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At least 415 records · Page 23

CFD modeling of pre-spark heat release in a boosted direct-injection spark-ignition engine

Accurate predictions of low-temperature heat release (LTHR) are critical for modeling auto-ignition processes in internal combustion engines. While LTHR is typically obscured by deflagration, extremely late ignition phasing can lead to LTHR prior to the spark, a behavior known as pre-spark heat release (PSHR). In this research, PSHR in a boosted direct-injection spark-ignition engine was studied using 3-D computational fluid dynamics (CFD) and detailed chemical kinetics. The turbulent combustion was modeled via a hybrid approach that incorporates the G-equation model for tracking the turbulent flame front, and the well-stirred reactor model with detailed chemistry for assessing the low-temperature reactions in unburnt gas. Simulations were conducted using Co-Optima alkylate and E30 fuels at operating conditions characterized by different PSHR intensities. The predicted in-cylinder pressure and heat release rate were found to agree well with experiments. It was found the estimate of previous-cycle trapped residuals is of utmost importance for capturing PSHR correctly. A simulation best practice was developed which keeps the detailed chemistry solver active throughout the entire simulation, allowing to track the evolution of intermediate species from one cycle to the next. Following the validation, the dynamics of PSHR were analyzed in detail employing the pressure-temperature (P-T) trajectory framework. It was shown that PSHR correlated with the first-stage ignition delay of the fuel, hence showing close relation to the in-cylinder P-T trajectory and the chemical kinetics. Besides, it was indicated that LTHR is a self-limiting process that has the effect of attenuating the thermal stratification in the combustion chamber. Furthermore, it was observed the occurrence of PSHR caused the P-T trajectory of end-gas to overlap with the negative temperature coefficient region of the fuel’s ignition-delay maps. This effect was more significant in the fuel-rich regions where engine knock tendency would be generally higher, with potential implications on knock control and mitigation.

42 ENGINEERING↗

Cell signaling by reactive nitrogen and oxygen species in atherosclerosis

The production of reactive oxygen and nitrogen species has been implicated in atherosclerosis principally as means of damaging low-density lipoprotein that in turn initiates the accumulation of cholesterol in macrophages. The diversity of novel oxidative modifications to lipids and proteins recently identified in atherosclerotic lesions has revealed surprising complexity in the mechanisms of oxidative damage and their potential role in atherosclerosis. Oxidative or nitrosative stress does not completely consume intracellular antioxidants leading to cell death as previously thought. Rather, oxidative and nitrosative stress have a more subtle impact on the atherogenic process by modulating intracellular signaling pathways in vascular tissues to affect inflammatory cell adhesion, migration, proliferation, and differentiation. Furthermore, cellular responses can affect the production of nitric oxide, which in turn can strongly influence the nature of oxidative modifications occurring in atherosclerosis. The dynamic interactions between endogenous low concentrations of oxidants or reactive nitrogen species with intracellular signaling pathways may have a general role in processes affecting wound healing to apoptosis, which can provide novel insights into the pathogenesis of atherosclerosis.

Review, Tutorial↗

Towards a Comprehensive Dynamic-chemistry Assimilation for Eos-Chem: Plans and Status in NASA's Data Assimilation Office

In order to support the EOS-Chem project, a comprehensive assimilation package for the coupled chemical-dynamical system is being developed by the Data Assimilation Office at NASA GSFC. This involves development of a coupled chemistry/meteorology model and of data assimilation techniques for trace species and meteorology. The model is being developed using the flux-form semi-Lagrangian dynamical core of Lin and Rood, the physical parameterizations from the NCAR Community Climate Model, and atmospheric chemistry modules from the Atmospheric Chemistry and Dynamics branch at NASA GSFC. To date the following results have been obtained: (i) multi-annual simulations with the dynamics-radiation model show the credibility of the package for atmospheric simulations; (ii) initial simulations including a limited number of middle atmospheric trace gases reveal the realistic nature of transport mechanisms, although there is still a need for some improvements. Samples of these results will be shown. A meteorological assimilation system is currently being constructed using the model; this will form the basis for the proposed meteorological/chemical assimilation package. The latter part of the presentation will focus on areas targeted for development in the near and far terms, with the objective of Providing a comprehensive assimilation package for the EOS-Chem science experiment. The first stage will target ozone assimilation. The plans also encompass a reanalysis (ReSTS) for the 1991-1995 period, which includes the Mt. Pinatubo eruption and the time when a large number of UARS observations were available. One of the most challenging aspects of future developments will be to couple theoretical advances in tracer assimilation with the practical considerations of a real environment and eventually a near-real-time assimilation system.

