for ionization fractions not exceeding about 0.1 and that such departures from a Maxwellian can lead to significant changes in the collisional excitation and ionization rates of ground-state hydrogen atoms. Expressions for the electron-hydrogen collision rates are derived which explicitly display their dependence on the hydrogen departure coefficients. The results are applied in order to compare self-consistent predictions with those based on the a priori assumption of a Maxwellian distribution for models of the thermal ionization equilibrium of hydrogen in the optically thin limit, spectral-line formation by a gas consisting of two-level atoms, and radiative transfer in finite slabs by a gas of four-level hydrogen atoms.

Shoub, E. C.↗

Robe Development for Electrical Conductivity Analysis in an Electron Gun Produced Helium Plasma

The use of magnetohydrodynamic (MHD) power conversion systems, potentially coupled with a fission power source, is currently being investigated as a driver for an advanced propulsion system, such as a plasma thruster. The efficiency of a MHD generator is strongly dependent on the electrical conductivity of the fluid that passes through the generator; power density increases as fluid conductivity increases. Although traditional MHD flows depend on thermal ionization to enhance the electrical conductivity, ionization due to nuclear interactions may achieve a comparable or improved conductivity enhancement while avoiding many of the limitations inherent to thermal ionization. Calculations suggest that nuclear-enhanced electrical conductivity increases as the neutron flux increases; conductivity of pure He-3 greater than 10 mho/m may be achievable if exposed to a flux greater than 10(exp 12) neutrons/cm2/s.) However, this remains to be demonstrated experimentally. An experimental facility has been constructed at the Propulsion Research Center at the NASA Marshall Space Flight Center, using helium as the test fluid. High energy electrons will be used to simulate the effects of neutron-induced ionization of helium gas to produce a plasma. These experiments will be focused on diagnosis of the plasma in a virtually static system; results will be applied to future tests with a MHD system. Initial experiments will utilize a 50 keV electron gun that can operate at up to a current of 200 micro A. Spreading the electron beam over a four inch diameter window results in an electron flux of 1.5x 10(exp 13) e/sq cm/s. The equivalent neutron flux that would produce the same ionization fraction in helium is 1x10(exp 12) n/sq cm/s. Experiments will simulate the neutron generated plasma modeled by Bitteker, which takes into account the products of thermal neutron absorption in He-3, and includes various ion species in estimating the conductivity of the resulting plasma. Several different probes will be designed and implemented to verify the plasma kinetics model. System parameters and estimated operating ranges are summarized. The predicted ionization fraction, electron density, and conductivity levels are provided in for an equivalent neutron flux of 1x10(exp 12) n/cm2/s. Understanding the complex plasma kinetics throughout a MHD channel is necessary to design an optimal power conversion system for space propulsion applications. The proposed experiments seek to fully characterize the helium plasma and to determine the reliability of each measurement technique, such that they may be applied to more advanced MHD studies. The expected value of each plasma parameter determined from theoretical models will be verified experimentally by several independent techniques to determine the most reliable method of obtaining each parameter. The results of these experiments will be presented in the final paper.

Bragg-Sitton, Shannon M.↗

Wire directed energy deposition of steel-aluminum structures using cold metal transfer process

In this study, a sharp transition from 316L stainless steel to 4043 aluminum alloy was fabricated using wire directed energy deposition (DED) via the cold metal transfer (CMT) process. The CMT process with its inherently low heat input, led to a significant reduction in intermetallic thickness at the bi-metallic interface compared to blown powder DED technique reported in the literature resulting in superior properties when compared to those of dissimilar steel-aluminum welds. Thermo-kinetic modeling confirmed that the intermetallic formation is through a classical nucleation and growth mechanism, and the fraction and thickness can be controlled by adjusting CMT process parameters to kinetically arrest or minimize the intermetallic formation. These findings underscore the efficacy of CMT-based wire DED for fabrication of steel-aluminum bi-metallic structures.

