Ricerc@Sapienza

The presence of stereogenic elements is a common feature in pharmaceutical compounds, and affording optically pure stereoisomers is a frequent issue in drug design. In this context, the study of the chiral molecular recognition mechanism fundamentally supports the understanding and optimization of chromatographic separations with chiral stationary phases.

We investigate the chiro-optical properties of the electromagnetic near-field associated with the excitation of collective optical resonances (surface lattice resonances) in achiral plasmonic lattices. These arrays are specially designed to support dispersive resonances with non-trivial, multipolar near-field distributions in the surroundings of the nanostructure, which gives rise to an enhanced chiro-optical response.

Chiral optical response is an inherent property of molecules and nanostructures, which cannot be superimposed on their mirror images. In specific cases, optical chirality can be observed also for symmetric structures. This so-called extrinsic chirality requires that the mirror symmetry is broken by the geometry of the structure together with the incident or emission angle of light. From the fabrication point of view, the benefit of extrinsic chirality is that there is no need to induce structural chirality at nanoscale.

Arrays of nanoholes in metal are important plasmonic devices proposed for applications spanning from biosensing to communications. In this work we show that in such arrays the symmetry can be broken by means of the elliptical shape of the nanoholes, combined with the in-plane tilt of the ellipse axes away from the array symmetry lines. The array then differently interacts with circular polarizations of opposite handedness at normal incidence, i.e. it becomes intrinsically chiral. The measure of this difference is called circular dichroism (CD).

We demonstrate the control of enhanced chiral field distribution at the surface of hybrid metallo-dielectric nanostructures composed of self-assembled vertical hexagonal GaAs-based nanowires having three of the six sidewalls covered with Au. We show that weakly-guided modes of vertical GaAs nanowires can generate regions of high optical chirality that are further enhanced by the break of the symmetry introduced by the gold layer.

Throughout the 19th and 20th century, chirality has mostly been associated with chemistry. However, while chirality can be very useful for understanding molecules, molecules are not well suited for understanding chirality. Indeed, the size of atoms, the length of molecular bonds and the orientations of orbitals cannot be varied at will. It is therefore difficult to study the emergence and evolution of chirality in molecules, as a function of geometrical parameters. By contrast, chiral metal nanostructures offer an unprecedented flexibility of design.

The infrared multiphoton dissociation (IRMPD) spectra of electrospray ionization (ESI)-formed proton-bound complexes between the axially chiral multifunctional macrocycle MaR and d- and l-phenylalanine (PD and PL ) or d- and l-3,4-dihydroxyphenylalanine (DD and DL ) are recorded in the ?˜ =2800-3700?cm-1 region. Whereas the diastereomeric [MaR ?H?PD ]+ and [MaR ?H?PL ]+ complexes do not show any significant spectral differences, the spectrum of [MaR ?H?DD ]+ clearly diverges from that of its [MaR ?H?DL ]+ diastereomer.

(+)-(S) and (−)-(R)-5-methyl-Wieland-Miescher ketone (+)-1 and (−)-1, are important synthons in the diastereo and enantioselective syntheses of biological and/or pharmacological interesting compounds. A key step in these syntheses is the chemoselective C(1)O acetalization to (+)-5 and (−)-5, respectively. Various procedures for this transformation have been described in the literature. Among them, the classical procedure based on the use of 1,2-ethanediol and TsOH in refluxing benzene in the presence of a Dean-Stark apparatus.

In the present article, we have investigated the possibility of forming propylene oxide (PO) from propylene (PE) by bi-molecular reactions. Propylene oxide is the first chiral molecule observed in the interstellar medium, and studying the thermodynamics and kinetics of formation can suggest possible synthetic routes. We have focused our attention on gas-phase reactions, and the presence of an environment is discussed in particular for the possibility of forming it by association reactions. In particular, we have considered radical and ion–molecule reactions.

The increasing interest for obtaining pure, single enantiomers of chiral organic compounds has greatly expanded the progress of new synthetic procedures, especially in the field of chiral drugs, agrochemicals, flavors, and natural products. A parallel trend has been observed in the development of stereoselective separation methods for the precise and accurate measurements of the enantiomeric purity of chiral compounds.