An adaptive Lagrangian boundary element approach for three‐dimensional transient free‐surface Stokes flow as applied to extrusion,thermoforming, and rheometry

An adaptive (Lagrangian) boundary element approach is proposed for the general three‐dimensional simulation of confined free‐surface Stokes flow. The method is stable as it includes remeshing capabilities of the deforming free surface and thus can handle large deformations. A simple algorithm is developed for mesh refinement of the deforming free‐surface mesh. Smooth transition between large and small elements is achieved without significant degradation of the aspect ratio of the elements in the mesh. Several flow problems are presented to illustrate the utility of the approach, particularly as encountered in polymer processing and rheology. These problems illustrate the transient nature of the flow during the processes of extrusion and thermoforming, the elongation of a fluid sample in an extensional rheometer, and the coating of a sphere. Surface tension effects are also explored. Copyright © 2001 John Wiley & Sons, Ltd.     

A simple and efficient synthesis of new cyclic ureas

A facile access to a wide range of original saturated N-heterocyclic ureas is described using, as a key step, a Michael-type reaction involving isocyanates or amines on a piperidine framework possessing an α,β-unsaturated ester functionality.     

Palladium mediated direct coupling of silylated arylalkynes with propargylic chlorides: an efficient access to functionalized conjugated allenynes

Pd/Cu-catalyzed one-pot reaction of 1-trimethylsilyl-2-arylalkynes with propargylic chlorides in the presence of TBAF is described. The present new procedure is applicable to a wide range of silylated arylalkynes with both electron-withdrawing and electron-donating substituents. Functionalized allenynes can thus be obtained in good yields without prior deprotection of the alkynes.     

Modulation of Relaxivity,Suspension Stability,and Biodistribution of Dendronized Iron Oxide Nanoparticles as a Function of the Organic Shell Design

Nanoparticles (NPs) with a mean diameter of 10 nm are functionalized with three dendrons: D1 a PEGylated PAMAM dendron of generation 0.5, D2 a hydrophilic oligoethyleneglycol‐derivatized dendron (D2) displaying a phosphonic acid at the focal point, and D2–2P the same dendron than D2 but with two phosphonic acid anchoring agents. Their grafting is confirmed by IR spectroscopy and elemental analysis. All dendronized NPs are stable over a long period of time in suspensions in water and in different physiological media and display a mean hydrodynamic diameter smaller than 50 nm whatever the molecule architecture. NMRD profiles and relaxivity measurements highlight the influence of the molecule architecture on the water diffusion close to the magnetic core thus influencing the relaxation properties at low magnetic field. The high hydrophilic architecture of the dendron D2 by contrast to dendron D1 allows maintaining the colloidal stability in different conditions while ensuring a very good accessibility of water molecule close to the magnetic core. Coupling of a fluorescent dye on dendrons have allowed investigating the biodistribution of dendronized NPs, which are found to be quickly eliminated through urinary and hepatobiliary pathways within 4 h. Furthermore, no enhanced permeation and retention effect in tumors can be observed.     

Determination of compound-specific Hg isotope ratios from transient signals using gas chromatography coupled to multicollector inductively coupled plasma mass spectrometry (MC-ICP/MS)

MeHg and inorganic Hg compounds were measured in aqueous media for isotope ratio analysis using aqueous phase derivatization, followed by purge-and-trap preconcentration. Compound-specific isotope ratio measurements were performed by gas chromatography interfaced to MC-ICP/MS. Several methods of calculating isotope ratios were evaluated for their precision and accuracy and compared with conventional continuous flow cold vapor measurements. An apparent fractionation of Hg isotopes was observed during the GC elution process for all isotope pairs, which necessitated integration of signals prior to the isotope ratio calculation. A newly developed average peak ratio method yielded the most accurate isotope ratio in relation to values obtained by a continuous flow technique and the best reproducibility. Compound-specific isotope ratios obtained after GC separation were statistically not different from ratios measured by continuous flow cold vapor measurements. Typical external uncertainties were 0.16‰ RSD (n = 8) for the ²⁰²Hg^/198Hg ratio of MeHg and 0.18‰ RSD for the same ratio in inorganic Hg using the optimized operating conditions. Using a newly developed reference standard addition method, the isotopic composition of inorganic Hg and MeHg synthesized from this inorganic Hg was measured in the same run, obtaining a value of δ ²⁰²Hg = −1.49 ± 0.47 (2SD; n = 10). For optimum performance a minimum mass of 2 ng per Hg species should be introduced onto the column.     

Manifestation of stereoelectronic effects on the calculated carbon-nucleophile bond lengths in nucleophilic addition to sterically unbiased ketones

Calculations at the B3LYP/6-311G(d,p) level of the structures of diastereoisomeric pairs of alcohols 1E-12E and 1Z-12Z, resulting from either reduction or methylation of sterically unbiased ketones show that the newly formed C-Nu bond lengths of the major isomers are larger than those of the minor isomers.