Pawson, Steven↗

Redox regulation in chloroplast thylakoid lumen: The pmf changes everything, again

Abstract Photosynthesis is the foundation of life on Earth. However, if not well regulated, it can also generate excessive reactive oxygen species (ROS), which can cause photodamage. Regulation of photosynthesis is highly dynamic, responding to both environmental and metabolic cues, and occurs at many levels, from light capture to energy storage and metabolic processes. One general mechanism of regulation involves the reversible oxidation and reduction of protein thiol groups, which can affect the activity of enzymes and the stability of proteins. Such redox regulation has been well studied in stromal enzymes, but more recently, evidence has emerged of redox control of thylakoid lumenal enzymes. This review/hypothesis paper summarizes the latest research and discusses several open questions and challenges to achieving effective redox control in the lumen, focusing on the distinct environments and regulatory components of the thylakoid lumen, including the need to transport electrons across the thylakoid membrane, the effects of pH changes by the proton motive force (pmf) in the stromal and lumenal compartments, and the observed differences in redox states. These constraints suggest that activated oxygen species are likely to be major regulatory contributors to lumenal thiol redox regulation, with key components and processes yet to be discovered.

Plant Sciences↗

Simplified jet-A kinetic mechanism for combustor application

Successful modeling of combustion and emissions in gas turbine engine combustors requires an adequate description of the reaction mechanism. For hydrocarbon oxidation, detailed mechanisms are only available for the simplest types of hydrocarbons such as methane, ethane, acetylene, and propane. These detailed mechanisms contain a large number of chemical species participating simultaneously in many elementary kinetic steps. Current computational fluid dynamic (CFD) models must include fuel vaporization, fuel-air mixing, chemical reactions, and complicated boundary geometries. To simulate these conditions a very sophisticated computer model is required, which requires large computer memory capacity and long run times. Therefore, gas turbine combustion modeling has frequently been simplified by using global reaction mechanisms, which can predict only the quantities of interest: heat release rates, flame temperature, and emissions. Jet fuels are wide-boiling-range hydrocarbons with ranges extending through those of gasoline and kerosene. These fuels are chemically complex, often containing more than 300 components. Jet fuel typically can be characterized as containing 70 vol pct paraffin compounds and 25 vol pct aromatic compounds. A five-step Jet-A fuel mechanism which involves pyrolysis and subsequent oxidation of paraffin and aromatic compounds is presented here. This mechanism is verified by comparing with Jet-A fuel ignition delay time experimental data, and species concentrations obtained from flametube experiments. This five-step mechanism appears to be better than the current one- and two-step mechanisms.

Lee, Chi-Ming↗

Elucidating Microbial Adaptation Dynamics via Autonomous Exposure and Sampling

The adaptation of micro-organisms to their environments is a complex process of interaction between the pressures of the environment and of competition. Reducing this multifactorial process to environmental exposure in the laboratory is a common tool for elucidating individual mechanisms of evolution, such as mutation rates. Although such studies inform fundamental questions about the way adaptation and even speciation occur, they are often limited by labor-intensive manual techniques. Current methods for controlled study of microbial adaptation limit the length of time, the depth of collected data, and the breadth of applied environmental conditions. Small idiosyncrasies in manual techniques can have large effects on outcomes; for example, there are significant variations in induced radiation resistances following similar repeated exposure protocols. We describe here a project under development to allow rapid cycling of multiple types of microbial environmental exposure. The system allows continuous autonomous monitoring and data collection of both single species and sampled communities, independently and concurrently providing multiple types of controlled environmental pressure (temperature, radiation, chemical presence or absence, and so on) to a microbial community in dynamic response to the ecosystem's current status. When combined with DNA sequencing and extraction, such a controlled environment can cast light on microbial functional development, population dynamics, inter- and intra-species competition, and microbe-environment interaction. The project's goal is to allow rapid, repeatable iteration of studies of both natural and artificial microbial adaptation. As an example, the same system can be used both to increase the pH of a wet soil aliquot over time while periodically sampling it for genetic activity analysis, or to repeatedly expose a culture of bacteria to the presence of a toxic metal, automatically adjusting the level of toxicity based on the number or growth rate of surviving cells. We are on our second prototype iteration, with demonstrated functions of microbial growth monitoring and dynamic exposure to UV-C radiation and temperature. We plan to add functionality for general chemical presence or absence by Nov. 2013. By making the project low-cost and open-source, we hope to encourage others to use it as a basis for future development of a common microbial environmental adaptation testbed.

