A new rearrangement of spiro[indane-1,3′-thiophene] and spiro[naphthalene-1,3′-thiophene] derivatives accompanied by opening of the cycloalkane ring

Abstract  

The new thioamides 2-oxoindane-1-carbothioamides and 2-oxo-1,2,3,4-tetrahydronaphthalene-1-carbothioamides underwent conjugated addition to (E)-β-nitrostyrenes followed by cyclization to give products containing 5-hydroxyimino-2-aryliminothiophene rings spiro-annulated to the 2-indanone or 2-tetralone system. On treatment with hydrochloric acid in boiling methanol the compounds underwent a new rearrangement, involving transformation of the 2-aryliminothiophene ring to a pyrrole and an opening of the alicyclic ring in the proximity of the carbonyl group, affording 2-(1,3-diaryl-2-oxo-5-thioxopyrrol-4-yl)benzeneacetic or 2-(1,3-diaryl-2-oxo-5-thioxopyrrol-4-yl)benzenepropanoic acid methyl esters. The structures of two selected pyrrole derivatives were determined by X-ray crystal analyses. The thioamides derived from 2-indanone showed unexpected reactivity towards primary alcohols and underwent conversion to 2-hydroxy-1H-indene-3-thiocarboxylic acid O-esters.     

Some Comments on “The Mathematical Universe”

I discuss some problems related to extreme mathematical realism, focusing on a recently proposed “shut-up-and-calculate” approach to physics (Tegmark in Found. Phys. 38:101, 2008; New Sci., September 15th, 2007). I offer arguments for a moderate alternative, the essence of which lies in the acceptance that mathematics is (at least in part) a human construction, and discuss concrete consequences of this—at first sight purely philosophical—difference in point of view.     

Estudio numérico-experimental de la interfaz hormigón-epoxi-FRP para una estructura reforzada sometida a doble corte

The strengthening of concrete structures with laminates of carbon fibers CFRP (Carbon Fibers Reinforced Polymer) began in the 1980's. Nowdays, this technology is one of the most promising one because of the good mechanical properties of laminates and their easy hand-work. Laminates are bonded to the concrete structure by means of epoxy resins. The load-carrying capacity of the strengthening depends directly on the proper behavior of the interface laminate-concrete. While the concrete is capable of transferring stresses to the laminate, this one becomes in charge and collaborates to the strength mechanism of the structure. The safety factor of the reinforcement can be guaranteed if we can predict the behavior at the interface between both materials. In this work we present a pure shear test and a simulation three-dimensional to characterize the behavior of the interface between the laminate and the concrete.     

3D polarimetric purity

From our previous definition of the indices of polarimetric purity for 3D light beams [J.J. Gil, J.M. Correas, P.A. Melero and C. Ferreira, Monogr. Semin. Mat. G. de Galdeano 31, 161 (2004)], an analysis of their geometric and physical interpretation is presented. It is found that, in agreement with previous results, the first parameter is a measure of the degree of polarization, whereas the second parameter (called the degree of directionality) is a measure of the mean angular aperture of the direction of propagation of the corresponding light beam. This pair of invariant, non-dimensional, indices of polarimetric purity contains complete information about the polarimetric purity of a light beam. The overall degree of polarimetric purity is obtained as a weighted quadratic average of the degree of polarization and the degree of directionality.     

The Immersed Structural Potential Method for haemodynamic applications

In this paper, a new fluid–structure interaction immersed computational methodology, based upon the original Immersed Boundary Method (IBM) [1] is outlined with the final aim of modelling cardiovascular phenomena, specifically, heart valve related problems. The principal characteristic of such immersed techniques is the representation of any deformable or rigid body immersed within an incompressible viscous flow field as a momentum forcing source in the Navier–Stokes equations. A number of shortcomings within the immersed formulation still require further investigation and improvement, including the excessive numerical diffusion caused by the interpolation/spreading process, the need to include realistic viscoelastic composite constitutive models describing more accurately the nature of cardiovascular tissues and also the need to capture more effectively stresses developed at the fluid–structure interface. By following the same philosophy as the original IBM, a more sophisticated formulation is derived in this paper, the “Immersed Structural Potential Method (ISPM)”. The method introduced presents an alternative approach to compute the equivalent fluid–structure interaction forces at the fluid mesh, accounts for a sophisticated viscoelastic fibre-reinforced constitutive model to better describe the mechanics of cardiovascular tissues and utilises a novel time-integration methodology for the computation of the deformation gradient tensor which ensures compliance with the incompressibility constraint. A series of numerical examples will be presented in order to demonstrate the robustness and applicability of this new methodology.     

Core structure of eremophilanes and bakkanes through niobium catalyzed Diels-Alder reaction: synthesis of (+/-)-bakkenolide A

A suitable intermediate for the synthesis of eremophilanes and bakkanes was prepared by a highly regioselective and stereoselective one-step synthesis through a niobium catalyzed Diels-Alder reaction. As a demonstration of the versatility of this intermediate, a total synthesis of (+/-)-bakkenolide A is described.     

Elementary building blocks of self-assembled peptide nanotubes

In the world of biology, "self-assembly" is the ability of biological entities to interact with one another to form supramolecular structures. One basic group of self-assembled structures is peptide nanotubes (PNTs). However, the self-assembly mechanism, with its special characteristics, is not yet fully understood. An exceptional quantum-confined approach is shown here for the self-assembly mechanism in bio-inspired materials. We found the elementary building block of the studied PNT, which is self-assembled from short peptides composed of two phenylalanine residues, to be 0D-quantum-confined (can be related to confinement in 3D), also called a quantum dot (QD). This elementary building block can further self-assemble to a PNT formation. It has been observed that the assembly process of dots to tubes and the disassembly process of tubes to dots are reversible. We further show that a similar dipeptide can also self-assemble to a QD-like structure, with different dimensions. The presented peptide QD structures are nanometer-sized structures, with pronounced exciton effects, which may promote the use of an entirely new kind of organic QDs.     

Highly collinear three-way photoinduced spectrofluorimetric data arrays modelled with bilinear least-squares: Determination of tetracyclines in surface water samples

A new sensitive method for the determination of three tetracyclines in surface water samples (tetracycline, chlortetracycline and oxytetracycline) using highly collinear data corresponding to photochemical-induced fluorescence excitation emission matrices, modelled with three-way data arrays chemometric tools has been developed. The method involves irradiation of aqueous basic solution of antibiotics with UV light and fluorescence determination of the generated photoproducts after solid phase preconcentration (SPE) with Oasis hydrophilic lipophilic balance (HLB) cartridges. The chemometric models were built by using an eight samples calibration set and samples corresponding to both a validation set and a test set. The latter set containing unsuspected interferents. Considering this latter samples, recoveries of 101.5, 97.9 and 102.2 were obtained for the three analytes. Evaluation of constant and proportional bias and precision were made by using the elliptical joint confidence region (EJCR) test for the estimated intercept and slope.     

Formation of gold-silver nanowires in thin surfactant solution films

Thin, long gold/silver nanowires were grown on substrates in thin surfactant solution films. This growth process occurred exclusively in thinning aqueous films as the water evaporated, and elongated surfactant template structures were formed. The nanowire growth depended on the presence of a relatively high concentration of silver ions (typical Ag:Au mole ratio of 1:1). Tuning the pH value to about 5 in the growth solution was crucial for the nanowire growth. Further development of this process may lead to a simple wet chemical technique for the fabrication of relatively uniform arrays of metal nanowires on surfaces.