Resonance expansions in quantum mechanics

The goal of this contribution is to discuss various resonance expansions that have been proposed in the literature. Presented at the 3rd International Workshop “Pseudo-Hermitian Hamiltonians in Quantum Physics”, Istanbul, Turkey, June 20–22, 2005.     

Indirect regioselective heteroarylation of indoles through a Friedel-Crafts reaction with (E)-1,4-diaryl-2-buten-1,4-diones

A two-step synthesis of 3-heteroaryl indoles has been developed. The first step of the sequence involves a Friedel-Crafts alkylation of indoles with 1,4-diaryl-2-buten-1,4-diones to give the corresponding indoles bearing a 1,4-dicarbonyl moiety. The reaction is catalyzed by InCl₃ and takes place with good yields. Cyclization of the diones under different Paal-Knorr conditions allows to prepare indoles substituted at the C3 position with 3-furanyl, 3-pyrrolyl- and 3-thienyl moieties.     

Ultrafast Decay of the Excited Singlet States of Thioxanthone by Internal Conversion and Intersystem Crossing

The experimental ultrafast photophysics of thioxanthone in several aprotic organic solvents at room temperature is presented, measured using femtosecond transient absorption together with high‐level ab initio CASPT2 calculations of the singlet‐ and triplet‐state manifolds in the gas phase, including computed state minima and conical intersections, transition energies, oscillator strengths, and spin–orbit coupling terms. The initially populated singlet ππ* state is shown to decay through internal conversion and intersystem crossing processes via intermediate nπ* singlet and triplet states, respectively. Two easily accessible conical intersections explain the favorable internal conversion rates and low fluorescence quantum yields in nonpolar media. The presence of a singlet–triplet crossing near the singlet ππ* minimum and the large spin–orbit coupling terms also rationalize the high intersystem crossing rates. A phenomenological kinetic scheme is proposed that accounts for the decrease in internal conversion and intersystem crossing (i.e. the very large experimental crescendo of the fluorescence quantum yield) with the increase of solvent polarity.     

Synthesis and characterization of an amethyrin-uranyl complex displaying aromatic character

Abstract

The reaction between amethyrin and non-aqueous uranyl silylamide (UO₂[N(SiMe₃)₂]₂) under anaerobic conditions affords a bench-stable uranyl complex. UV–vis spectroscopy, cyclic voltammetry, as well as proton NMR spectroscopic analyses provide support for the conclusion that all six pyrrole subunits participate in coordination of the uranyl dication and that, upon complexation, the amethyrin-core undergoes a 2-electron oxidation to yield a formal 22 π-electron aromatic species.     

Synthesis of (S)-(+)-sotalol and (R)-(−)-isoproterenol via a catalytic enantioselective Henry reaction

A unified approach for the synthesis of (S)-(+)-sotalol and (R)-(?)-isoproterenol has been developed. The enantioselective Henry reaction of the appropriate aldehyde in the presence of a camphor-derived amino pyridine–Cu(II) complex was the key step of the synthesis. The reduction of the nitro group to give the corresponding amino alcohols followed by reductive alkylation of the amine provided the target products with high enantiomeric excesses.     

Dynamic chirality in selected diaryl methane containing drugs. An exploratory ab initio conformational study

Diaryl methane molecules (Ar–CH₂–Ar) represent double rotor conformational problems. The simplest diaryl methane, diphenyl methane (Ph–CH₂–Ph), governs certain symmetric conformational potential energy surface (PES) topology. With the replacement of one of the phenyl groups by a heterocyclic moiety, the PES topology may change dramatically. The induction of point-chirality, in the prochiral CH₂ group, by axis-chirality or plane-chirality is explored within the framework of ‘dynamic chirality’.     

The hausdorff dimension of the harmonic class on negatively curved surfaces

We study the regularity of the Hausdorff dimension of the harmonic class of a surface M of negative curvature as a function of the riemannian metric. We prove that it is a C^{r− 3} function of the metric in the Banach manifold of C^r riemannian metrics on M. We also prove regularity results for some asymptotic quantities associated to the Brownian motion on M.     

Determination of parathion in the presence of paraoxon and p-nitrophenol by flow-injection analysis with amperometric detection

The amperometric determination of parathion in the presence of its metabolites paraoxon and p-nitrophenol in a flow-injection system is reported. The method is based on the measurement of the oxidation signal yielded by p-nitrophenol on hydrolysis of parathion in the presence of Pd(II) or Hg(II). The oxidation of the metabolite was preferred to its reduction as it avoids the removal of oxygen, which poses major problems in flow-through configurations.