Air‐Stable Solid Aryl and Heteroaryl Organozinc Pivalates: Syntheses and Applications in Organic Synthesis

A wide range of air‐stable, solid, polyfunctional aryl and heteroarylzinc pivalates were efficiently prepared by either magnesium insertion or Hal/Mg exchange followed by transmetalation with Zn(OPiv)₂ (OPiv=pivalate). By reducing the amount of LiCl the air stability could be significantly enhanced compared with previously prepared reagents. An alternative route is directed magnesiation using TMPMgCl ? LiCl (TMP=2,2,6,6‐tetramethylpiperidyl) followed by transmetalation with Zn(OPiv)₂ or, for very sensitive substrates, direct zincation by using TMPZnOPiv. These zinc reagents not only show excellent stability towards air, but they also undergo a broad range of C?C bond‐formation reactions, such as allylation and carbocupration reactions, as well as addition to aldehydes and 1,4‐addition reactions. Acylation reactions can be performed by using an excess of TMSCl to overcome side reactions of the omnipresent pivalate anion.     

Switchable dielectric permittivity with temperature and Dc-bias in a semifluorinated azobenzene derivative

The thermodynamic, optical, structural, and dynamic properties of the semifluorinated (E)-1-(4-octylphenyl)-2-(4-(perfluorooctyl)phenyl)diazene (4) and the corresponding (E)-1,2-bis(4-octylphenyl)diazene (5) have been studied with differential scanning calorimetry, polarizing optical microscopy, X-ray diffraction, and dielectric spectroscopy. 4 combines the azobenzene properties with the fluorophobic effect and gives rise to a responsive material with a temperature and dc-bias-driven switchable dielectric permittivity within the narrower nematic phase. This is caused by the nematic potential that inevitably brings some fluorocarbon chains in proximity to the hydrocarbon chains from adjacent molecules. Frustration is alleviated by reducing the nematic-to-isotropic transition temperature and by increasing the crystalline-to-nematic transition temperature, thus limiting the stability of the nematic phase. Unlike the normal isotropic phase of compound 5, the isotropic phase of compound 4 contains dipoles with short-range orientation correlations. Optimizing the type of interactions may result in materials with applications as molecular switches and electrooptic devices.     

Distributions with Heavy Tails in Orlicz Spaces

This paper relies on the application of Kantorovich functionals on quasi-interior points of the positive cone for certain classes of Orlicz spaces. Particularly we provide the asymptotic calculation of the ruin probability in the renewal risk model under heavy-tailed claims in the Orlicz spaces. This application assures the extension of classical asymptotic theory of regular variation.     

Resource contention games in multiclass stochastic flow models

We consider resource contention games in a stochastic hybrid system setting using Stochastic Flow Models (SFM) with multiple classes and class-dependent objectives. We present a general modeling framework for such games, where Infinitesimal Perturbation Analysis (IPA) estimators are derived for the derivatives of various class-dependent objectives. This allows us to study these games from the point of view of system-centric optimization of a performance metric and compare it to the user-centric approach where each user optimizes its own performance metric. We derive explicit solutions for a specific model in which the competing user classes employ threshold control policies and service is provided on a First Come First Serve (FCFS) basis. The unbiasedness of the IPA estimators is established in this case and it is shown that under certain conditions the system-centric and user-centric optimization solutions coincide.     

Spectra of Some Interesting Combinatorial Matrices Related to Oriented Spanning Trees on a Directed Graph

The Laplacian of a directed graph G is the matrix L(G) = O(G) –, A(G) where A(G) is the adjaceney matrix of G and O(G) the diagonal matrix of vertex outdegrees. The eigenvalues of G are the eigenvalues of A(G). Given a directed graph G we construct a derived directed graph D(G) whose vertices are the oriented spanning trees of G. Using a counting argument, we describe the eigenvalues of D(G) and their multiplicities in terms of the eigenvalues of the induced subgraphs and the Laplacian matrix of G. Finally we compute the eigenvalues of D(G) for some specific directed graphs G. A recent conjecture of Propp for D(H _n ) follows, where H _n stands for the complete directed graph on n vertices without loops.     

Formation of sulfines in the peroxyacid oxidation of neopentyl neopentanethiolsulfinate

Low temperature ¹H NMR and ¹³C NMR, and IR suggest that the $\text{m}$-chloroperbenzoic acid (MCPBA) oxidation of neopentyl neopentanethiolsulfinate leads to the formation of (E)- and (Z)-2,2-dimethylpropanethial S-oxide, neopentyl neopentanethiolsulfonate, and other products.     

Modelling of discontinuities through dipole distribution

An indirect boundary element method using dipole distribution is employed in order to model discontinuities inside the flow region. The problem of flow under a dam is treated with a sheet-pile in its foundation. The discontinuity across the sheet-pile is demonstrated, a general boundary element procedure for a mixed problem is outlined and the coefficients of the linear system are given in analytical form. Very good agreement with existing analytical results is obtained.     

Mesostructured selenides with cubic MCM-48 type symmetry: large framework elasticity and uncommon resiliency to strong acids

The metal mesostructured Pt/Sn/Se chalcogenides with cubic MCM-48 type pore symmetry are found to be surprisingly stable in concentrated oxidizing acids. Their metal chalcogenide framework exhibits high flexibility during reversible proton exchange as it expands and contracts in an apparent breathing-like action.     

Spectroscopic determination of the degree of esterification of pectic substances from kenaf

Pectins were isolated from bark, wood and pith of four kenaf (Hibiscus cannabinus L.) varieties. The degree of esterification of isolated pectins was studied using Fourier transform infrared spectroscopy. It was determined as being between 57 and 90% and there were no notable differences between kenaf varieties. The higher value of the degree of esterification was presented in wood pectins (86-90%), the interim in pith (75-83%) and the lower in bark (57-64%).