36 MATERIALS SCIENCE↗

Effect of the abolition of intersubunit salt bridges on allosteric protein structural dynamics

A salt bridge, one of the representative structural factors established by non-covalent interactions, plays a crucial role in stabilizing the structure and regulating the protein function, but its role in dynamic processes has been elusive. Here, to scrutinize the structural and functional roles of the salt bridge in the process of performing the protein function, we investigated the effects of salt bridges on the allosteric structural transition of homodimeric hemoglobin (HbI) by applying time-resolved X-ray solution scattering (TRXSS) to the K30D mutant, in which the interfacial salt bridges of the wild type (WT) are abolished. The TRXSS data of K30D are consistent with the kinetic model that requires one monomer intermediate in addition to three structurally distinct dimer intermediates (I 1 , I 2 , and I 3 ) observed in WT and other mutants. The kinetic and structural analyses show that K30D has an accelerated biphasic transition from I 2 to I 3 by more than nine times compared to WT and lacks significant structural changes in the transition from R-like I 2 to T-like I 3 observed in WT, unveiling that the loss of the salt bridges interrupts the R–T allosteric transition of HbI. Besides, the correlation between the bimolecular CO recombination rates in K30D, WT, and other mutants reveals that the bimolecular CO recombination is abnormally decelerated in K30D, indicating that the salt bridges also affect the cooperative ligand binding in HbI. These comparisons of the structural dynamics and kinetics of K30D and WT show that the interfacial salt bridges not only assist the physical connection of two subunits but also play a critical role in the global structural signal transduction of one subunit to the other subunit via a series of well-organized structural transitions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Temperature and density dependence of Kr L-shell spectrum in hot dense plasmas

Kr L-shell spectroscopy modeling results are discussed in this paper, focusing on the n = 4 to n = 2 line transitions of Be- and Li-like Kr ions. Collisional radiative atomic kinetic and Stark-broadened spectral line shape calculations show electron temperature Te and density ne sensitivity in the spectrum. The combination of the Te dependence due to the relative intensity of Be-like to Li-like line emissions in the range from 1.5 to 3 keV and the ne sensitivity from the Stark broadening effect on the line shapes in the range from 5×1023 to 2×1024/ cc results in a spectrum that can be employed to diagnose Te and ne. Two different collisional radiative atomic kinetic models i.e., Prismspect [J. J. MacFarlane, et al., Int. Fusion Sci. Appl. Conf. Proc. 457 (2003)] and ABAKO [Florido, et al., PRE, 80, 056402 (2009)] produce similar results in level populations and spectra. In x-ray spectroscopy of implosion cores, this Kr L-shell spectrum may prove useful in an intermediate Te range in which Ar is too ionized for its K-shell to be of diagnostic value and Kr is not ionized enough for its K-shell emission to be useful.

