The Chemoselective Cleavage of Acylthioaryltioacetals with Tributyltin Hydride

Acylthioarylthioacetals are cleaved selectively by tributyltin hydride/AIBN affording thioacyls radicals, which can react with tethered carbon-carbon double or triple bond to form functionalized cyclopentanes.     

Gradient augmented reinitialization scheme for the level set method

A hybrid scheme for reinitializing the level set function and its gradient within the frame work of the augmented level set method is presented. It is based on first dividing the domain into an interfacial region (i.e. nodes close to the interface) and its complement. Within the interfacial region, the level set and its gradient are updated explicitly through a modified version of Newton's method (Chopp, 2001, SIAM J. Sci. Comput. 23 230‐244) and is implemented here within the context of Hermite polynomials. In the region away from the interface, the solution pertains to a semi‐Lagrangian implementation of the reinitialization equations, which are solved based on Hermite polynomials and are time marched with a single step and a multipoint scheme. It is shown that for various exercises, the present method predicts the signed distance function and its gradient to 4^th and 3^rd order (in space), respectively with regards to the L₁, L₂, and L _∞ norms, provided the level set field is sufficiently smooth. A range of test cases are also considered from the literature, where the present method is compared with existing methods and shown to be generally more accurate. Moreover, the well‐known issue of volume loss due to reinitialization is addressed successfully with the current implementation, even for objects that are of the size of one grid cell, and whose local radius of curvature falls below the local grid size. For both time marching schemes, it is shown that the L₂ and L _∞ errors decay to negligible levels, are smooth in space, and do not exhibit temporal oscillations. Finally the performance of the hybrid scheme is evaluated by applying it on various kinematic test cases. For solid body rotation problems (zero deformation flow field), the benefit stemming from hybrid reinitialization is marginal. When applied to kinematic cases involving severe deformation, such as the standard vortex flow, the reinitialization strategy helps maintain a smooth level set field, which prevents serious numerical errors from developing.Copyright © 2013 John Wiley & Sons, Ltd.     

Two-sided networks for completely simple semigroups

Let S be a completely simple semigroup represented as a Rees matrix semigroup M(I,G,P) with normalized sandwich matrix P. On the congruence lattice C(S) of S we consider the relations T _i, K and T _r which identify congruences with the same left trace, kernel and right trace, respectively. These are equivalences whose classes are intervals. The upper and lower ends of these intervals induce the following operators on C(S) T_l, K, T_r, t_l, k and t_r .We construct here the semigroup generated by these operators as a homomorphic image of a semigroup given by generators and relations and demonstrate the minimality of the latter.     

New ethyl cellulose/acrylic hybrid latexes and coatings via miniemulsion polymerization

Ethyl cellulose (EC) was incorporated into copolymer latexes via miniemulsion polymerization. The effects of EC viscosity and EC content on droplet size, particle size, and polymerization kinetics were investigated. The higher the EC content and viscosity, the larger the droplet size and the less stable the latex suspension. Small droplets that could be efficiently nucleated were formed for the lower‐viscosity EC but the latex still showed limited colloidal stability. This was attributed to some phase‐incompatibility between EC and the acrylic polymer. These stability issues were overcome by using an oil‐soluble initiator and a crosslinker. The later enabled to physically entrap EC inside the polymer particles, whereas the former allowed in situ grafting of the growing acrylic radicals to the EC backbone decreasing thereby the extent of phase separation. Thermal‐mechanical analyses evidenced that the films obtained from the hybrid latexes displayed better properties than the EC‐free latex films or the physical blends. This supports the hypothesis of formation of hybrid latexes that synergistically combine the properties of the acrylic matrix and the EC polymer. Interestingly, a significant increase of the elastic modulus was observed between 50 and 90 °C. This mechanical reinforcement was tentatively attributed to the formation of a percolating EC‐based hybrid phase. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2329–2339, 2010     

GC models for separation optimization in pressure‐tunable tandem capillary columns operated isothermally

In the previous part of this study, a significant improvement of the fundamental relationships that control GC resolution in a pressure‐tunable assembly operating in isothermal conditions inside a single oven was made. A theoretical approach for the correct choice of the working temperature was proposed for the first time. In this second part of our report, a new interfacing device has been proposed for a rapid and reliable alignment of the two columns at the midpoint junction. Moreover, the results of a series of experimental tests have confirmed the validity of the proposed mathematical models.