Reactivite d'hydrocarbures methylenecyclo-hexaniques—I : Stereochimie de la reaction d'oxymercuration-demercuration

Methylenecyclohexanes, prepared in excellent yield by Corey and Chaykovsky then Cornforth reactions, give on oxymercuration followed by reductive demercuration tertiary alcohols resulting from axial attack by solvent. The attack takes place trans to the substiuent when the latter is at the 2 position. α-Hydroxy or methoxy compounds behave similarly to each other. For acetoxy compounds, the cis alcohols are obtained preferentially, by intramolecular attack of acetoxy group on the mercurinium ion intermediate. The results can be explained satisfactorily on the assumption that the factors inducing stereochemistry are short distance interactions.     

Latex Fractionation by Sedimentation and Colloidal Crystallization: The Case of Poly(styrene-co-acrylamide)

Poly(styrene-co-acrylamide) (PS-AAM) latex was prepared, fractionated by sedimentation under gravity, and characterized by PCS, infrared spectra, secondary and backscattered electron imaging in the scanning electron microscope, and electron spectroscopy imaging in an analytical transmission electron microscope. Three latex fractions were obtained. The lower fraction was opalescent and its particles were the more uniform, concerning size, chemical composition, and topochemical features. This lower fraction was still further fractionated by zonal centrifugation in a density gradient, yielding two fractions with similar macrocrystal-forming abilities but different sizes and chemical compositions. These results confirm those previously obtained for the PS-HEMA latex. Copyright 2000 Academic Press.     

APPLICATIONS OF MULTICOMPONENT ASSEMBLY PROCESSES TO THE FACILE SYNTHESES OF DIVERSELY FUNCTIONALIZED NITROGEN HETEROCYCLES

Several multicomponent assembly processes have been developed for the synthesis of intermediates that may be elaborated by a variety of cyclizations to generate a diverse array of highly functionalized heterocycles from readily-available starting materials. The overall approach enables the efficient preparation of libraries of small molecules derived from fused, privileged scaffolds.     

Matched-field depth estimation for active sonar

This work concerns the problem of estimating the depth of a submerged scatterer in a shallow-water ocean by using an active sonar and a horizontal receiver array. As in passive matched-field processing (MFP) techniques, numerical modeling of multipath propagation is used to facilitate localization. However, unlike passive MFP methods where estimation of source range is critically dependent on relative modal phase modeling, in active sonar source range is approximately known from travel-time measurements. Thus the proposed matched-field depth estimation (MFDE) method does not require knowledge of the complex relative multipath amplitudes which also depend on the unknown scatterer characteristics. Depth localization is achieved by modeling depth-dependent relative delays and elevation angle spreads between multipaths. A maximum likelihood depth estimate is derived under the assumption that returns from a sequence of pings are uncorrelated and the scatterer is at constant depth. The Cramér-Rao lower bound on depth estimation mean-square-error is computed and compared with Monte Carlo simulation results for a typical range-dependent, shallow-water Mediterranean environment. Depth estimation performance to within 10% of the water column depth is predicted at signal-to-noise ratios of greater than 10 dB. Real data results are reported for depth estimation of an echo repeater to within 10-m accuracy in this same shallow water environment.     

The hydrological response of heavy clay grassland soils to rainfall in south‐west England using δ2H

Stable isotopes of water have been previously used in catchment studies to separate rain‐event water from pre‐event groundwater. However, there are a lack of studies at the smaller scale looking at the separation of event water from pre‐event water. This is particularly relevant for heavy clay soil systems through which the movement of water is uncertain but is thought to be rainwater‐dominated. The data presented here were collected at a rural site in the south‐west of England. The historic rainfall at the site was isotopically varied but similar to the global meteoric water line, with annual weighted means of ?37‰ for δ²H and ?5.7‰ for δ¹⁸O and with no seasonal variation. Drainage was sampled from the inter‐flow (surface runoff + lateral through‐flow) and drain‐flow (55 cm deep mole drains) pathways of two 1 ha lysimeters during two rainfall events, which had δ²H values of ?68‰ and ?92‰, respectively. The δ²H values of the lysimeter drainage water suggest that there was no contribution of event water during the first, small discharge (Q) event; however, the second larger event did show isotopic variation in δ²H values negatively related to Q indicating that rainwater was contributing to Q. A hydrograph separation indicated that only 49–58% of the inter‐flow and 18–25% of the drain‐flow consisted of event water. This was surprising given that these soil types are considered retentive of soil water. More work is needed on heavy clay soils to understand better the nature of water movement from these systems. Copyright © 2010 John Wiley & Sons, Ltd.     

13C and 77Se NMR of some organometallic derivatives with Ti,Zr and Hf

¹³C and ⁷⁷Se NMR was carried out on dicyclopentadienyl derivatives of Ti, Zr and Hf with selenium bonded directly to the metal. Although ¹³C NMR is not sensitive to different substitution, ⁷⁷Se NMR is valuable and reflects the influence of the different organic substituents and the nature of the metals bonded to the selenium atom.