Physics↗

A Structural and Molecular Approach for the Study Biomarkers

Investigation of the nucleation and growth of crystals in both abiotic and biotic systems is critical to seemingly diverse disciplines of geology, biology, environmental science, and astrobiology. While there are abundant studies devoted to the determination of the structure and composition of inorganic crystals, as well as to the development of thermodynamic and kinetic models, it is only recently that research efforts have been directed towards understanding mineralization in biological systems (i.e., biomineralization). Biomineralization refers to the processes by which living organisms form inorganic solids. Studies of the processes of biomineralization under low temperature aqueous conditions have focused primarily on magnetite forming bacteria and shell forming marine organisms. Many of the biological building materials consist of inorganic minerals (calcium carbonate, calcium phosphate, silica or iron oxide) intricately combined with organic polymers (like proteins). More recently, efforts have been undertaken to explore the nature of biological activities in ancient rocks. In the absence of well-preserved microorganisms or genetic material required for the polmerase chain reaction (PCR) method in molecular phylogenetic studies, using biominerals as biomarkers offers an alternative approach for the recognition of biogenic activity in both terrestrial and extraterrestrial environments. The primary driving force in biomineralization is the interaction between organic and inorganic phases. Thus, the investigation of the ultrastructure and the nature of reactions at the molecular level occurring at the interface between inorganic and organic phases is essential to understanding the processes leading to the nucleation and growth of crystals. It is recognized that crystal surfaces can serve as the substrate for the organization of organic molecules that lead to the formation of polymers and other complex organic molecules, and in discussions of the origins of life, is referred to as organic synthesis on mineral surfaces. Furthermore, it is suggested that the interaction between mineral surfaces and simple organic molecules resulted in the formation of amino acids, RNA, and perhaps other more complex molecules such as proteins. On the other hand, in natural systems, it is recognized that functional groups on cell walls or membranes of microorganisms serve as sites of nucleation and crystallization. The precise replication of biominerals with controlled structure, morphology, size and texture is not confined to higher organisms as it also occurs in primitive prokaryotic cells such as magnetotactic bacteria and cyanobacteria. This suggests that the principal strategies of biomineralization were established early on in the evolutionary history of organisms. It is critical, therefore, to search for common mechanisms within diverse biological systems. One such common factor is the capability for organization and self-assembly. Organic macromolecules such as proteins and lipids can aggregate and polymerize forming membranes or extracellular matrix. At the organic-inorganic interface, several factors such as lattice geometry, polarity, stereochemistry and topography may act in concert to control nucleation and growth of crystals. Although several models have been proposed that discuss the significance of these factors for biomineralization, no comprehensive experimental data are available. In contrast to crystallization in exclusively inorganic systems, the kinetics of reaction and structural relationships between organic and inorganic phases in biominerals or biomimetic material is poorly understood. For example, it is not clear if the concept of epitactic growth (geometrical matching of unit cells at the interface of a secondary crystal growing on a primary crystal) applies to organic-inorganic systems. In contrast to inorganic templates that often have a smooth and rigid surface that promotes epitactic growth, biological substrates are usually rough and result in a large degree of mismatch. It is apparent that factors controlling the reaction at the crystal-matrix interface are strongly dependent upon the nature of the substrate. Therefore, characterization of the assembled organic surface and surface structure of the inorganic phase is crucial to understanding the processes of biomineralization. The focus of our research is the investigation of the processes leading to the nucleation and growth of crystals on both natural and synthetic systems through an interdisciplinary approach that integrates molecular biology, morphology and mineralogy using advanced preparation and analytical techniques. We have studied run-products, particularly magnetite, siderite and other carbonates, that resulted from extracellular biomineralization by extremophiles isolated from a variety of extreme environments ranging from permafrost to hydrothermal vent systems. The results of this study are critical to recognizing biomarkers in terrestrial and extraterrestrial environments.

Thomas-Keprta, Kathie↗

Flow diagnostics, chemically reacting turbulent flow modeling and turbulent mixing: A summary of project studies in combustion

This report includes copies of relevant publications, including conference proceedings, resulting from studies funded by NAG3-1010. Topics include flow visualization, LDV (laser doppler velocimeter), straight and curved simulations, and kinetics modeling of nitrogen oxides, including a turbulent mixing model for O2 and a maximum mixedness model.

Ghorashi, Bahman↗

Reversible Reactions, Mesh Size, and Segmental Dynamics Control Penetrant Diffusion in Ethylene Vitrimers

The diffusion of two aromatic dyes with nearly identical sizes was measured in ethylene vitrimers with precise linker lengths and borate ester cross-links using fluorescence recovery after photobleaching (FRAP). One dye possessed a reactive hydroxyl group, while the second was inert. The reaction of the hydroxyl group with the network is slow relative to the hopping times of the dye, resulting in a large slowdown by a factor of 50 for a reactive probe molecule. A kinetic model was fit to the fluorescence intensity data to determine rate constants for the reversible reaction of the dye from the network, which confirms the role of slow reaction kinetics. A second network cross-linker was also investigated with a substituted boronic ester showing ∼10,000 times faster exchange kinetics. In this system, the two dyes show the same diffusion coefficient, as the reaction is no longer the rate-limiting step. The role of dense meshes on small and large dyes is also discussed in the context of the existing theories. Finally, these results highlight the potential of dynamic networks to control penetrant transport through synergistic effects of the mesh size, dynamic bond kinetics, and penetrant–network interactions.

confinement↗

Fast dynamics of a hydrogen-bonding glass forming liquid: Chemical exchange-induced spectral diffusion in 2D IR spectroscopy