Microbiology↗

A fresh perspective on the role of band bending, and related contributors, in light-driven production of electricity and chemicals

It is widely known that semiconductor-based solar energy conversion could power our planet. This is in part because high-quality semiconductor structures are unrivalled in their ability to separate photogenerated electrons and holes. One effective approach to achieving this photoinduced charge separation relies on a phenomenon known as “band bending”. But details to justify why band bending results in photoinduced charge separation are more complex than often appreciated. This underappreciation is an impediment to the rational, hypothesis-driven design of next-generation approaches to solar energy conversion. Herein we show, by means of derivations rooted in physical chemistry, that several phenomena – not just band bending – can facilitate photoinduced charge separation, and that each is influenced by nonequilibrium species concentration and a parameter, such as diffusion coefficient or rate coefficient, that introduces dynamics. To help visualize the impact of each phenomenon, we introduce plots that depict their contributions as free energy, force, flux, force constant, and rate. We reveal that spatial dopant distributions that define band bending are predictors of initial photogenerated species transport rates. But charge separation alone does not guarantee high-efficiency operation. A photogenerated change in energy that is freely available to do useful work is also essential, and is strongly dependent on semiconductor optical properties and reaction kinetics. Notably, this information reveals that specificity of interfacial chemical reactions – even when they are not preceded by charge separation elsewhere – can result in efficient solar energy conversion. We expect that this tutorial will guide researchers in their pursuit to uncover new mechanisms for light to perform useful work.

14 SOLAR ENERGY↗

dynamics of organic-mineral interactions at the metal oxide-solution interface as studied via binding energetics (Final report)

This project focused on addressing longstanding fundamental and experimental uncertainties on how dissolved organic substances (DOS) interact with metal oxide surface under environmentally relevant conditions. By leveraging a custom-built real-time, in-tandem flow adsorption microcalorimetry-UV-Vis/fluorescence spectroscopy platform, we characterized the binding energetics, kinetics and mechanistic pathways driving DOS-metal oxide interactions at temporal resolution on the order of 1-5 seconds. We studied a diverse suite of model organic compounds/substances – including monocarboxylates (e.g. acetate and benzoate), di-carboxylates (oxalate and succinate), amino acids, amino-based nanparticles and natural organic matter – interacting at the mineral-water interface of structurally- and/or chemically distinct metal oxides (including SiO2, boehmite, ferrihydrite, and γ-Al2O3). Our results indicated that DOS-metal oxide interactions are governed by multi-step reaction pathways, often switching between distinct, resolvable enthalpy- and entropy-driven non-electrostatic or electrostatic configurations. To quantify these interactions, we developed and implemented an analytical workflow that integrates peak deconvolution and Monte-Carlo based error propagation to determine site-specific thermodynamic and kinetic parameters for individual binding/debinding events. In addition to resolving apparent first-order rate constants of each event, we were able to quantify associated apparent equilibrium constants as well as free energy, enthalpy and entropy contribution to the activation and subsequent progression of the binding/debinding process across compounds, compound class and metal oxide surfaces. The kinetic-thermodynamic data produced in this study captured how the interplay between oxide surface reactivity and DOS molecular structure jointly drives binding-debinding dynamics. Notably, that at pH below PZC of the oxide surface, neutral species were heavily involved in monocarboxylate binding, while anionic species drove dicarboxylate binding. Also, that among amino acids 1) positional isomers show distinctive binding characteristics to each other while enantiomers show no significant differences in binding characteristics, 2) molecules that bind via outer-sphere complexation show a larger entropic shift between binding and debinding with no impact on oxide surface while 3) inner-sphere interactions increased anion exchange capacity of the oxide surface. The new insights and data from this work has great potential for improving predictive modeling of carbon dynamics and specifically organic-mineral interactions in environmental and industrial systems.

