Supramolecular stabilization of N(2)H(7)(+)

The cation N(2)H(7)(+) has been stabilized in a largely hydrophobic supramolecular environment and characterized in the solid state. The cation is situated in the bowl-shaped cavity of calix[4]arene. All of the hydrogen atoms are clearly discernible owing to high-quality X-ray data as well as lack of disorder and symmetry-imposed ambiguity. It appears that electrostatic interactions play a critical role in stabilizing the structure.     

Surface order large deviations for high-density percolation

Summary We derive surface order large deviation estimates for the volume of the largest cluster and for the volume of the largest region surrounded by a cluster of a Bernoulli percolation process restricted to a big finite box, with sufficiently large parameter. We also establish a useful version of the isoperimetric inequality, which is the main tool of our proofs.     

Stereoselective synthesis of 3,3-diarylacrylonitriles as tubulin polymerization inhibitors

A series of 3,3-diarylacrylonitriles were synthesized stereoselectively as tubulin polymerization inhibitors for potential use in cancer chemotherapy. This synthetic route features stannylcupration and palladium-catalyzed Stille cross-coupling chemistry, allowing both E and Z isomers of 3,3-diarylacrylonitriles to be prepared in a very short sequence of reactions.     

Water-repellent acylated and silylated wood samples and their surface analytical characterization

The interest for chemical modification of wood with the aim of preserving it from physical and biochemical deterioration is rapidly increasing. Among the possibilities, acetylation has a great potential for improving the dimension instability of wood against moisture and the durability of wooden objects. Recently, a new acetylating agent, isopropenyl acetate has attracted attention giving an improved acetylating method. By increasing the size of the acyl group, a positive effect on the wood hydrophobicity can be reached. The anhydrides, however, are less reactive. Another applicable surface modification is the silylation of wood that renders the wood surface hydrophobic.

In this paper, we report about the acylation and silylation of different wood samples. A new manufacturing process is tested in which low-value Eucalyptus wood is mixed acylated. The reagent mixture contains at least two kinds of acyl group. One of them is acetyl group; the other(s) can be user-defined. We also report about a silylation method, in which catalyst facilitates the chemisorption process. The extent of modification of the treated wood samples was evaluated by means of weight percent gain, ATR-FTIR, and pyrolysis-gas chromatography–mass spectrometry (Py-GC/MS). Methylene blue adsorption of selected samples was also studied. The result of analytical measurements was in agreement with that of wettability studies.     

Precise large deviation estimates for a one-dimensional random walk in a random environment

ω_x } (taking values in the interval [1/2, 1)), which serve as an environment. This environment defines a random walk {X _k } (called a RWRE) which, when at x, moves one step to the right with probability ω _x , and one step to the left with probability 1 −ωx. Solomon (1975) determined the almost-sure asymptotic speed (= rate of escape) of a RWRE, in a more general set-up. Dembo, Peres and Zeitouni (1996), following earlier work by Greven and den Hollander (1994) on the quenched case, have computed rough tail asymptotics for the empirical mean of the annealed RWRE. They conjectured the form of the rate function in a full LDP. We prove in this paper their conjecture. The proof is based on a “coarse graining scheme” together with comparison techniques. Received: 22 July 1997/Revised version: 15 June 1998     

Evaluate the flammability of a PU foam with double-scale analysis

Two-scale tests, microscale and bench scale, are conducted to analyze the flammability of a flexible polyurethane foam. Microscale tests include simultaneous thermal analysis coupled to Fourier transform infrared spectroscopy, and microscale combustion calorimeter (MCC). Evolved gas components, heat release rate per unit mass, total heat release, derived heat release capacity, and minimum ignition temperature are obtained. Bench scale tests are performed on cone calorimeter. Peak heat release rate per unit area, effective heat of combustion, minimum incident heat flux for ignition, and total heat release per unit area of different incident heat fluxes are obtained. FO-category of the PU foam is estimated by multiple discriminant function analysis based on the results of cone calorimeter test. The relationship between the two-scale tests is analyzed. The minimum ignition temperatures derived from multi heating rate MCC tests are used to predict the time to ignition and compared with the results from cone calorimeter tests. This PU foam is evaluated as a high fire hazard polymer having low heat release capacity, low ignition temperature, and short ignition time.

     

Surface order large deviations for Ising,Potts and percolation models

Summary We derive uniform surface order large deviation estimates for the block magnetization in finite volume Ising (or Potts) models with plus or free (or a combination of both) boundary conditions in the phase coexistence regime ford3. The results are valid up to a limit of slab-thresholds, conjectured to agree with the critical temperature. Our arguments are based on the renormalization of the random cluster model withq1 andd3, and on corresponding large deviation estimates for the occurrence in a box of a largest cluster with density close to the percolation probability. The results are new even for the case of independent percolation (q=1). As a byproduct of our methods, we obtain further results in the FK model concerning semicontinuity (inp andq) of the percolation probability, the second largest cluster in a box and the tail of the finite cluster size distribution.     

Synthesis of hydroxylated hexahydropyrrolo[2,1-b]thiazoles

An unexpected ring contraction of 7,5-fused bicyclic thiazolidinelactams yields hexahydropyrrolo[2,1-b]thiazoles in a single synthetic step. Three stereocentres are inverted along the highly stereoselective reaction path. The title compounds are further transformed into thio-analogues of polyhydroxylated pyrrolizidine alkaloids.