Nature of halide binding to the molybdenum site of sulfite oxidase

Valuable information on the active sites of molybdenum enzymes has been provided from both Mo(V) electron paramagnetic resonance (EPR) spectroscopy and X-ray absorption spectroscopy (XAS). One of three major categories of Mo(V) EPR signals from the molybdenum enzyme sulfite oxidase is the low-pH signal, which forms in the presence of chloride. Two alternative structures for this species have been proposed, one in which the chloride is coordinated directly to Mo and a second in which chloride is held in the arginine-rich basic pocket some 5 ? from Mo. Here we present an independent assessment of the structure of this species by using XAS of the analogous bromide and iodide complexes. We show that there is no evidence of direct Mo-I coordination, and that the data are consistent with a structure in which the halide is bound at ～5 ? from Mo.     

Fourier transform infrared studies of ionic interactions in perfluorinated acid copolymer blends

Ionic interactions have been shown to enhance polymer–polymer miscibility in several highly dissimilar blend systems. In some cases, the miscibility is due to proton transfer from an acidic site on one polymer to a basic site on another, which leads to ion–ion interactions. Studies that have focused on the formation of ionomer blends from highly dissimilar materials, such as fluorocarbons and hydrocarbons or aromatics and aliphatics of widely differing glass transitions, have shown that in the absence of ionic interactions, these materials are immiscible. In this study, we have used Fourier transform infrared (FTIR) spectroscopy techniques, both qualitatively and semiquantitatively, to evaluate the extent of the proton‐transfer mechanism in the enhancement of miscibility in perfluorinated acid copolymer/poly(ethyl acrylate) blends. The perfluorinated acid copolymer contains sulfonic acid groups, whereas the poly(ethyl acrylate) has been modified by the introduction of various amounts of 4‐vinyl pyridine groups as comonomers in the polymer chains. The proton‐transfer mechanism in this case consists of the transfer of the proton on the sulfonic acid group to the nitrogen on the pyridine group, forming a pyridinium cation and a sulfonate anion pair. FTIR has been used to distinguish between the pyridine and pyridinium groups through their absorption bands at 1416 and 1642 cm^?1, respectively. The relative intensities of these bands, as a function of the molar concentration of the pyridine comonomers in the blend, provides a direct quantitative indication of the extent of proton transfer occurring in the system. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1814–1823, 2003     

Design of Practical and Provably Good Random Number Generators

We present a construction for a family of pseudo-random generators that are very fast in practice, yet possess provable statistical and cryptographic unpredictability properties. Such generators are useful for simulations, randomized algorithms, and cryptography.Our starting point is a slow but high quality generator whose use can be mostly confined to a preprocessing step. We give a method of stretching its outputs that yields a faster generator. The fast generator offers smooth memory–time–security trade-offs and also has many desired properties that are provable. The slow generator can be based on strong one-way permutations or block ciphers. Our implementation based on the block cipher DES is faster than popular generators.     

Secondary flow of Rivlin-Ericksen fluids between two concentric spheres oscillating about a fixed diameter

Summary The paper deals with the study of the nature of secondary flow of aRivlin-Ericksen fluid, contained between two concentric spheres, which perform oscillations about a fixed diameter. The steady part of the secondary flow is discussed in detail in the following three cases (i) the outer sphere at rest, the inner oscillating, (ii) the two spheres oscillating with the same angular velocity in the same sense and (iii) the spheres oscillating with the same angular velocity in opposite sense. In a previous paper, a similar problem was discussed for theOldroyd fluids. We find that the secondary flow is strongly dependent on the common frequency of oscillation of the two spheres and on the rotational nature of the motion for the present investigation also. Certain contrasting features of interest between the secondary flow field of the two fluids are also noted.     

Flow around a circular cylinder—structure of the near wake shear layer

The separated shear layer in the near wake of a circular cylinder was investigated using a single hot wire probe, with special attention given to the shear layer instability characteristics. Without end plates to force parallel vortex shedding, the critical Reynolds number for the onset of the instability was 740. The present data, together with all previously published data, show that the ratio of the instability frequency f_sl to the vortex shedding frequency f_v varies as Re^0.65, which is in agreement with the Re^0.67 dependence obtained by Prasad and Williamson [1997, J Fluid Mech 333:375–402]. However, the distribution of f_sl/f_v and the spectra of the longitudinal velocity fluctuation (u) suggest that, on either side of Re=5,000, the shear layer exhibits lower and upper subcritical regimes, in support of the observations by Norberg [1987, publication no. 87/2, Chalmers University of Technology, Sweden] and Prasad and Williamson [1997, J Fluid Mech 343:235–265]. The spectra of u provide strong evidence for the occurrence of vortex pairing in wake shear layers, suggesting that the near wake develops in a similar manner to a mixing layer.     

Turbulence reduction in the mixing layer of a plane jet using small cylinders

 The influence of small diameter cylinders placed at the nozzle exit plane on the development of a plane jet mixing layer is investigated using a single hot wire at a jet Reynolds number of about 23000. There is a reduction in both the growth rate and the momentum thickness of the jet as well as a 20% reduction in the maximum value of u′, the rms longitudinal velocity fluctuation u. The jet virtual origin is shifted downstream and distributions of the normalized mean velocity, u′, skewness and flatness factors of u exhibit much better similarity than in the absence of the cylinder. Spectral measurements indicate that downstream of the cylinder, the peak amplitude at the roll-up or instability frequency is greatly reduced or even suppressed. Two different diameter cylinders, placed independently at several locations in the shear layer yielded similar results. A model based on an interaction between the organized motion in the mixing layer and the vortical structures shed by the cylinder is consistent with our observations. Received: 23 June 1997 / Accepted: 8 December 1997     

RMS spanwise vorticity measurements in a turbulent boundary layer

Turbulent boundary layer measurements of the rms spanwise vorticity t_z with a four hot-wire probe are in reasonable agreement with direct numerical simulations and other published measurements at comparable Reynolds numbers. It is shown that a reasonable accurate approximation for _z can be obtained with only two parallel hot wires.     

Developing effective meta-heuristics for a probabilistic location model via experimental design

This article employs a statistical experimental design to guide and evaluate the development of four meta-heuristics applied to a probabilistic location model. The meta-heuristics evaluated include evolutionary algorithm, tabu search, simulated annealing, and a hybridized hill-climbing algorithm. Comparative results are analyzed using ANOVA. Our findings show that all four implementations produce high quality solutions. In particular, it was found that on average tabu search and simulated annealing find their best solutions in the least amount of time, with relatively small variability. This is especially important for large-size problems when dynamic redeployment is required.