54 ENVIRONMENTAL SCIENCES↗

Nonequilibrium plasma in water vapor

A kinetic model of a non-equilibrium water vapor plasma created by a nanosecond pulsed discharge at elevated temperatures and at low pressure is presented. The model includes equations for electron, vibrational and gas temperatures combined with equations for neutral, charged, electronically and vibrationally excited species. Simulation results are compared with the available experimental data and show good agreement in dynamics of the plasma decay and electron drift velocities. It is shown that the plasma decay in pure water vapor is controlled by the dissociative recombination. Under the conditions simulated, the concentration of electronically excited species is low, but we observe a formation of vibrationally excited species. Finally, a significant decrease in the electrical conductivity of water plasma with time, which depends on the level of initial ionization, is shown.

42 ENGINEERING↗

Photoionization of seeded combustion products as a method of enhancing the efficiency of magnetohydrodynamic power generators

Here, in this study, we performed an experimental and computational investigation into the feasibility of utilizing photoionization to enhance the electrical conductivity of seeded oxy-fuel combustion products and improve the performance of magnetohydrodynamic (MHD) power generators. We applied a variety of optical and microwave diagnostics to study the ionization and recombination processes of potassium excited by an excimer laser in a high-velocity oxy-fuel free jet. Computational fluid dynamic (CFD) simulations were performed to model the thermophysical properties and species densities of the free jet. The CFD results were validated with position-dependent potassium concentration measurements. Electron recombination exponential lifetimes were measured through time-resolved microwave transmission. The experimental electron lifetimes were compared with lifetimes calculated from CFD-predicted species densities and literature recombination rates. It was determined that K + or O 2 are the most likely recombination partners for photoionized electrons. Time-resolved fluorescence measurements provided evidence of an ionization pathway involving a two-photon ionization of KOH . Finally, a zero-dimensional chemical kinetic model was developed to assess the fundamental viability of inducing a non-equilibrium electron population to provide a net energy return in combustion-driven MHD power generators. We determined that a high energy return is feasible for targeting electrode boundary layers with ultraviolet photoionization. We also found that photoionization could potentially lower the required temperature of the bulk gas flow.

20 FOSSIL-FUELED POWER PLANTS↗

Nanoparticle dynamics in the spatial afterglows of nonthermal plasma synthesis reactors

Nonthermal plasma flow tube reactors are industrially scalable systems for the production of nanocrystal (NC) based materials and coatings. One key advantage of nonthermal plasma synthesis is the ability to both synthesize NCs and deposit films in a single reactor, as at the reactor outlet, NCs can be inertially deposited onto a target substrate. The size and morphology of deposited particles can substantially influence the film structure and function. Though NCs are typically near-spherical and monodispersed as-produced in plasma synthesis reactors, NC charge and growth dynamics can be altered substantially when NCs are sampled out of the plasma and through the spatial afterglow region, affecting deposition. Experiments have demonstrated changes of NC size and charge in the spatial afterglow; however, these dynamics remain unexplored and unexplained via theory and simulation. To address this, we developed a constant number Monte Carlo (CNMC) simulation model to examine the mechanisms of NC decharging and growth in the spatial afterglow of plasma flow tube reactors. Collisions between NC and plasma species, diffusive deposition, and electron desorption from NCs are incorporated in the CNMC simulation. The simulation results are specifically compared with previous experiments on Si NCs synthesized from a low pressure Ar-SiH 4 nonthermal plasma reactor. Furthermore, the experiment-model comparison shows that CNMC models can be implemented which accurately model NC size distribution evolution in a spatial afterglow. Simultaneously, results show that improved collision models, energetic species diffusion models, and electron desorption models will be necessary to accurately depict NC dynamics in spatial afterglows.

