Enantiodiscrimination of racemic electrophiles by diketopiperazine enolates: asymmetric synthesis of methyl 2-amino-3-aryl-butanoates and 3-methyl-aspartates

Enolates of (S)-N,N′-bis-(p-methoxybenzyl)-3-iso-propylpiperazine-2,5-dione exhibit high levels of enantiodiscrimination in alkylations with (RS)-1-aryl-1-bromoethanes and (RS)-2-bromoesters, affording substituted diketopiperazines containing two new stereogenic centres in high de. Deprotection and hydrolysis of the resultant substituted diketopiperazines provides a route to the asymmetric synthesis of homochiral methyl 2-amino-3-aryl-butanoates and 3-methyl-aspartates in high de and ee.     

Mod 2 cohomology of combinatorial Grassmannians

Matroid bundles, introduced by MacPherson, are combinatorial analogues of real vector bundles. This paper sets up the foundations of matroid bundles. It defines a natural transformation from isomorphism classes of real vector bundles to isomorphism classes of matroid bundles. It then gives a transformation from matroid bundles to spherical quasifibrations, by showing that the geometric realization of a matroid bundle is a spherical quasifibration. The poset of oriented matroids of a fixed rank classifies matroid bundles, and the above transformations give a splitting from topology to combinatorics back to topology. A consequence is that the mod 2 cohomology of the poset of rank k oriented matroids (this poset classifies matroid bundles) contains the free polynomial ring on the first k Stiefel-Whitney classes.     

A finite model property for RMImin

It is proved that the variety of relevant disjunction lattices has the finite embeddability property. It follows that Avron's relevance logic RMI _min has a strong form of the finite model property, so it has a solvable deducibility problem. This strengthens Avron's result that RMI _min is decidable. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Segregation in the Falicov--Kimball Model

The Falicov–Kimball model is a simple quantum lattice model that describes light and heavy electrons interacting with an on-site repulsion; alternatively, it is a model of itinerant electrons and fixed nuclei. It can be seen as a simplification of the Hubbard model; by neglecting the kinetic (hopping) energy of the spin up particles, one gets the Falicov–Kimball model. We show that away from half-filling, i.e. if the sum of the densities of both kinds of particles differs from 1, the particles segregate at zero temperature and for large enough repulsion. In the language of the Hubbard model, this means creating two regions with a positive and a negative magnetization. Our key mathematical results are lower and upper bounds for the sum of the lowest eigenvalues of the discrete Laplace operator in an arbitrary domain, with Dirichlet boundary conditions. The lower bound consists of a bulk term, independent of the shape of the domain, and of a term proportional to the boundary. Therefore, one lowers the kinetic energy of the itinerant particles by choosing a domain with a small boundary. For the Falicov- Kimball model, this corresponds to having a single “compact” domain that has no heavy particles. Received: 21 June 2001 / Accepted: 4 January 2002     

Elektrische und thermische Eigenschaften von Salzlösungen

Ohne Zusammenfassung     

Hypernormal form theory: foundations and algorithms

Hypernormal forms (unique normal forms, simplest normal forms) are investigated both from the standpoint of foundational theory and algorithms suitable for use with computer algebra. The Baider theory of the Campbell-Hausdorff group is refined, by a study of its subgroups, to determine the smallest substages into which the hypernormalization process can be divided. This leads to a linear algebra algorithm to compute the generators needed for each substage with the least amount of work. A concrete interpretation of Jan Sanders’ spectral sequence for hypernormal forms is presented. Examples are given, and a proof is given for a little-known theorem of Belitskii expressing the hypernormal form space (in the inner product style) as the kernel of a higher-order differential operator.     

Experimental analysis, modeling, and theoretical design of McMaster pore-filled nanofiltration membranes

A side-by-side comparison of the performance of McMaster pore-filled (MacPF) and commercial nanofiltration (NF) membranes is presented here. The single-salt and multi-component performance of these membranes is studied using experimental data and using a mathematical model. The pseudo two-dimensional model is based on the extended Nernst–Planck equation, a modified Poisson–Boltzmann equation, and hydrodynamic calculations. The model includes four structural properties of the membrane: pore radius, pure water permeability, surface charge density and the ratio of effective membrane thickness to water content. The analysis demonstrates that the rejection and transport mechanisms are the same in the commercial and MacPF membranes with different contributions from each type of mechanism (convection, diffusion and electromigration). Solute rejection in NF membranes is determined primarily by a combination of steric and electrostatic effects. The selectivity of MacPF membranes is primarily determined by electrostatic effects with a significantly smaller contribution of steric effects compared to commercial membranes. Hence, these membranes have the ability to reject ions while remaining highly permeable to low molecular weight organics. Additionally, a new theoretical membrane design approach is presented. This design procedure potentially offers the optimization of NF membrane performance by tailoring the membrane structure and operating variables to the specific process, simultaneously. The procedure is validated at the laboratory scale.     

Transport of Neutrally Buoyant and Dense Variably Sized Colloids in a Two-Dimensional Fracture with Anisotropic Aperture

The transport of monodisperse as well as polydisperse colloid suspensions in a two-dimensional, water saturated fracture with spatially variable and anisotropic aperture is investigated with a particle tracking model. Both neutrally buoyant and dense colloid suspensions are considered. Although flow and transport in fractured subsurface formations have been studied extensively by numerous investigators, the transport of dense, polydisperse colloid suspensions in a fracture with spatially variable and anisotropic aperture has not been previously explored. Simulated snapshots and breakthrough curves of ensemble averages of several realizations of a log-normally distributed aperture field show that polydisperse colloids exhibit greater spreading than monodisperse colloids, and dense colloids show greater retardation than neutrally buoyant colloids. Moreover, it is demonstrated that aperture anisotropy oriented along the flow direction substantially increases colloid spreading; whereas, aperture anisotropy oriented transverse to the flow direction retards colloid movement.     

Solid-phase approach towards the synthesis of functionalized imidazo[1,2-b]pyrazol-2-ones

The solid-phase synthesis of a series of imidazo[1,2-b]pyrazol-2-ones, an interesting 5,5-fused ring system, based on diverse set of hydrazine acids and malanonitriles is described. The method involves formation of 5-aminopyrazoles on solid support and subsequent cyclizative cleavage off the resin. Compounds were obtained in acceptable to excellent yields and are suitable for biological evaluation without further purification.     

Anionic iron(II) alkoxides as initiators for the controlled ring‐opening polymerization of lactide

Hetero‐bimetallic Fe(II) alkoxide/aryloxides were evaluated as initiators for the ring‐opening polymerization of rac‐lactide. [(THF)NaFe(O^tBu)₃]₂ ( 1 ) and [(THF)₄Na₂Fe(2,6‐diisopropylphenolate)₄] ( 2 ) (THF = tetrahydrofuran) both polymerized lactide efficiently at room temperature, with complex 1 affording better control over the molecular weight parameters of the resultant polymer. At conversions below 70%, a linear increase in molecular weight with conversion was observed, indicative of a well‐controlled polymerization process. Complex 2 is the first example of a dianionic Fe(II) alkoxide and has been structurally characterized to reveal a distorted square planar FeO₄ array in which both Na counterions bridge two aryloxide ligands and are further complexed by two THF ligands. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3798–3803, 2003