Synthesis of highly decorated chiral 2-nitro-cyclohexane carboxylic esters through microwave-assisted organocatalyzed cascade reactions

Starting from (E)-β-substituted-β-nitroacrylates and α,β-unsaturated ketones, a stereoselective organocatalyzed one-pot methodology allowed to synthesize highly decorated chiral 2-nitro-cyclohexane carboxylic esters. The reaction is promoted by Cinchona alkaloid-derived primary amines in the presence of an acidic co-catalyst and affords two diastereoisomers, in good yields and high enantiomeric excess (often higher than 90% ee). By replacing conventional heating with microwave irradiation, cleaner reactions in shortened times (from 48 h to 30 min) were obtained, with improved dr (80:20) and high ee (up to 94%). The application of microwave technology to this organocatalytic methodology allowed also employing C1 substituted enones, leading to cyclohexanones with four contiguous stereocenters in two isomers only, and up to 99% enantioselectivity.     

Conformational and electronic study of dopamine interacting with the D2 dopamine receptor

We report an exhaustive conformational and electronic study on dopamine (DA) interacting with the D₂ dopamine receptor (D₂DR). For the first time, the complete surface of the conformational potential energy of the complex DA/D₂DR is reported. Such a surface was obtained through the use of QM/MM calculations. A detailed study of the molecular interactions that stabilize and destabilize the different molecular complexes was carried out using two techniques: Quantum Theory of Atoms in Molecules computations and nuclear magnetic shielding constants calculations. A comparative study of the behavior of DA in the gas phase, aqueous solution, and in the active site of D₂DR has allowed us to evaluate the degree of deformation suffered by the ligand and, therefore, analyze how rustic are the lock-key model and the induced fit theory in this case. Our results allow us to propose one of the conformations obtained as the “biologically relevant” conformation of DA when it is interacting with the D₂DR.     

Phase transitions in gallium nanodroplets detected by dielectric spectroscopy

Both theoretical and experimental works give evidence that gallium exhibits solid phases labelled , , , besides the stable phase strongly dependent both on the size and the confinement conditions. An experimental technique was used based on capacitance and conductance measurements vs. temperature in the audiofrequency range. This technique is particularly sensitive to the conditions of the investigated particle surface that plays a fundamental role in the melting and more generally in the phase transition processes. In particular the strict relation between the derivative of the capacitance with respect to the temperature, dC/dT, and the entropy of the system is considered. In gallium nanoparticles 20 nm in radius, only the phase is shown to occur. Further the transition to liquid phase was detected. The melting process was found to start about 65 K below the full melting temperature value. In the case of particles 10 nm in radius, where different metastable phases may occur, the capacitance vs. temperature curve was found to display abrupt changes of the slope. The singularities are associated to a well defined transition temperature.     

Electronic transmission through a ladder with a single side-attached impurity

We study the electronic transmission of a model system composed by two coupled chains with an impurity attached to one of them. Analytical espressions for the transmittivity and for the diagonal and the off-diagonal Green’s function matrix elements are derived. Green’s function behaviour as function of the charge carrier energy is exploited to interpret the system transmittivity calculated by the scattering matrix formalism. We find that while a single substitutional impurity in the ladder may generate a Fano resonance in the transmittivity in the lower or in the higher energy part of the spectrum, in the case of a single side-attached impurity to the ladder, a resonance is found in each energy region. We interpret such resonances in terms of local density of states and off-diagonal Green’s function matrix elements.     

Electroless silver plating of the surface of organic semiconductors

The integration of nanoscale processes and devices demands fabrication routes involving rapid, cost-effective steps, preferably carried out under ambient conditions. The realization of the metal/organic semiconductor interface is one of the most demanding steps of device fabrication, since it requires mechanical and/or thermal treatments which increment costs and are often harmful in respect to the active layer. Here, we provide a microscopic analysis of a room temperature, electroless process aimed at the deposition of a nanostructured metallic silver layer with controlled coverage atop the surface of single crystals and thin films of organic semiconductors. This process relies on the reaction of aqueous AgF solutions with the nonwettable crystalline surface of donor-type organic semiconductors. It is observed that the formation of a uniform layer of silver nanoparticles can be accomplished within 20 min contact time. The electrical characterization of two-terminal devices performed before and after the aforementioned treatment shows that the metal deposition process is associated with a redox reaction causing the p-doping of the semiconductor.     

A self-consistent method for treating point impurities with arbitrary range potentials

We propose a generalized Green's function technique for treating impurities whose potential has an arbitrary short, intermediate, or long-range nature. The approach exploits the recursion method, and can be formulated in a self-consistent way for point impurities.     

Self-trapped excitons in rare-gas dimers and solids

The excited electron states in isolated rare-gas dimers are described by a model Hamiltonian with appropriate simplifications for the short-range terms. Then the energies of self-trapped excitons are obtained by including solid state effects. The results are compared with the available transient absorption spectroscopy measurements.     

Dynamic formulation of the moment and the recursion methods

The dynamic equations at the basis of the recursion method and of the moment method are discussed using the projection techniques borrowed from statistical mechanics. A local orbital is regarded as the system of interest and the rest of the crystal takes the place of a highly non-Markovian reservoir. A rewarding aspect of the formalism is an improved relation between the chain parameters of the recursion method and the moments. It is speculated that the concepts of random forces and their dynamics could be of help in determining the asymptotic behaviour of the chain variables.     

Short-range interaction in the exciton effective-mass Hamiltonian

The integral equation for excitons is considered in the weak binding limit. The expression of the short-range electron-hole interaction is provided in terms of the Wannier functions.