42 ENGINEERING↗

Ion Measurements During Pioneer Venus Reentry: Implications for Solar Cycle Variation of Ion Composition and Dynamics

During the final, low solar activity phase of the Pioneer Venus mission, the Orbiter Ion Mass Spectrometer measurements found all ion species, in the midnight-dusk sector, reduced in concentration relative to that observed at solar maximum. Molecular ion species comprised a greater part of the total ion concentration as O(+) and H(+) had the greatest depletions. The nightside ionospheric states were strikingly similar to the isolated solar maximum "disappearing" ionospheres. Both are very dynamic states characterized by a rapidly drifting plasma and 30-100 eV superthermal O(+) ions.

Grebowsky, J. M.↗

Pervasive shifts in forest dynamics in a changing world

Forest dynamics arise from the interplay of environmental drivers and disturbances with the demographic processes of recruitment, growth, and mortality, subsequently driving biomass and species composition. However, forest disturbances and subsequent recovery are shifting with global changes in climate and land use, altering these dynamics. Changes in environmental drivers, land use, and disturbance regimes are forcing forests toward younger, shorter stands. Rising carbon dioxide, acclimation, adaptation, and migration can influence these impacts. Recent developments in Earth system models support increasingly realistic simulations of vegetation dynamics. In parallel, emerging remote sensing datasets promise qualitatively new and more abundant data on the underlying processes and consequences for vegetation structure. In combination, these advances hold promise for improving the scientific understanding of changes in vegetation demographics and disturbances.

54 ENVIRONMENTAL SCIENCES↗

Polysaccharide utilization loci in Bacteroides determine population fitness and community-level interactions

Polysaccharide utilization loci (PULs) are co-regulated bacterial genes that sense nutrients and enable glycan digestion. Human gut microbiome members, notably Bacteroides, contain numerous PULs that enable glycan utilization and shape ecological dynamics. To investigate the role of PULs on fitness and inter-species interactions, we develop a CRISPR-based genome editing tool to study 23 PULs in Bacteroides uniformis (BU). BU PULs show distinct glycan-degrading functions and transcriptional coordination that enables the population to adapt upon loss of other PULs. Exploiting a BU mutant barcoding strategy, we demonstrate that in vitro fitness and BU colonization in the murine gut are enhanced by deletion of specific PULs and modulated by glycan availability. PULs mediate glycan-dependent interactions with butyrate producers that depend on the degradation mechanism and glycan utilization ability of the butyrate producer. Thus, PULs determine community dynamics and butyrate production and provide a selective advantage or disadvantage depending on the nutritional landscape.

59 BASIC BIOLOGICAL SCIENCES↗

Quantifying selective solvent transport under an electric field in mixed-solvent electrolytes

Electrolytes in lithium-ion batteries comprise solvent mixtures, but analysis of ion transport is always based on treating the solvents as a single-entity. We combine electrophoretic NMR (eNMR) measurements and molecular dynamics (MD) simulations to quantify electric-field-induced transport in a concentrated solution containing LiPF 6 salt dissolved in an ethylene carbonate/ethyl methyl carbonate (EC/EMC) mixture. The selective transport of EC relative to EMC is reflected in the difference between two transference numbers, defined as the fraction of current carried by cations relative to the velocity of each solvent species. This difference arises from the preferential solvation of cations by EC and its dynamic consequences. The simulations reveal the presence of a large variety of transient solvent-containing clusters which migrate at different velocities. Rigorous averaging over different solvation environments is essential for comparing simulated and measured transference numbers. Our study emphasizes the necessity of acknowledging the presence of four species in mixed-solvent electrolytes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Supported Electrophilic Organoruthenium Catalyst for the Hydrosilylation of Olefins

