The effect of extra framework species on the intrinsic negative thermal expansion property of zeolites with the LTA topology

X-Ray powder diffraction studies have been used to measure the thermal expansion properties of three zeolites with the LTA topology and provide details of the underlying structural changes. Siliceous ITQ-29 and dehydrated and hydrated silver zeolite A have large negative, moderate negative and positive thermal expansion coefficients, respectively.     

Total synthesis of azumamide A and azumamide E, evaluation as histone deacetylase inhibitors, and design of a more potent analogue

The unprecedented diastereoselective Mannich reaction of a Z-allylsulfoximine was a key step in the total synthesis of the marine natural products azumamide A and E, and an unnatural analogue. Their relative potency as histone deacetylase inhibitors was evaluated and found to correlate with predicted zinc-binding affinity. [reaction: see text]     

Formation of stable Meisenheimer adduct ion pairs in apolar solvents: implications for stereoselective reactions

[reaction: see text] A detailed study concerning the formation of Meisenheimer adducts in biphasic solvent systems is described. The process relies on utilizing a significantly lipophilic quaternary ammonium salt to transfer a nucleophile (e.g., hydroxide ion) between an aqueous and organic layer containing the electron-deficient aromatic substrate. Provided that the organic layer is sufficiently apolar, the resultant Meisenheimer adduct is considerably stable, likely the result of a strong ion-pairing interaction between the large polarizable anionic complex and the diffusively charged tetraalkylammonium cation. Using the diethylamide of 3,5-dinitrobenzoic acid as a model compound, the influence of ion-pairing reagents and solvents on adduct formation was investigated. Dramatically increased equilibrium formation of the Meisenheimer adduct is observed in the biphasic medium (e.g., benzene/2 M NaOH) relative to the same adduct generated in single-phase systems. Spectroscopic studies on this adduct are consistent with those conducted in single-phase polar or dipolar aprotic solvents. The methodology is extended to performing highly enantioselective biphasic kinetic resolutions of several racemic electron-deficient amides.     

Steinberg symbols modulo the trace class, holonomy, and limit theorems for Toeplitz determinants

Suppose that where and , and the Toeplitz operator is invertible. Let be the determinant of the Toeplitz matrix where . Let be the orthogonal projection onto where ; set , let denote the Hankel operator associated to , and set for . For the Wiener-Hopf factorization where and , put , Theorem A.    

Let be a decomposition into invariant subspaces, and , so that restricted to is invertible, is finite dimensional, and restricted to is nilpotent. Let be the basis for the null space of , and let be the top vector in a Jordan root vector chain of length lying over , i.e., where . Theorem B.     , the holonomy of a Deligne bundle with connection defined by the factorization . Note that the generalizations of the Szegö limit theorem for which have appeared in the literature with instead of have the defect that the limit of does not exist in general. An example is given with yet for infinitely many .

     

A Model,Algorithms and Strategy for Train Pathing

We set out a model, algorithms and strategies for the train pathing and timetabling problem for rail lines of the type normally found in Britain and Europe; that is, lines having separate tracks for trains in each direction. As the pathing problem is combinatorially difficult we propose solution heuristics and strategies analogous to those which have enabled ‘expert’ train pathers to plan large-scale complex rail systems by traditional manual graphical methods. This approach also has the potential advantage of facilitating user interaction, understanding and acceptance. We report computational results for several examples. Without the above strategies we found even very small problems intractable. With these strategies we could solve realistic size problems in acceptable times, while exploring more options and trade-offs than do traditional methods. More work is needed and we suggest natural extensions, and directions for further research and development.     

Curing of dental composites by use of InGaN light-emitting diodes

A potential application of blue-light-emitting InGaN LED's as a polymerizing source for dental composite materials is described. We compared a basic LED device with a conventional curing light in vitro to determine the polymerization parameters and to examine the effect of the curing process on the physical properties of these materials. It was determined that an array of six LED's was able to set a range of composite materials more quickly than a conventional light source, with the cured compounds showing similar hardness and material shrinkage parameters but with a lower material temperature rise during the curing process using the array. These findings indicate that a device consisting of several InGaN LED's would be an effective instrument for curing certain light-sensitive materials, particularly dental composites.