A modular approach to a new class of phosphinohydrazones and their use in asymmetric allylic alkylation reactions

A group of five phosphino hydrazones with a pendant binaphthyl unit as a chiral modifier has been synthesized from non-racemic 2,2′-bis(bromomethyl)-1,1′-binaphthyl and 3,3′-diiodo-2,2′-bis(bromomethyl)-1,1′-binaphthyl as the key intermediates. Their efficiency as chiral ligands in palladium-catalyzed allylic alkylation reactions has been investigated showing up to 95% ee under optimized conditions. X-ray diffraction structures of mono- and dimeric Pd complexes are also reported.     

Electron paramagnetic resonance of some lanthanide ions in yttrium and lutetium vanadate

The electron paramagnetic resonance (EPR) parameters have been determined for the trivalent ions neodymium, erbium and ytterbium, at low abundance in lutetium vanadate. Crystal field splittings produce ground states which are Kramers doublets, and measurements were made of theg-values both parallel and perpendicular to the tetragonal axis; they are compared with previous measurements in yttrium vanadate. Two of the crystal field splitting parameters of the trivalent gadolinium ion (S = 7/2) in LuVO₄ show noticeable difference from those in YVO₄.     

Control limits for two-state partially observable Markov decision processes

A production process can be in either a GOOD or a BAD state. The true state is unknown and can only be inferred from observations. If the state is good during one period it may deteriorate and become bad during the next period. Two actions are available: CONTINUE or REPLACE (for a fixed cost). The objective is to maximize the expected discounted value of the total future profits.     

Preparation and characterization of some unusually transparent poly(dimethylsiloxane) nanocomposites

A technique was developed for preparing poly(dimethylsiloxane) nanocomposites having unusually high transparencies as quantitatively judged by ultraviolet–visible spectroscopy. The method was the in situ generation of silica particles by a two‐step sol–gel procedure in which the required water of hydrolysis was simply absorbed from the air, and the catalyst was generated in situ from a tin salt. Electron microscopy showed that the phase‐separated silica domains were very small (30–50 nm in diameter) and well dispersed, as expected from the transparency of the composites. Stress‐strain measurements in tension indicated that the particles provide very good reinforcement. Ultra‐small‐angle X‐ray scattering data showed that the domain morphology depends strongly on catalyst, but weakly on loading level. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1897–1901, 2003     

Biodegradable polycaprolactone–polyanhydrides blends

Biodegradable polymers based on a blend of polycaprolactone (PCL) and aliphatic polyanhydrides with various monomer lengths were prepared to obtain desired polymer blends for use as drug carriers. The physicochemical, mechanical, and drug‐release properties of these blends were investigated by various techniques to evaluate the uniformity degree of the polymer blends to establish their potential applications in drug delivery. The results demonstrated that the heat of fusion (ΔH) of the polyanhydride or the blend is increased in relation to the length of the aliphatic chain. However, the blends had different properties than pure polyanhydride, and the crystallization degree of the blends, as expressed by the ΔH, decreased in relation to the ΔH of the pure polyanhydride. Drug‐release studies from blends of PCL and aliphatic polyanhydrides demonstrated first‐order kinetics of the release rate. Polymer degradation was independent at the polyanhydride monomer length. On the basis of theoretical calculation of the interaction factor, a blend of PCL and poly(dodecanedeoic anhydride) was chosen for further elucidation of its thermal, mechanical, and degradation properties. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3781–3787, 2003     

Identification of regions of fastest mixing in a system of point vortices

This paper describes a numerical method for efficiently identifying the regions of fastest mixing of a passive dye in a flow due to a system of point vortices. Results obtained from computations are presented for systems of three and four point vortices, both in the unbounded domain and inside a circular cylinder. The flow is two‐dimensional and the fluid is incompressible. The regions where mixing is possible are found by studying the largest Lagrangian Lyapunov exponent distribution with respect to various initial positions of tracer particles. The regions of fastest mixing are then identified from the Lyapunov exponent distribution at small times. The results of the method are verified by quantifying the mixing by using a traditional box counting technique. The technique is then applied to several different initial configurations of vortices and some interesting results are obtained. Some numerical findings about the nature of the exponents computed are also discussed. Copyright © 2002 John Wiley Sons, Ltd.     

Long-range acoustic scattering from a shallow-water mud-volcano cluster

Analysis of reverberation measurements in the Straits of Sicily shows high intensity, discrete, scattered returns 10-20 dB above background reverberation. These returns are due to scattering from mud volcanoes. The reverberation from the mud volcanoes at ranges of 15-22 km is reasonably consistent over these spatial scales (i.e., kilometers) and temporal scales of several hours; measurements separated by 4 years are also similar. Statistical characterization indicates that the reverberation associated with a mud-volcano cluster is strongly non-Rayleigh and that the reverberation can be characterized by a single (shape) parameter, roughly independent of frequency. The non-Rayleigh statistics, with a concomitant increase in the probability of false alarm, indicate that mud volcanoes are a likely source of clutter. Mean target strengths were estimated at 1-11 dB over 160-1400 Hz and are consistent with target strengths measured during a different year at short (direct-path) ranges. Accumulated evidence points to small (order 10 m diameter and several meters high) carbonate chimneys on the mud-volcano edifice as the scattering mechanism as opposed to the edifice itself or scattering from gas bubbles in the water column. Thus, the results represent acoustic scattering from mud volcanoes in a quiescent state.     

Influence of root resistivity on plant water uptake mechanism,Part II: analytical solutions for low/moderate soil-root conductivity ratio

A one-dimensional approximate analytical model, which preserves the main features of soil-crop-atmospheric hydrodynamics, has been suggested for plant roots of low soil-root conductivity ratio (SRCR). The proposed approach involves physically based concepts, such as mass balance equation, Darcy’s law, and related water uptake and plant transpiration functions. Two main assumptions have been made to derive the analytical solution: (1) gravitational flow is adopted and (2) the uniform soil moisture distribution within the root water activity zone is supposed. The mass balance equation in its integral form is solved by the method of characteristics. This leads to the two functional equations for soil pressure head and root potential, which can be solved simultaneously by using common software. The model has been further verified against the numerical one. The model represents a reasonable compromise between the complicated mechanism of unsaturated water flow with root water uptake (RWU) and still insufficient knowledge of the soil-plant-atmospheric continuum. It is able to account for temporal fluctuations in root activity zone and provides a relatively simple algorithm for investigation of RWU-mechanism. Besides the theoretical and applicative importance, this flow model yields water and velocity distributions within soil profile, and, thereby, constitutes a preliminary step toward solution of contaminant transport problems in vadose zone. Deceased