Intramolecular Baylis-Hillman Reaction: A Pathway to Substituted Coumarins

The acrylate ester of salicylaldehyde, in the presence of DABCO, affords a crystalline coumarin salt. Formation of this derivative confirms a vital intermediate in the mechanism of the reaction. Salicylaldehyde, suitably protected, reacts with methyl acrylate to afford a novel coumarin not unlike the vasodilator chromonar.     

Spatial updating, spatial transients, and regularities of a complex automaton with nonperiodic architecture

We study the dynamics of patterns exhibited by rule 52, a totalistic cellular automaton displaying intricate behaviors and wide regions of active/inactive synchronization patches. Systematic computer simulations involving 2(30) initial configurations reveal that all complexity in this automaton originates from random juxtaposition of a very small number of interfaces delimiting active/inactive patches. Such interfaces are studied with a sidewise spatial updating algorithm. This novel tool allows us to prove that the interfaces found empirically are the only interfaces possible for these periods, independently of the size of the automata. The spatial updating algorithm provides an alternative way to determine the dynamics of automata of arbitrary size, a way of taking into account the complexity of the connections in the lattice.     

Synthesis and hydrophobic binding studies on a water- soluble tritriptycene

The water soluble tritriptycene 1 was synthesized starting with triptycene trisquinone and anthracene. The hydrophobic binding of substrates to the benzene-walled cavities in 1 was studied by noting the up-field shift of substrate protons in the NMR of the substrate in the presence of aqueous 1. Small substrates, negatively charged substrates or substrates larger than the cavities do not bind as strongly as substrates about the same size as the cavities or those bearing a positive charge. Based on differences in AH_z'S, the bound substrates position themselves in the cavities so that polar groups are at the water interface.     

Synthesis and characterisation of phosphane-substituted Co3C clusters having a pendant allyl side-chain

Substituted μ₃-carbido-capped tricobalt carbonyl clusters have been synthesised by reaction of [Co₃(μ₃-C(O)OCH₂CHCH₂)(CO)₉] with a range of monodentate and chelating phosphane ligands. The products have been characterised by microanalysis, IR and NMR spectroscopy, mass spectrometry and, in the case of [Co₃(μ₃-CR)(CO)₇(dppe)], [Co₃(μ₃-CR)(CO)₇(dppm)], [Co₃(μ₃-CR)(CO)₇(PPh₃)₂], [Co₃(μ₃-CR)(CO)₇(PMe₃)₂] and [Co₃(μ₃-CR)(CO)₆(PEt₃)₃] (R=C(O)OCH₂CHCH₂), single crystal X-ray diffraction.     

The expansion of wet steam through a compressible confined vortex in a fluidic vortex diode

The pressure-flow characteristics of a Zobel-type vortex diode have been measured using a working fluid of compressible wet steam. Tests using superheated steam with inlet/outlet pressure ratios across the diode of up to 30 have shown clearly the effects of compressibility and choking on the diode characteristics. Repeating the tests using wet steam, with known dryness fractions, has shown separately the effects of wetness on the diode performance.

When the diode was installed into the pipwork in the high-resistance direction, excessive steam wetness (quality <0.93) led to a build-up of water and when this was eventually swept through to the diode the resistance was seen to fall substantially as the strong internal vortex was destroyed.     

Melting Point and Composition Distribution of Polyolefins by Fractionation

The fractionation technique described in this paper was used to characterize the melting-point, monomer, and blocking distributions for polymers and copolymers. It is different from the molecular-weight fractionation technique in that the fractions are obtained by using a single solvent to extract the solid polymer below its melting point at stepwise-increasing temperatures. The reproducibility of this technique is excellent, and the technique is sufficient to distinguish pellet-to-pellet variation in a commercially available polypropylene. It was used to show the influence of preparation variables on the melting-point distributions of polyethylene and polypropylene and on the monomer and blocking distribution of copolymers, and to distinguish copolymers from blends.     

Numerical rheometry of bulk materials using a power law fluid and the lattice Boltzmann method

In the present study, the flow of bulk materials is characterised as a non-Newtonian fluid and modelled using the lattice Boltzmann method. A power law and a Bingham model is implemented in the LBM, which is hydrodynamically coupled to the discrete element method (DEM) for structural interaction. The performance of both non-Newtonian models is assessed, both qualitatively and quantitatively, in benchmark problems. The validated, non-Newtonian LBM–DEM framework is then applied to the geometry of a cylindrical Couette rheometer to numerically determine the constitutive response of a sample of Leighton Buzzard sand. The numerical results, which employ the power law, are compared with experimental data, and a number of other synthetic soil samples are defined using the presented process of numerical rheometry. Finally, the numerical stress–strain rate response of the synthetic soil samples is interpreted within the context of a regularised Bingham model, and the similarities discussed.     

Values of games without side payments

A value forn-person games without side payments is given which coincides with theShapley value for games with side payments, and with theNash value for two-person games.