Polarization-selective Two Dimensional Infrared (2D IR) and IR pump-probe spectroscopies have been performed on the hydrogen bonding glass forming liquid 2-biphenylmethanol doped with the long-lived vibrational probe phenylselenocyanate over a wide range of temperatures. The spectral diffusion seen in the 2D spectra was found to have a large polarization dependence, in large excess of what is predicted by standard theory. This anomaly was explained by decomposing the 2D spectra into hydrogen-bonding and non-bonding components, which exchange through large-angle orientational motion. By adapting chemical exchange theories, parameters for the component peaks were then calculated by fitting the polarization-dependent spectral diffusion and the pump-probe anisotropy. A model of highly heterogeneous exchange and orientational dynamics was used to explain the observed time dependences as a function of temperature on fast time scales. The experimental observations, the kinetic modeling, and physical arguments lead to the determination of the times for interconversion of slow dynamics structural domains to fast dynamics structural domains in the supercooled liquid as a function of temperature. The slow to fast domain interconversion times range from 40 ps at 355 K to 5000 ps at 270 K.

14 SOLAR ENERGY↗

ECUT (Energy Conversion and Utilization Technologies) program: Biocatalysis project

The Annual Report presents the fiscal year (FY) 1988 research activities and accomplishments, for the Biocatalysis Project of the U.S. Department of Energy, Energy Conversion and Utilization Technologies (ECUT) Division. The ECUT Biocatalysis Project is managed by the Jet Propulsion Laboratory, California Institute of Technology. The Biocatalysis Project is a mission-oriented, applied research and exploratory development activity directed toward resolution of the major generic technical barriers that impede the development of biologically catalyzed commercial chemical production. The approach toward achieving project objectives involves an integrated participation of universities, industrial companies and government research laboratories. The Project's technical activities were organized into three work elements: (1) The Molecular Modeling and Applied Genetics work element includes research on modeling of biological systems, developing rigorous methods for the prediction of three-dimensional (tertiary) protein structure from the amino acid sequence (primary structure) for designing new biocatalysis, defining kinetic models of biocatalyst reactivity, and developing genetically engineered solutions to the generic technical barriers that preclude widespread application of biocatalysis. (2) The Bioprocess Engineering work element supports efforts in novel bioreactor concepts that are likely to lead to substantially higher levels of reactor productivity, product yields and lower separation energetics. Results of work within this work element will be used to establish the technical feasibility of critical bioprocess monitoring and control subsystems. (3) The Bioprocess Design and Assessment work element attempts to develop procedures (via user-friendly computer software) for assessing the energy-economics of biocatalyzed chemical production processes, and initiation of technology transfer for advanced bioprocesses.

Baresi, Larry↗

Numerical modeling of chemical looping oxidative dehydrogenation of ethane in parallel packed beds

Chemical looping oxidative dehydrogenation (CL-ODH) of ethane has the potential to be a highly efficient alternative to steam cracking for ethylene production. Accurate reactor modeling is of critical importance to efficiently scale up and optimize this new technology. This study reports a one-dimensional, heterogeneous packed bed model to simulate the CL-ODH of ethane to ethylene with a Na 2 MoO 4 -promoted CaTi 0.1 Mn 0.9 O 3 redox catalyst. Here, the overall reaction kinetics was well-described by coupling the gas-phase steam cracking of ethane with the reduction kinetics of the redox catalyst by H 2 and C 2 H 4 . The impact of H 2 on the formation rate of CO 2 byproduct from C 2 H 4 conversion was also thoroughly investigated to validate the applicability of the kinetic model under operational environments. The temperature variation within the different CL-ODH steps and the temperature distribution along the bed were also carefully considered. The accuracy of the model was validated by experiments conducted in a large lab-scale packed bed reactor (200 g catalyst loading), with an average deviation of 2.8% in terms of ethane conversion and ethylene yield. The model was subsequently used to optimize the operating parameters of the CL-ODH reactor, indicating that up to 63.7% single-pass C 2 +olefin yield can be achieved with the current redox catalyst bed whereas further optimization of the redox catalyst to inhibit C 2 H 4 activation can result in 69.4% single-pass C 2 +yield while maintaining low CO 2 selectivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Formation of phenanthrenyl radicals via the reaction of acenaphthyl with acetylene

