Understanding Overhauser Dynamic Nuclear Polarisation through NMR relaxometry

Overhauser dynamic nuclear polarisation (DNP) represents a potentially outstanding tool to increase the sensitivity of solution and solid state NMR experiments, as well as of magnetic resonance imaging. DNP signal enhancements are strongly linked to the spin relaxation properties of the system under investigation, which must contain a paramagnetic molecule used as DNP polariser. In turn, nuclear spin relaxation can be monitored through NMR relaxometry, which reports on the field dependence of the nuclear relaxation rates, opening a route to understand the physical processes at the origin of the Overhauser DNP in solution. The contributions of dipole–dipole and Fermi-contact interactions to paramagnetic relaxation are here described and shown to be responsible to both the relaxometry profiles and the DNP enhancements, so that the experimental access to the former can allow for predictions of the latter.     

4-Stannylcoumarins as Useful Reagents in a New Approach to Neoflavonoids

4-Trimethylstannylcoumarins 2, conveniently obtained from the corresponding 4-triflyloxycoumarins 1, undergo Pd(0)/CuI-cocatalyzed cross-coupling reactions with a variety of aryl iodides to afford 4-arylcoumarins 4 in moderate to good yields. Aryl triflates are less effective as coupling partners.     

Derivation of the Dirac Equation by Conformal Differential Geometry

A rigorous ab initio derivation of the (square of) Dirac’s equation for a particle with spin is presented. The Lagrangian of the classical relativistic spherical top is modified so to render it invariant with respect conformal changes of the metric of the top configuration space. The conformal invariance is achieved by replacing the particle mass in the Lagrangian with the conformal Weyl scalar curvature. The Hamilton-Jacobi equation for the particle is found to be linearized, exactly and in closed form, by an ansatz solution that can be straightforwardly interpreted as the “quantum wave function” of the 4-spinor solution of Dirac’s equation. All quantum features arise from the subtle interplay between the conformal curvature acting on the particle as a potential and the particle motion which affects the geometric “pre-potential” associated to the conformal curvature itself. The theory, carried out here by assuming a Minkowski metric, can be easily extended to arbitrary space-time Riemann metric, e.g. the one adopted in the context of General Relativity. This novel theoretical scenario appears to be of general application and is expected to open a promising perspective in the modern endeavor aimed at the unification of the natural forces with gravitation.     

Triptycene‐Roofed Quinoxaline Cavitands for the Supramolecular Detection of BTEX in Air

Two novel triptycene quinoxaline cavitands ( DiTriptyQxCav and MonoTriptyQxCav ) have been designed, synthesized, and applied in the supramolecular detection of benzene, toluene, ethylbenzene, and xylenes (BTEX) in air. The complexation properties of the two cavitands towards aromatics in the solid state are strengthened by the presence of the triptycene moieties at the upper rim of the tetraquinoxaline walls, promoting the confinement of the aromatic hydrocarbons within the cavity. The two cavitands were used as fiber coatings for solid‐phase microextraction (SPME) BTEX monitoring in air. The best performances in terms of enrichment factors, selectivity, and LOD (limit of detection) values were obtained by using the DiTriptyQxCav coating. The corresponding SPME fiber was successfully tested under real urban monitoring conditions, outperforming the commercial divinylbenzene–Carboxen–polydimethylsiloxane (DVB–CAR–PDMS) fiber in BTEX adsorption.