Inherently Chiral Macrocyclic Oligothiophenes: Easily Accessible Electrosensitive Cavities with Outstanding Enantioselection Performances

Linear conjugated oligothiophenes of variable length and different substitution pattern are ubiquitous in technologically advanced optoelectronic devices, though limitations in application derive from insolubility, scarce processability and chain‐end effects. This study describes an easy access to chiral cyclic oligothiophenes constituted by 12 and 18 fully conjugated thiophene units. Chemical oxidation of an “inherently chiral” sexithiophene monomer, synthesized in two steps from commercially available materials, induces the formation of an elliptical dimer and a triangular trimer endowed with electrosensitive cavities of different tunable sizes. Combination of chirality with electroactivity makes these molecules unique in the current oligothiophenes literature. These macrocycles, which are stable and soluble in most organic solvents, show outstanding chiroptical properties, high circularly polarized luminescence effects and an exceptional enantiorecognition ability.     

Molecular Fluorescence Imaging Spectroscopy for Mapping Low Concentrations of Red Lake Pigments: Van Gogh's Painting The Olive Orchard

Vincent van Gogh used fugitive red lake pigments that have faded in some paintings. Mapping their distribution is key to understanding how his paintings have changed with time. While red lake pigments can be identified from microsamples, in situ identification and mapping remain challenging. This paper explores the ability of molecular fluorescence imaging spectroscopy to identify and, more importantly, map residual non‐degraded red lakes. The high sensitivity of this method enabled identification of the emission spectra of eosin (tetrabromine fluorescein) lake mixed with lead or zinc white at lower concentrations than elemental X‐ray fluorescence (XRF) spectroscopy used on account of bromine. The molecular fluorescence mapping of residual eosin and two carmine red lakes in van Gogh's The Olive Orchard is demonstrated and compared with XRF imaging spectroscopy. The red lakes are consistent with the composition of paint tubes known to have been used by van Gogh.     

The notion of observable and the moment problem for $$*$$∗-algebras and their GNS representations

Letters in Mathematical Physics - We address some usually overlooked issues concerning the use of $$*$$-algebras in quantum theory and their physical interpretation. If $${\mathfrak {A}}$$ is a...     

The MAST-edge centred lumped scheme for the flow simulation in variably saturated heterogeneous porous media

A novel methodology is proposed for the solution of the flow equation in a variably saturated heterogeneous porous medium. The computational domain is descretized using triangular meshes and the governing PDEs are discretized using a lumped in the edge centres numerical technique. The dependent unknown variable of the problem is the piezometric head. A fractional time step methodology is applied for the solution of the original system, solving consecutively a prediction and a correction problem. A scalar potential of the flow field exists and in the prediction step a MArching in Space and Time (MAST) formulation is applied for the sequential solution of the Ordinary Differential Equation of the cells, ordered according to their potential value computed at the beginning of the time step. In the correction step, the solution of a large linear system with order equal to the number of edges is required. A semi-analytical procedure is also proposed for the solution of the prediction step. The computational performance, the order of convergence and the mass balance error have been estimated in several tests and compared with the results of other literature models.     

Investigation of a Pt–Fe/C catalyst for oxygen reduction reaction in direct ethanol fuel cells

Three cathode catalysts (60% Pt/C, 30% Pt/C and 60% Pt–Fe/C), with a particle size of about 2–3 nm, were prepared to investigate the effect of ethanol cross-over on cathode surfaces. All samples were studied in terms of structure and morphology by using X-ray diffraction (XRD) and transmission electron microscopy (TEM) analyses. Their electrocatalytic behavior in terms of oxygen reduction reaction (ORR) was investigated and compared using a rotating disk electrode (RDE). The tolerance of cathode catalysts in the presence of ethanol was evaluated. The Pt–Fe/C catalyst showed both higher ORR activity and tolerance to ethanol cross-over than Pt/C catalysts. Moreover, the more promising catalysts were tested in 5 cm² DEFC single cells at 60 and 80 °C. An improvement in single cell performance was observed in the presence of the Pt–Fe catalyst, due to an enhancement in the oxygen reduction kinetics. The maximum power density was 53 mW cm⁻² at 2 bar rel. cathode pressure and 80 °C.     

The reaction-annihilator distribution and the nonholonomic Noether theorem for lifted actions

We consider nonholonomic systems with linear, time-independent constraints subject to positional conservative active forces. We identify a distribution on the configuration manifold, that we call the reaction-annihilator distribution ℜ°, the fibers of which are the annihilators of the set of all values taken by the reaction forces on the fibers of the constraint distribution. We show that this distribution, which can be effectively computed in specific cases, plays a central role in the study of first integrals linear in the velocities of this class of nonholonomic systems. In particular we prove that, if the Lagrangian is invariant under (the lift of) a group action in the configuration manifold, then an infinitesimal generator of this action has a conserved momentum if and only if it is a section of the distribution ℜ°. Since the fibers of ℜ° contain those of the constraint distribution, this version of the nonholonomic Noether theorem accounts for more conserved momenta than what was known so far. Some examples are given.      

Regularity of multivariate vector subdivision schemes

In this paper we discuss methods for investigating the convergence of multivariate vector subdivision schemes and the regularity of the associated limit functions. Specifically, we consider difference vector subdivision schemes whose restricted contractivity determines the convergence of the original scheme and describes the connection between the regularity of the limit functions of the difference subdivision scheme and the original subdivision scheme.     

Deterministic impulse control in native forest ecosystems management

This paper illustrates an application of impulse control systems analysis to the management of renewable resources. We obtain an explicit definition for the impulse optimal strategy in the case of a nonlinear natural system which models certain types of forests. The result is in agreement with an econo-ecological conservative action on the forest. The examples developed in this paper associate new theories on impulse or jump control with natural forest management. In addition, we compare our results with the classical ones. We also show that a nonoptimal managing action on the forest is frequently the cause for significant medium-term losses.This work was supported by CONICET, Consejo Nacional de Investigaciones Científicas y Técnicas, and by the Universidad Nacional del Litoral, Argentina.