Unsteady axisymmetric stagnation flow on a circular cylinder

Unsteady, axisymmetric stagnation flow about a circular cylinderis examined when the far-field flow is a periodic function oftime with a fixed time average and an oscillatory part of prescribedamplitude and frequency. Solutions are computed for arbitraryvalues of the Reynolds number, quantifying the effects of surfacecurvature, and a frequency parameter based on the period ofthe far-field flow. It is found that solutions remain regularand periodic provided that the far-field amplitude lies belowa critical value. Above this value, solutions terminate in afinite-time singularity. The blow-up time is delayed by increasingthe curvature of the surface. These results are corroboratedby asymptotic predictions valid in the limits of small and largeamplitude and frequency. For large Reynolds number, the problemreduces to the two-dimensional stagnation-point flow againsta plane wall studied by previous authors.     

Understanding the Deactivation Pathways of Iridium(III) Pyridine-Carboxiamide Catalysts for Formic Acid Dehydrogenation

The degradation pathways of highly active [Cp*Ir(κ²-N,N-R-pica)Cl] catalysts (pica=picolinamidate; 1 R=H, 2 R=Me) for formic acid (FA) dehydrogenation were investigated by NMR spectroscopy and DFT calculations. Under acidic conditions (1 equiv. of HNO₃), 2 undergoes partial protonation of the amide moiety, inducing rapid κ²-N,N to κ²-N,O ligand isomerization. Consistently, DFT modeling on the simpler complex 1 showed that the κ²-N,N key intermediate of FA dehydrogenation ( I_NH ), bearing a N-protonated pica, can easily transform into the κ²-N,O analogue ( I_NH2 ; ΔG^≠≈11 kcal mol⁻¹, ΔG ≈−5 kcal mol⁻¹). Intramolecular hydrogen liberation from I_NH2 is predicted to be rather prohibitive (ΔG^≠≈26 kcal mol⁻¹, ΔG≈23 kcal mol⁻¹), indicating that FA dehydrogenation should involve mostly κ²-N,N intermediates, at least at relatively high pH. Under FA dehydrogenation conditions, 2 was progressively consumed, and the vast majority of the Ir centers (58 %) were eventually found in the form of Cp*-complexes with a pyridine-amine ligand. This likely derived from hydrogenation of the pyridine-carboxiamide via a hemiaminal intermediate, which could also be detected. Clear evidence for ligand hydrogenation being the main degradation pathway also for 1 was obtained, as further confirmed by spectroscopic and catalytic tests on the independently synthesized degradation product 1 c . DFT calculations confirmed that this side reaction is kinetically and thermodynamically accessible.     

Robust Optimal Service Analysis of Single-Server Re-Entrant Queues

We generalize the analysis of J.A. Ball, M.V. Day, and P. Kachroo (Mathematics of Control, Signals, and Systems, vol. 12, pp. 307–345, 1999) to a fluid model of a single server re-entrant queue. The approach is to solve the Hamilton-Jacobi-Isaacs equation associated with optimal robust control of the system. The method of staged characteristics is generalized from Ball et al. (1999) to construct the solution explicitly. Formulas are developed allowing explicit calculations for the Skorokhod problem involved in the system equations. Such formulas are particularly important for numerical verification of conditions on the boundary of the nonnegative orthant. The optimal control (server) strategy is shown to be of linear-index type. Dai-type stability properties are discussed. A modification of the model in which new customers are allowed only at a specified entry queue is considered in 2 dimensions. The same optimal strategy is found in that case as well.     

Polyethylene glycol matrix reduces the rates of photochemical and thermal release of nitric oxide from S-nitroso-N-acetylcysteine

