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.     

Nilpotent Subgroups of Groups with All Subgroups Subnormal

It is proved that in groups with all subgroups subnormal everynilpotent subgroup is contained in a normal nilpotent subgroup.     

Surface models and reaction barrier in Eley-Rideal formation of H2 on graphitic surfaces

The exothermic, collinearly-dominated Eley-Rideal hydrogen formation on graphite is studied with electronic structure and quantum dynamical means. In particular, the focus is on the importance of the model used to describe the graphitic substrate, in light of the marked discrepancies present in available literature results. To this end, the collinear reaction is considered and the potential energy surface is computed for a number of different graphitic surface models using Density Functional Theory (DFT) for different dynamical regimes. Quantum dynamics is performed with wavepacket techniques down to the cold collision energies relevant for the chemistry of the interstellar medium. Results show that the reactivity at moderate-to-high collision energies sensitively depends on the shape of the PES in the entrance channel, which in turn is related to the adopted surface model. At low energies we rule out the presence of any barrier to reaction, thereby highlighting the importance of quantum reflection in limiting the reaction efficiency.     

Nil-automorphisms of groups with residual properties

Let G be any group and x an automorphism of G. The automorphism x is said to be nil if, for every g ∈ G, there exists n = n(g) such that [g, _n x] = 1. If n can be chosen independently of g, we say that x is n-unipotent. A nil (resp. unipotent) automorphism x could also be seen as a left Engel element (resp. left n-Engel element) in the group G〈x〉. When G is a finite dimensional vector space, groups of unipotent linear automorphisms turn out to be nilpotent, so that one might ask to what extent this result can be extended to a more general setting. In this paper we study finitely generated groups of nil or unipotent automorphisms of groups with residual properties (e.g. locally graded groups, residually finite groups, profinite groups), proving that such groups are nilpotent.     

Bond-based peridynamic modelling of singular and nonsingular crack-tip fields

A static meshfree implementation of the bond-based peridynamics formulation for linearly elastic solids is applied to the study of the transition from local to nonlocal behavior of the stress and displacement fields in the vicinity of a crack front and other sources of stress concentration. The long-range nature of the interactions between material points that is intrinsic to and can be modulated within peridynamics enables the smooth transition from the square-root singular stress fields predicted by the classical (local) linear theory of elasticity, to the nonsingular fields associated with nonlocal theories. The accuracy of the peridynamics scheme and the transition from local to nonlocal behavior, which are dictated by the lattice spacing and micromodulus function, are assessed by performing an analysis of the boundary layer that surrounds the front of a two dimensional crack subjected to mode-I loading and of a cracked plate subjected to far-field tension.     

Torsion-free groups in which every subgroup is subnormal

We prove that a torsion-free group in which every subgroup is subnormal is nilpotent. This work is a contribution to MURST project “Teoria dei gruppi e applicazioni”     

Inherently Chiral Spider‐Like Oligothiophenes

The racemate of an inherently chiral “spider‐like” octathiophene monomer T8₃ , in which chirality is generated by torsion in its backbone, was synthesized. The racemate was resolved into configurationally stable antipodes by HPLC on a chiral stationary phase. Electrooxidation of the enantiomers resulted in materials displaying high enantiorecognition ability towards the antipodes of some chiral probes. Moreover, the T8₃ racemate demonstrated great aptitude to stimulate formation of 3D rigid architectures if used as a cross‐linking monomer for molecular imprinting. This feature was exploited to devise a molecularly imprinted polymer‐based chemosensor selective for a thymine–adenine oligonucleotide.     

Homogenization towards a mechanistic Rigid Body and Spring Model (HRBSM) for the non-linear dynamic analysis of 3D masonry structures

A mechanistic model with rigid elements and interfaces suitable for the non-linear dynamic analysis of full scale 3D masonry buildings is presented. The model relies into two steps: in the first step, a simplified homogenization is performed at the meso-scale to deduce the mechanical properties of a macroscopic material, to be used in structural applications; the second step relies into the implementation of a Rigid Body and Spring Model (RBSM) constituted by rigid elements linked with homogenized interfaces. In the homogenization step, a running bond elementary cell is discretized with 24 three-node plane-stress elastic triangular elements and non-linear interfaces representing mortar joints. It is shown how the mechanical problem in the unit cell is characterized by few displacement variables and how homogenized stress–strain curves can be evaluated by means of a semi-analytical approach. The second step relies on the implementation of the homogenized curves into a RBSM, where an entire masonry structure can be analyzed in the non-linear dynamic range through a discretization with rigid elements and inelastic interfaces. Non-linear structural analyses are conducted on a church façade interconnected with a portion of the perpendicular walls and on a small masonry building, for which experimental and numerical data are available in the literature, in order to show how quite reliable results may be obtained with a limited computational effort.