Flexible synthesis of enantiomerically pure 2,8-dialkyl-1,7-dioxaspiro[5.5]undecanes and 2,7-dialkyl-1,6-dioxaspiro[4.5]decanes from propargylic and homopropargylic alcohols

A new approach to enantiomerically pure 2,8-dialkyl-1,7-dioxaspiro[5.5]undecanes and 2,7-dialkyl-1,6-dioxaspiro [4.5] decanes is described and utilizes enantiomerically pure homopropargylic alcohols obtained from lithium acetylide opening of enantiomerically pure epoxides, which are, in turn, acquired by hydrolytic kinetic resolution of the corresponding racemic epoxides. Alkyne carboxylation and conversion to the Weinreb amide may be followed by triple-bond manipulation prior to reaction with a second alkynyllithium derived from a homo- or propargylic alcohol. In this way, the two ring components of the spiroacetal are individually constructed, with deprotection and cyclization affording the spiroacetal. The procedure is illustrated by acquisition of (2S,5R,7S) and (2R,5R,7S)-2-n-butyl-7-methyl-1,6-dioxaspiro[4.5]-decanes (1), (2S,6R,8S)-2-methyl-8-n-pentyl-1,7-dioxaspiro[5.5]undecane (2), and (2S,6R,8S)-2-methyl-8-n-propyl-1,7-dioxaspiro[5.5]undecane (3). The widely distributed insect component, (2S,6R,8S)-2,8-dimethyl-1,7-dioxaspiro[5.5]undecane (4), was acquired by linking two identical alkyne precursors via ethyl formate. In addition, [H-2(4)]-regioisomers, 10,10,11,11-[H-2(4)] and 4,4,5,5-[H-2(4)] of 3 and 4,4,5,5-[H-2(4)]-4, were acquired by triple-bond deuteration, using deuterium gas and Wilkinson's catalyst. This alkyne-based approach is, in principle, applicable to more complex spiroacetal systems not only by use of more elaborate alkynes but also by triple-bond functionalization during the general sequence.

Nanocrystalline zirconia as catalyst support in methanol synthosis

Nanocrystalline zirconia was synthesized and used as catalyst support for methanol synthesis. The nanocrystallite particles have new physical and textural properties which are critical in determining the catalytic performance. Nanocrystalline zirconia changes the electronic structure and affects the metal and support interactions on the catalyst. leading to facile reduction. intimate interaction between copper and zirconia, more corner defects and oxygen vacancies on the surface of the catalyst. All these changes are beneficial to the reaction of methanol synthesis from hydrogenation of CO2. As a result. higher conversion of CO2 and selectivity of methanol are achieved compared to the catalysts prepared by conventional co-precipitation method. (C) 2004 Elsevier B.V. All rights reserved.

Minimal Homogeneous Latin Trades

A latin trade is a subset of a latin square which may be replaced with a disjoint mate to obtain a new latin square. A d-homogeneous latin trade is one which intersects each row, each column and each entry of the latin square either 0 or d times. In this paper we give a construction for minimal d-homogeneous latin trades of size dm, for every integer d >= 3, and m >= 1.75d(2) + 3. We also improve this bound for small values of d. Our proof relies on the construction of cyclic sequences whose adjacent sums are distinct. (c) 2006 Elsevier B.V. All rights reserved.

Modulational Instability in Periodic Quadratic Nonlinear Materials

We investigate the modulational instability of plane waves in quadratic nonlinear materials with linear and nonlinear quasi-phase-matching gratings. Exact Floquet calculations, confirmed by numerical simulations, show that the periodicity can drastically alter the gain spectrum but never completely removes the instability. The low-frequency part of the gain spectrum is accurately predicted by an averaged theory and disappears for certain gratings. The high-frequency part is related to the inherent gain of the homogeneous non-phase-matched material and is a consistent spectral feature.

Simulations of Bose fields at finite temperature

We introduce a time-dependent projected Gross-Pitaevskii equation to describe a partially condensed homogeneous Bose gas, and find that this equation will evolve randomized initial wave functions to equilibrium. We compare our numerical data to the predictions of a gapless, second order theory of Bose-Einstein condensation [S. A. Morgan, J. Phys. B 33, 3847 (2000)], and find that we can determine a temperature when the theory is valid. As the Gross-Pitaevskii equation is nonperturbative, we expect that it can describe the correct thermal behavior of a Bose gas as long as all relevant modes are highly occupied. Our method could be applied to other boson fields.

Review of recent results on excursion set models

Many images consist of two or more 'phases', where a phase is a collection of homogeneous zones. For example, the phases may represent the presence of different sulphides in an ore sample. Frequently, these phases exhibit very little structure, though all connected components of a given phase may be similar in some sense. As a consequence, random set models are commonly used to model such images. The Boolean model and models derived from the Boolean model are often chosen. An alternative approach to modelling such images is to use the excursion sets of random fields to model each phase. In this paper, the properties of excursion sets will be firstly discussed in terms of modelling binary images. Ways of extending these models to multi-phase images will then be explored. A desirable feature of any model is to be able to fit it to data reasonably well. Different methods for fitting random set models based on excursion sets will be presented and some of the difficulties with these methods will be discussed.

Personal Reflexive Instruments for Monitoring Engineering Development (PRIMED) Project

This was an early pre-Catalyst collaboration about developing reflexivity in student engineers. It was funded by (then) CUTSD.

On the validity of the shrinking core model in noncatalytic gas solid reaction

By using a matched asymptotic expansion technique, the shrinking core model (SCM) used in non-catalytic gas solid reactions with general kinetic expression is rigorously justified in this paper as a special case of the homogeneous model when the reaction rate is much faster than that of diffusion. The time-pendent velocity of the moving reacted-unreacted interface is found to be proportional to the gas flux at that interface for all geometries of solid particles, and the thickness order of the reaction zone and also the degree of chemical reaction at the interface is discussed in this paper.

Approximate analytical solutions for porous catalysts with nonuniform activity

Using a novel finite integral transform technique, the problem of diffusion and chemical reaction in a porous catalyst with general activity profile is investigated theoretically. Analytical expressions for the effectiveness factor are obtained for pth order and Michaelis-Menten kinetics. Perturbation methods are employed to provide useful asymptotic solutions for large or small values of Thiele modulus and Biot number.