The reaction of carbanions from 3-methyl-5-phenylisoxazole with electrophilic compounds

The reactivity of 3-methyl-5-phenylisoxazole against electrophilic compounds in the presence of different bases is studied. With n-BuLi, alkylated products at C-4 position and C-3 methyl group, and, in a few cases, dialkylated isoxazoles are obtained. When the reactions are carried out with LICA, the nature of the alkylated products depends on the alkyl halide used. By using LICA-TMEDA, as deprotonating system, regio-selective reaction at the C-3 methyl group is found.     

Copper-assisted oxidation of catechols into quinone derivatives

Catechols are ubiquitous substances often acting as antioxidants, thus of importance in a variety of biological processes. The Fenton and Haber–Weiss processes are thought to transform these molecules into aggressive reactive oxygen species (ROS), a source of oxidative stress and possibly inducing degenerative diseases. Here, using model conditions (ultrahigh vacuum and single crystals), we unveil another process capable of converting catechols into ROSs, namely an intramolecular redox reaction catalysed by a Cu surface. We focus on a tri-catechol, the hexahydroxytriphenylene molecule, and show that this antioxidant is thereby transformed into a semiquinone, as an intermediate product, and then into an even stronger oxidant, a quinone, as final product. We argue that the transformations occur via two intramolecular redox reactions: since the Cu surface cannot oxidise the molecules, the starting catechol and the semiquinone forms each are, at the same time, self-oxidised and self-reduced. Thanks to these reactions, the quinone and semiquinone are able to interact with the substrate by readily accepting electrons donated by the substrate. Our combined experimental surface science and ab initio analysis highlights the key role played by metal nanoparticles in the development of degenerative diseases.

An antioxidant catechol transforms following intramolecular redox reactions into highly reactive oxygen species, a semiquinone and a quinone, on copper.     

13C-NMR relaxation studies of alkali metal cryptate complexes

The ¹³C spin-lattice relaxation times (T₁'s) of cryptands [2.1.1], [2.2.1] and [2.2.2] as well as those of the corresponding cryptate complexes with Li⁺, Na⁺, and K⁺ in CDCl₃ and CH₃OH:D₂O (90:10) were measured and the results are interpreted in terms of molecular compression and desolvation effects.     

Merging the Isonitrile-Tetrazine (4+1) Cycloaddition and the Ugi Four-Component Reaction into a Single Multicomponent Process

Multicomponent reactions are of utmost importance at generating a unique, wide, and complex chemical space. Herein we describe a novel multicomponent approach based on the combination of the isonitrile-tetrazine (4+1) cycloaddition and the Ugi four-component reaction to generate pyrazole amide derivatives. The scope of the reaction as well as mechanistic insights governing the 4H-pyrazol-4-imine tautomerization are provided. This multicomponent process provides access to a new chemical space of pyrazole amide derivatives and offers a tool for peptide modification and stapling.     

MIRHA: multi-start biased randomization of heuristics with adaptive local search for solving non-smooth routing problems

This paper discusses the use of probabilistic or randomized algorithms for solving vehicle routing problems with non-smooth objective functions. Our approach employs non-uniform probability distributions to add a biased random behavior to the well-known savings heuristic. By doing so, a large set of alternative good solutions can be quickly obtained in a natural way and without complex configuration processes. Since the solution-generation process is based on the criterion of maximizing the savings, it does not need to assume any particular property of the objective function. Therefore, the procedure can be especially useful in problems where properties such as non-smoothness or non-convexity lead to a highly irregular solution space, for which the traditional optimization methods—both of exact and approximate nature—may fail to reach their full potential. The results obtained so far are promising enough to suggest that the idea of using biased probability distributions to randomize classical heuristics is a powerful one that can be successfully applied in a variety of cases.     

Predicting initial erosion during the hole erosion test by using turbulent flow CFD simulation

CFD simulation with enhanced modeling of turbulence and near-wall treatment is used to model water–clay mixtures flowing through a cylindrical pipe domain. Effects on the wall-shear stress resulting from varying water clay content and applied hydraulic gradient are analyzed. Various parametric studies were performed and had shown that the two-dimensional modelling introduced in the present study does not yield a uniform wall-shear stress along the pipe wall and that clay concentration affects significantly the wall-shear stress value. This is in contrast with the common hypothesis used in one-dimensional modeling approaches where this stress is assumed constant and which gives rise to uniform erosion along the pipe wall. The obtained results had enabled predicting more realistically erosion amount and had allowed for understanding the irregular eroded hole wall shape as observed experimentally after performing the standard hole erosion test.     

Products of Jacobians as Prym-Tyurin varieties

Let X ₁, ..., X _m denote smooth projective curves of genus g _i ≥ 2 over an algebraically closed field of characteristic 0 and let n denote any integer at least equal to . We show that the product JX ₁ × ... × JX _m of the corresponding Jacobian varieties admits the structure of a Prym-Tyurin variety of exponent n ^m-1. This exponent is considerably smaller than the exponent of the structure of a Prym-Tyurin variety known to exist for an arbitrary principally polarized abelian variety. Moreover it is given by explicit correspondences.      

Noncommutative Jordan C*-algebras

We introduce noncommutative JB*-algebras which generalize both B*-algebras and JB*-algebras and set up the bases for a representation theory of noncommutative JB*-algebras. To this end we define noncommutative JB*-factors and study the factor representations of a noncommutative JB*-algebra. The particular case of alternative B*-factors is discussed in detail and a Gelfand-Naimark theorem for alternative B*-algebras is given.     

Abelian varieties with finite abelian group action

An automorphism of an abelian variety induces a decomposition of the variety up to isogeny. There are two such results, namely the isotypical decomposition and Roan’s decomposition theorem. We show that they are essentially the same. Moreover, we generalize in a sense this result to abelian varieties with action of an arbitrary finite abelian group. An early version of this article was inadvertently published before all the revisions had been completed and then retracted [https://doi.org/10.1007/s00013-018-1244-3]. This article is the final peer reviewed version.

     

On the adjacencies of triangular meshes based on skeleton-regular partitions

For any 2D triangulation τ, the 1-skeleton mesh of τ is the wireframe mesh defined by the edges of τ, while that for any 3D triangulation τ, the 1-skeleton and the 2-skeleton meshes, respectively, correspond to the wireframe mesh formed by the edges of τ and the “surface” mesh defined by the triangular faces of τ. A skeleton-regular partition of a triangle or a tetrahedra, is a partition that globally applied over each element of a conforming mesh (where the intersection of adjacent elements is a vertex or a common face, or a common edge) produce both a refined conforming mesh and refined and conforming skeleton meshes. Such a partition divides all the edges (and all the faces) of an individual element in the same number of edges (faces). We prove that sequences of meshes constructed by applying a skeleton-regular partition over each element of the preceding mesh have an associated set of difference equations which relate the number of elements, faces, edges and vertices of the nth and (n−1)th meshes. By using these constitutive difference equations we prove that asymptotically the average number of adjacencies over these meshes (number of triangles by node and number of tetrahedra by vertex) is constant when n goes to infinity. We relate these results with the non-degeneracy properties of longest-edge based partitions in 2D and include empirical results which support the conjecture that analogous results hold in 3D.