S -nitrosothiols have many biological activities and may act as nitric oxide (NO) carriers and donors, prolonging NO half-life in vivo. In spite of their great potential as therapeutic agents, most S -nitrosothiols are too unstable to isolate. We have shown that the S -nitroso adduct of N -acetylcysteine (SNAC) can be synthesized directly in aqueous and polyethylene glycol (PEG) 400 matrix by using a reactive gaseous (NO/O₂) mixture. Spectral monitoring of the S–N bond cleavage showed that SNAC, synthesized by this method, is relatively stable in nonbuf-fered aqueous solution at 25°C in the dark and that its stability is greatly increased in PEG matrix, resulting in a 28-fold decrease in its initial rate of thermal decomposition. Irradiation with UV light (λ= 333 nm) accelerated the rate of decomposition of SNAC to NO in both matrices, indicating that SNAC may find use for the photogeneration of NO. The quantum yield for SNAC decomposition decreased from 0.65 ± 0.15 in aqueous solution to 0.047 ± 0.005 in PEG 400 matrix. This increased stability in PEG matrix was assigned to a cage effect promoted by the PEG microenvironment that increases the rate of geminated radical pair recombination in the homolytic S–N bond cleavage process. This effect allowed for the storage of SNAC in PEG at −20°C in the dark for more than 10 weeks with negligible decomposition. Such stabilization may represent a viable option for the synthesis, storage and handling of S -nitrosothiol solutions for biomedical applications.     

Bursting as a source for predictability in biological neural network activity

The role of bursting as a unit of neural information has received considerable support in the recent years. Experimental evidence shows that in many different neural systems, e.g. visual cortex or hippocampus, bursting is essential for coding and processing. We have recently demonstrated (Menendez de la Prida et al., 1996) the spontaneous presence of bursts in in vitro hippocampal slices from newborn animals, providing a good system to investigate bursting dynamics in physiological conditions. Here we analyze the interspike intervals (ISIs) of five intracellularly recorded cells from immature hippocampal networks. First, we test the time series against Poisson processes, typical of pure random behavior, using the Kolmogorov-Smirnov test. Only 2/5 records strongly deviate from Poisson process. Nonlinear diction tests are then applied to compare original series with its Gaussian-scaled random phase surrogates and signs of short time predictability are observed (1/5). This predictability is originated by the intrinsic structure of bursts, in an otherwise purely random process, and can be removed completely by eliminating the bursts from the original time series. Here we introduce this method of eliminating bursts to get insight into the nonlinear dynamics of firing. Also the interburst intervals are indistinguishable from pure noise. The analysis of unstable periodicities within the bursts in the original ISIs shows that signs of nonlinearities can be statistically differentiated from their surrogate realizations (Pierson-Moss method). We discuss the computational implication of these results.     

Prediction of periodic boundary layers

A relatively simple, yet efficient and accurate finite difference method is developed for the solution of the unsteady boundary layer equations for both laminar and turbulent flows. The numerical procedure is subjected to rigorous validation tests in the laminar case, comparing its predictions with exact analytical solutions, asymptotic solutions, and/or experimental results. Calculations of periodic laminar boundary layers are performed from low to very high oscillation frequencies, for small and large amplitudes, for zero as well as adverse time-mean pressure gradients, and even in the presence of significant flow reversal. The numerical method is then applied to predict a relatively simple experimental periodic turbulent boundary layer, using two well-known quasi-steady closure models. The predictions are shown to be in good agreement with the measurements, thereby demonstrating the suitability of the present numerical scheme for handling periodic turbulent boundary layers. The method is thus a useful tool for the further development of turbulence models for more complex unsteady flows.     

Fiber-to-the-curb systems: Architectural alternatives

Several fiber-to-the-curb (FTTC) systems have been proposed in response to the present high cost of fiber-to-the-home (FTTH) systems for plain old telephone service (POTS). With FTTC systems, fiber is brought only as far as the service access point (SAP). From there, copper drops carry POTS signals from the SAP to several residences. Due to the extensive sharing of optical sources and the fibers running to the SAP, the per-subscriber system cost is reduced to levels comparable to that of a copper-bused digital loop currier distribution system.

This paper presents an analysis of three different fiber-to-the-curb distribution networks that serve up to 96 customers, initially providing two POTS channels to each customer. These systems serve four customers per SAP through star, distributed star, or bus topologies that offer differing levels of sharing of fiber and optoelectronic components. We estimate the installed first costs (IFC) of the distribution link (remote node to customer) for the three FTTC scenarios and find them comparable to the IFC of copper distribution system with similar capabilities. We also look at the evolution of these systems to broadband ETTH systems as well as near-term upgrades providing entertainment video services.