Ab initio G3(MP2,CC)/B3LYP/6–31G** calculations of the potential energy surface for the reaction of 3-acenaphthyl radical with acetylene were combined with Rice-Ramsperger-Kassel-Marcus Master Equation calculations of the temperature- and pressure-dependent reaction rate constants and product branching ratios with the goal to examine the transformation of an edge five-membered ring into a six-membered one. The reaction mechanism has been shown to contain two stages: (1) the formation of 3-ethynylacenaphthylene + H in the 3-acenaphthyl + C 2 H 2 reaction via acetylene addition to the radical site and an H loss, (2) the formation of the 1-phenanthrenyl radical in the 3-ethynylacenaphthylene + H reaction via H addition to the five-membered ring followed by the ring flip. The results of kinetic modeling show this pathway being faster than the pathway proposed earlier featuring the CCH chemisorption on the six-membered ring without involvement of the five-membered ring. A kinetic test demonstrated the dominance of the former pathway for the formation of pyrene from naphthalene. Here, it is expected that the new mechanism plays a major role in the transformation of five-membered rings on edges of PAH structures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The tarantula toxin GxTx detains K + channel gating charges in their resting conformation

Allosteric ligands modulate protein activity by altering the energy landscape of conformational space in ligand–protein complexes. Here we investigate how ligand binding to a K + channel’s voltage sensor allosterically modulates opening of its K + -conductive pore. The tarantula venom peptide guangxitoxin-1E (GxTx) binds to the voltage sensors of the rat voltage-gated K + (Kv) channel Kv2.1 and acts as a partial inverse agonist. When bound to GxTx, Kv2.1 activates more slowly, deactivates more rapidly, and requires more positive voltage to reach the same K + -conductance as the unbound channel. Further, activation kinetics are more sigmoidal, indicating that multiple conformational changes coupled to opening are modulated. Single-channel current amplitudes reveal that each channel opens to full conductance when GxTx is bound. Inhibition of Kv2.1 channels by GxTx results from decreased open probability due to increased occurrence of long-lived closed states; the time constant of the final pore opening step itself is not impacted by GxTx. When intracellular potential is less than 0 mV, GxTx traps the gating charges on Kv2.1’s voltage sensors in their most intracellular position. Gating charges translocate at positive voltages, however, indicating that GxTx stabilizes the most intracellular conformation of the voltage sensors (their resting conformation). Kinetic modeling suggests a modulatory mechanism: GxTx reduces the probability of voltage sensors activating, giving the pore opening step less frequent opportunities to occur. This mechanism results in K + -conductance activation kinetics that are voltage-dependent, even if pore opening (the rate-limiting step) has no inherent voltage dependence. We conclude that GxTx stabilizes voltage sensors in a resting conformation, and inhibits K + currents by limiting opportunities for the channel pore to open, but has little, if any, direct effect on the microscopic kinetics of pore opening. The impact of GxTx on channel gating suggests that Kv2.1’s pore opening step does not involve movement of its voltage sensors.

Physiology↗

Phosphocreatine kinetics at the onset of contractions in skeletal muscle of MM creatine kinase knockout mice

Phosphocreatine (PCr) depletion during isometric twitch stimulation at 5 Hz was measured by (31)P-NMR spectroscopy in gastrocnemius muscles of pentobarbital-anesthetized MM creatine kinase knockout (MMKO) vs. wild-type C57B (WT) mice. PCr depletion after 2 s of stimulation, estimated from the difference between spectra gated to times 200 ms and 140 s after 2-s bursts of contractions, was 2.2 +/- 0.6% of initial PCr in MMKO muscle vs. 9.7 +/- 1.6% in WT muscles (mean +/- SE, n = 7, P < 0.001). Initial PCr/ATP ratio and intracellular pH were not significantly different between groups, and there was no detectable change in intracellular pH or ATP in either group after 2 s. The initial difference in net PCr depletion was maintained during the first minute of continuous 5-Hz stimulation. However, there was no significant difference in the quasi-steady-state PCr level approached after 80 s (MMKO 36.1 +/- 3.5 vs. WT 35.5 +/- 4.4% of initial PCr; n = 5-6). A kinetic model of ATPase, creatine kinase, and adenylate kinase fluxes during stimulation was consistent with the observed PCr depletion in MMKO muscle after 2 s only if ADP-stimulated oxidative phosphorylation was included in the model. Taken together, the results suggest that cytoplasmic ADP more rapidly increases and oxidative phosphorylation is more rapidly activated at the onset of contractions in MMKO compared with WT muscles.

NASA Discipline Cell Biology↗