On the aromatic stabilization of corannulene and coronene

The application of set of homodesmotic reactions allowed us to estimate the aromatic stabilization energy (ASE) of corannulene and coronene. Appropriate reactions have been applied to balance syn/anti mismatches in di-, tetra- and hexamethylene substituted derivatives. Based on many different polycyclic reference structures that compensate the effect of strain in the corannulene moiety the value of ASE comes to 44.5 kcal mol(-1). Planar corannulene is more stabilized by cyclic π-electron delocalization by ca. 10.7 kcal mol(-1), as compared with a bowl-shaped system. A similar approach for coronene leads to an ASE equal to 58.4 kcal mol(-1).     

Hydrogen-Bonded Cyclic Dimers at Large Compression: The Case of 1H-pyrrolo[3,2-h]quinoline and 2-(2′-pyridyl)pyrrole

1H-pyrrolo[3,2-h]qinoline (PQ) and 2-(2′-pyridyl)pyrrole (PP) are important systems in the study of proton-transfer reactions. These molecules possess hydrogen bond donor (pyrrole) and acceptor (pyridine) groups, which leads to the formation of cyclic dimers in their crystals. Herein, we present a joint experimental (Raman scattering) and computational (DFT modelling) study on the high-pressure behaviour of PQ and PP molecular crystals. Our results indicate that compression up to 10 GPa (100 kbar) leads to considerable strengthening of the intermolecular hydrogen bond within the cyclic dimers. However, the intramolecular N–H∙∙∙N interaction is either weakly affected by pressure, as witnessed in PQ, or weakened due to compression-induced distortions of the molecule, as was found for PP. Therefore, we propose that the compression of these systems should facilitate double proton transfer within the cyclic dimers of PQ and PP, while intramolecular transfer should either remain unaffected (for PQ) or weakened (for PP).     

Neutral fermion excitations in the Moore-Read state at filling factor ν = 5/2

We present evidence supporting the weakly paired Moore-Read phase in the half-filled second Landau level, focusing on some of the qualitative features of its excitations. Based on numerical studies, we show that systems with odd particle number at the flux N(?)=2N-3 can be interpreted as a neutral fermion mode of one unpaired fermion, which is gapped. The mode is found to have two distinct minima, providing a signature that could be observed by photoluminescence. In the presence of two quasiparticles the same neutral fermion excitation is shown to be gapless, confirming expectations for non-abelian statistics of the Ising model with degenerate fusion channels 1 and ψ.     

On the Łojasiewicz numbers

Let f be a holomorphic function of two complex variables with an isolated critical point at $\text{0∈}\text{C}{}^2$. We give some necessary conditions for a rational number to be the smallest θ>0 in the ?ojasiewicz inequality |gradf(z)|?C|z|^θ for z near $\text{0∈}\text{C}{}^2$. To cite this article: E. Garc??a Barroso, A. P?oski, C. R. Acad. Sci. Paris, Ser. I 336 (2003).     

Interacting electrons on a two-dimensional surface: planar vs. spherical geometries

The center-of-mass excitations are identified in the spectrum of electrons on a two-dimensional surface in the lowest Landau level. The correspondence between the quantum numbers labeling electron states on a sphere and on a plane is drawn. The excitation spectrum on a sphere with increasing radius is shown to converge to that on a plane. In particular, in the presence of a lateral confinement (i.e. for the case of quantum dots), identical series of magic states appear in both cases. Also, a class of interaction potentials which lead to the fractional quantum Hall effect in an extended system are identified.     

A Functional Role for Aβ in Metal Homeostasis? N‐Truncation and High‐Affinity Copper Binding

Accumulation of the β‐amyloid (Aβ) peptide in extracellular senile plaques rich in copper and zinc is a defining pathological feature of Alzheimer′s disease (AD). The Aβ1–x (x=16/28/40/42) peptides have been the primary focus of Cu^II binding studies for more than 15 years; however, the N‐truncated Aβ4–42 peptide is a major Aβ isoform detected in both healthy and diseased brains, and it contains a novel N‐terminal FRH sequence. Proteins with His at the third position are known to bind Cu^II avidly, with conditional log K values at pH 7.4 in the range of 11.0–14.6, which is much higher than that determined for Aβ1–x peptides. By using Aβ4–16 as a model, it was demonstrated that its FRH sequence stoichiometrically binds Cu^II with a conditional K_d value of 3×10^?14 M at pH 7.4, and that both Aβ4–16 and Aβ4–42 possess negligible redox activity. Combined with the predominance of Aβ4–42 in the brain, our results suggest a physiological role for this isoform in metal homeostasis within the central nervous system.     

Carbon and secondary deuterium kinetic isotope effects on SN2 methyl transfer reactions

Carbon and secondary deuterium kinetic isotope effect (KIE) for three types of S_N2 methyl transfer reactions have been predicted theoretically at a DFT level in gas phase and in aqueous solution modelled by the PCM continuum solvent model. No correlation between these isotope effects and geometrical features of the corresponding transition states (TSs), force constants of the imaginary frequency or Gibbs free energies of the studied reactions has been found. These findings suggest that comparative analysis of the magnitudes of the studied KIEs should be constrained to interpretation of the TS localization on the reaction coordinate only in a series of very closely related reactions. Copyright © 2007 John Wiley & Sons, Ltd.     

Stereoselective Synthesis of [Rp]-Dinucleoside (3′,5′)-Methanephosphonates

Abstract

DBU-assisted phosphonylating properties of diastereomerically pure 5′-O-DMT- thymidine (O-2,4,6-trimetylbenzoyl methanephosphonothiate)(1) towards alcohols [1] have been used for the synthesis of [Rp]-dithymidylyl(3′,5′)-methanephosphonothiótes (2) and metanephosphonates (3). Substrates (4) and (5) have been obtained according to the previously described methods [2].