Vortex ring generation due to the coalescence of a water drop at a free surface

 Results are presented of an experimental investigation of vortex ring formation by a fluid drop contacting a free surface with negligible velocity. The pool fluid is mixed with fluorescein dye, and a laser sheet is used to illuminate a plane of the flow. A series of representative images is recorded by a CCD camera and speculation is made regarding specific sources of vorticity flux through the free surface. Two scaling analyses previously presented by other investigators are demonstrated to be equivalent under the assumptions of this experiment, and they provide the motivation for a series of test runs in which the duration of the coalescence process, τ_*, is related to variations in drop diameter L and fluid surface tension σ. Experimental results are in agreement with the analyses, showing τ_*∼σ^-1/2 and τ_*∼L ^3/2. Received: 22 December 1995 / Accepted: 15 October 1996     

New chiral phosphine-phosphite ligands in the enantioselective palladium-catalyzed allylic alkylation

A series of chiral phosphine-phosphite ligands 1-6 have been synthesized and used in the enantioselective palladium-catalyzed reaction of rac-1,3-diphenyl-2-propenyl acetate with dimethyl malonate as nucleophile. Ligands 1a, 2, 3, 5a, 6a, and 6b have been synthesized starting from racemic tert-butylphenylphosphinoborane. The use of dynamically resolved Li phosphide (-)-sparteine provided the optically pure ligands. Crystals of the allylpalladium (6a) complex were obtained, suitable for X-ray crystal structure determination. The X-ray crystal structure of the allylpalladium (6a) complex revealed a longer palladium-carbon bond distance trans to the phosphine moiety indicating that the attack of the nucleophile takes place at the carbon trans to the phosphine moiety. This was confirmed by the fact that the phosphine moiety did not affect the enantioselectivity directly. Under mild reaction conditions, enantioselectivities up to 83% were obtained (25 degrees C) with ligand 1e. Systematic variation of the ligand bridge and the phosphite moiety showed that the configuration of the product is controlled by the atropisomerism of the biphenyl substituent at the phosphite moiety. The conformation of the biphenyl group, in turn, is controlled by the substituent at the chiral carbon in the bridge. Ligands with large bite angles yielded higher enantioselectivities.     

The mass spectra of 2-alkyl N-methyl pyrrolidines

The mass spectra of a series of 2-alkyl N-methyl pyrrolidines have been examined and fragments which may be pyrrole type structures are apparent. These ions are most prominent in the spectra of the long chain alkyl derivatives.     

Aminosulf(ox)ides as ligands for Iridium(I)-catalyzed asymmetric transfer hydrogenation

A new class of efficient catalysts was developed for the asymmetric transfer hydrogenation of unsymmetrical ketones. A series of chiral N,S-chelates (6-22) was synthesized to serve as ligands in the iridium(I)-catalyzed reduction of ketones. Both formic acid and 2-propanol proved to be suitable as hydrogen donors. Sulfoxidation of an (R)-cysteine-based aminosulfide provided a diastereomeric ligand family containing a chiral sulfur atom. The two chiral centers of these ligands showed a clear effect of chiral cooperativity. In addition, aminosulfides containing two asymmetric carbon atoms in the backbone were synthesized. Both the sulfoxide-containing beta-amino alcohols and the aminosulfides derived from 1,2-disubstituted amino alcohols gave rise to high reaction rates and moderate to excellent enantioselectivities in the reduction of various ketones. The enantioselective outcome of the reaction was favorably affected by selecting the most appropriate hydrogen donor. Enantioselectivities of up to 97% were reached in the reduction of aryl-alkyl ketones.     

A model of the chemical composition and pyrolysis kinetics of lignin

This study presents a novel approach for the chemical representation of lignin for modelling the reaction kinetics of lignin in lignocellulosic biomass. This methodology relies on the definition of dimeric pseudo-components containing phenolic functionalities, i.e., p-hydroxyphenyl, guaiacyl and syringyl groups, as measured in real biomass and native lignin through wet chemistry and spectroscopic techniques. The reactivities of the lignin pseudo-components are modelled through a series of lumped unidirectional reactions, whose product formation and reaction rate constants are optimised to replicate a comprehensive experimental dataset gathered from several works available in the literature. The new kinetic model contributes to the state-of-the-art by providing a more accurate depiction of the conversion rates, selectivity of char vs. volatiles, and aromatic composition in condensable products in line with the inherent reactivity of lignin functionalities and the empirical observations of lignin depolymerisation and thermal degradation at low (<1?K/s) and high heating rates (>50?K/s).     

Molecular Fluorescence Imaging Spectroscopy for Mapping Low Concentrations of Red Lake Pigments: Van Gogh's Painting The Olive Orchard

Vincent van Gogh used fugitive red lake pigments that have faded in some paintings. Mapping their distribution is key to understanding how his paintings have changed with time. While red lake pigments can be identified from microsamples, in situ identification and mapping remain challenging. This paper explores the ability of molecular fluorescence imaging spectroscopy to identify and, more importantly, map residual non‐degraded red lakes. The high sensitivity of this method enabled identification of the emission spectra of eosin (tetrabromine fluorescein) lake mixed with lead or zinc white at lower concentrations than elemental X‐ray fluorescence (XRF) spectroscopy used on account of bromine. The molecular fluorescence mapping of residual eosin and two carmine red lakes in van Gogh's The Olive Orchard is demonstrated and compared with XRF imaging spectroscopy. The red lakes are consistent with the composition of paint tubes known to have been used by van Gogh.     

Spherical functions on harmonic extensions ofH-type groups

We consider the harmonic extension AN of an H-type group N with Lie algebra n = v + z, and [v, v] = z. We characterize the positive definite spherical functions on AN.