2 resultados para Dispersion Stabilization
em Illinois Digital Environment for Access to Learning and Scholarship Repository
Resumo:
Simulations of droplet dispersion behind cylinder wakes and downstream of icing tunnel spray bars were conducted. In both cases, a range of droplet sizes were investigated numerically with a Lagrangian particle trajectory approach while the turbulent air flow was investigated with a hybrid Reynolds-Averaged Navier-Stokes/Large-Eddy Simulations approach scheme. In the first study, droplets were injected downstream of a cylinder at sub-critical conditions (i.e. with laminar boundary layer separation). A stochastic continuous random walk (CRW) turbulence model was used to capture the effects of sub-grid turbulence. Small inertia droplets (characterized by small Stokes numbers) were affected by both the large-scale and small-scale vortex structures and closely followed the air flow, while exhibiting a dispersion consistent with that of a scalar flow field. Droplets with intermediate Stokes numbers were centrifuged by the vortices to the outer edges of the wake, yielding an increased dispersion. Large Stokes number droplets were found to be less responsive to the vortex structures and exhibited the least dispersion. Particle concentration was also correlated with vorticity distribution which yielded preferential bias effects as a function of different particle sizes. This trend was qualitatively similar to results seen in homogenous isotropic turbulence, though the influence of particle inertia was less pronounced for the cylinder wake case. A similar study was completed for droplet dispersion within the Icing Research Tunnel (IRT) at the NASA Glenn Research Center, where it is important to obtain a nearly uniform liquid water content (LWC) distribution in the test section (to recreate atmospheric icing conditions).. For this goal, droplets are diffused by the mean and turbulent flow generated from the nozzle air jets, from the upstream spray bars, and from the vertical strut wakes. To understand the influence of these three components, a set of simulations was conducted with a sequential inclusion of these components. Firstly, a jet in an otherwise quiescent airflow was simulated to capture the impact of the air jet on flow turbulence and droplet distribution, and the predictions compared well with experimental results. The effects of the spray bar wake and vertical strut wake were then included with two more simulation conditions, for which it was found that the air jets were the primary driving force for droplet dispersion, i.e. that the spray bar and vertical strut wake effects were secondary.
Resumo:
Orotidine 5′-monophosphate decarboxylase (OMPDC) achieves a rarely paralleled rate acceleration, yet the catalytic basis prompting this enhancement have yet to be fully elucidated. To accomplish decarboxylation, OMPDC must overcome the high energy barrier due to the localized anionic charge of the intermediate. Mechanistic studies employing enzyme mutagenesis and product or intermediate analogues were used to investigate possible transition state stabilization by a carbene resonance structure. Viability of the carbene structure depends upon a key hydrogen bond between O4 of the substrate and the amide backbone of a conserved serine or threonine. Substitution of the conserved residue with Pro resulted in a kcat/KM of 1 M-1s-1; deletion of the FUMP O4 resulted in a product analogue that does not undergo H6 exchange or inhibit decarboxylation. Hence, indirect evidence reveals the O4-backbone interaction plays an important role for binding and catalysis. OMPDC likely has honed multiple mechanisms to attain its remarkable catalysis. The successful crystallizations of OMPDC a decade ago sparked hypotheses that structure and sequence conserved residues induced productive strain on the substrate-enzyme complex. Here, we demonstrate a new source of stress: a hydrophobic pocket adjacent to the OMP carboxylate that exhibits kinetic parameters characteristic of substrate destabilization. Substitution of these residues with hydrophilic side-chains, by providing hydrogen-bonding partners, decreased kcat by 10 to 10^4–fold. The same substitutions display very little change in the rate of product H6 exchange, supporting that this hydrophobic pocket affects the substrate-enzyme complex before the transition state. We also provide evidence that hydrophilic residues can insert water molecules into the pocket with detrimental effects to catalysis.