Dipolar and V-shaped structures incorporating methylenepyran and diazine fragments

Thirteen novel dipolar and V-shaped chromophores with pyranylidene electron-donating part, diazine electron-withdrawing part and various π-linkers were synthesized. The extent of intramolecular charge transfer, structure-property relationships and optical properties were further investigated by UV/Vis absorption, electrochemistry, and DFT calculations.     

On the liquid-crystalline properties of methacrylic polymers containing 4′-(4-alkyloxyphenyl)azobenzene mesogens

In this article, we report on the synthesis and thermotropic behaviour of methacrylic polymers containing 4′-(4-alkyloxyphenyl)azobenzene mesogens attached to the backbone through n-alkyloxy spacers of 6 or 10 methylene groups. Polymerisations were carried out via free radicals using azobisisobutyronitrile (AIBN) as initiator. Chemical structures of polymers and their precursors were characterised by ¹H NMR spectroscopy. Thermogravimetric analysis showed that azopolymers are thermally stable up to temperatures around 300°C. The thermotropic liquid-crystalline (LC) behaviour was studied by differential scanning calorimetry (DSC), polarized optical microscopy (POM) and X-ray diffraction (XRD). Results indicate that all synthesised mesogens, monomers and polymers developed two or more orthogonal LC phases in wide temperature ranges. Mesogens and monomers developed nematic and smectic phases, whereas polymers exhibited only smectic phase. In polymers, the arrangement of mesogens depends on the relative length of the spacer and the terminal flexible chain; two distinct structural models were proposed based on chemical interactions and steric constrains. The trans–cis photoisomerisation of monomers and polymers in solution was also studied. High cis-isomer contents (>80%) were reached in relative short irradiation times despite the steric constrains imposed by the polymer backbone.     

Hartley’s oscillator: The simplest chaotic two-component circuit

This paper shows an experimental evidence of chaos in one of the simplest imaginable autonomous implicit Hartley’s oscillator made simply of a junction field effect transistor (JFET) and a tapped coil. The experimental setup is implemented. The variations of amplitude of the oscillations through the control element are obtained showing the domain of existence of chaos. Phase portraits of the PSpice simulation, of the numerical integration and of the experiment are displayed, confirming a good agreement between theory and praxis.     

Philicity of Acetonyl and Benzoyl Radicals: A Comparative Experimental and Computational Study

In this work, the reactivities of acetonyl and benzoyl radicals in aromatic substitution and addition reactions have been compared in an experimental and computational study. The results show that acetonyl is more electrophilic than benzoyl, which is rather nucleophilic. A Hammett plot analysis of the addition reactions of the two radicals to substituted styrenes clearly support the nucleophilicity of benzoyl, but in the case of acetonyl, no satisfactory linear correlation with a single substituent-related parameter was found. Computational calculations helped to rationalize this effect, and a good linear correlation was found with a combination of polar parameters (σ⁺) and the radical stabilization energies of the formed intermediates. Based on the calculated philicity indices for benzoyl and acetonyl, a quantitative comparison of these two radicals with many other reported radicals is possible, which may help to predict the reactivities of other aromatic radical substitution reactions.     

Existence and uniqueness of optimal dynamic pricing and advertising controls without concavity

We consider a pricing and advertising dynamic-optimization problem where the goodwill dynamics evolve à la Nerlove–Arrow. The firm maximizes its profit over a finite-planning horizon corresponding to the product’s lifespan, and it turns out that the Hamiltonian is non-concave. We show the existence and uniqueness of an optimal solution under some mild conditions.