A series of supported electrophilic organoruthenium complexes has been synthesized via surface organometallic chemistry (SOMC) techniques and applied to the selective hydrosilylation of olefins. The air-sensitive 16e - complex Cp*RuMes(PCy 3 ) (1) (Cp* = pentamethylcyclopentadienyl, Mes = mesityl) was synthesized by the treatment of Cp*RuCl(PCy 3 ) with mesityl Grignard MesMgBr. This species was chemisorbed onto sulfated zirconia SO 4 /ZrO 2 , but the resulting material was inactive toward cyclohexene hydrosilylation with phenylsilane. Instead, Cp*RuMes(PCy 3 ) was treated with phenylsilane (PhSiH 3 ) to provide a ruthenium disilyl hydride complex Cp*RuH(SiH 2 Ph) 2 (PCy 3 ) (3), which was fully characterized by NMR spectroscopy and single-crystal X-ray diffraction. Grafting this species onto SO 4 /ZrO 2 resulted in the formation of phenylsilane along with the surface electrophilic species [Cp*RuH(R)(X-SiHPh)(PCy 3 )] (R = H, O 3 S-O or O 3 Zr-O; 4a, 4b, X = O 3 S-O, and O 3 Zr-O, respectively) as the major species. Material 4 was characterized via a combination of spectroscopic techniques including dynamic nuclear polarization (DNP)-enhanced solid-state NMR spectroscopy, diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), X-ray absorption spectroscopy (XAS), and density function theory (DFT) calculations. Further, capping the remaining acid sites on 4 with Me 3 Si-SiMe 3 provides 5, which significantly reduces side reactions, such as olefin isomerization and silane redistribution. Catalyst 5 is a highly robust and selective hydrosilylation catalyst and can be recycled up to 5 times without significant diminishment of activity. Exclusive anti-Markovnikov regiochemistry, cis-addition selectivity, and the inactivity of secondary and tertiary silanes provide support for the proposed Glaser-Tilley mechanism involving cationic ruthenium silylene species analogous to homogeneous systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dynamically Unveiling Metal–Nitrogen Coordination during Thermal Activation to Design High‐Efficient Atomically Dispersed CoN 4 Active Sites

Abstract We elucidate the structural evolution of CoN 4 sites during thermal activation by developing a zeolitic imidazolate framework (ZIF)‐8‐derived carbon host as an ideal model for Co 2+ ion adsorption. Subsequent in situ X‐ray absorption spectroscopy analysis can dynamically track the conversion from inactive Co−OH and Co−O species into active CoN 4 sites. The critical transition occurs at 700 °C and becomes optimal at 900 °C, generating the highest intrinsic activity and four‐electron selectivity for the oxygen reduction reaction (ORR). DFT calculations elucidate that the ORR is kinetically favored by the thermal‐induced compressive strain of Co−N bonds in CoN 4 active sites formed at 900 °C. Further, we developed a two‐step (i.e., Co ion doping and adsorption) Co‐N‐C catalyst with increased CoN 4 site density and optimized porosity for mass transport, and demonstrated its outstanding fuel cell performance and durability.

He, Yanghua↗

Rational design of heterogeneous single-site catalysts via surface organometallic chemistry

Single-site heterogeneous catalysts offer an attractive route to unite the molecular precision of homogeneous catalysis with the durability and practical advantages of solids. Surface organometallic chemistry (SOMC) provides a particularly powerful strategy for this purpose by grafting molecular precursors onto tailored surfaces and converting support functionalities into ligand environments for isolated metal centers. As a result, SOMC brings the language and logic of coordination chemistry to heterogeneous catalysis, where the support becomes an integral part of the active site coordination sphere. This Review surveys recent progress in the rational design of SOMC-derived single-site catalysts, with emphasis on synthetic routes, post synthetic transformations, and the deliberate tuning of catalytic behavior through metal-support interactions. Discussions are made on how support identity, hydroxyl topology, acidity, and redox activity shape the geometry, electronic structure, and oxidation state of supported metal sites, as well as how these factors determine activity, selectivity, and stability. We also examine a central limitation of these systems: despite their molecularly informed design, supported single sites often exist as structurally distributed ensembles rather than uniform species, particularly on amorphous supports. This site heterogeneity, along with catalyst dynamics under operating conditions, remains a major barrier to definitive structure-activity relationships. Therefore, emerging approaches that combine advanced characterization, first-principles modeling, ensemble kinetics, and machine learning to resolve active-site structure and guide catalyst development are highlighted. Together, these advances position SOMC as a versatile coordination chemistry framework for the predictive design of heterogeneous catalysts with well-defined molecularly tailored active sites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