Helicity Induction in Helicate Self-Organisation from Chiral Tris(bipyridine) Ligand Strands

The chiral tris, and pentakis(bipyridine) ligand strands 3a and 4 were synthesised, each in optically pure form with (S,S)-configuration. Ligand 3a yielded substituted double-helical metal complexes, derived from the parent trihelicate structure 2 , with Cu^I and Ag^I ions. The spectral data, in particular the ¹H-NMR spectra and the large positive Cotton effect, indicate that helicate formation occurs with very high induction of helicity. Together with consideration of the steric effects in the two possible helical diastereoisomers (P)- 1 and (M)- 1 that may be formed, the data favour the preferential generation of the right-handed double helicate (P)- 1 from the tris(bipyridine) strand 3a of(S,S)-configuration.     

Variance of the virtual displacement

We show that the affine structure of the 3-dimensional space is deeply enmeshed with the static laws expression. The relevance of tensorial rules for calculus in mechanics is thus enhanced. The virtual work principle is stated precisely but a little twist is given to the usual statements: the tensorial nature of the so-called virtual displacement vector is asserted to be covariant. To cite this article: C. Vallée et al., C. R. Mecanique 332 (2004).

Résumé

Nous montrons que la structure affine de l'espace tridimensionnel est fortement imbriquée avec l'expression des lois de la statique. La pertinence de l'application des règles du calcul tensoriel à la mécanique est ainsi renforcée. Le principe des travaux virtuels est établi précisément avec une seule entorse aux exposés classiques : la nature tensorielle de l'habituel vecteur déplacement virtuel est affirmée covariante. Pour citer cet article : C. Vallée et al., C. R. Mecanique 332 (2004).     

Intramolecular Cyclization of 1-(ω-Phenylalkyl)-2-(nitromethylene)pyrrolidines in Triflic Acid

1-(ω-Phenylalkyl)-2-(nitromethylene)pyrrolidines in triflic acid undergo a C,O-diprotonation, followed by loss of water, to form conjugated iminium–hydroxynitrilium dications, which react with the tethered phenyl ring by electrophilic aromatic substitution to afford tricyclic iminium compounds as triflate salts. The scope and mechanism of this reaction are discussed.     

Non-invasive vibrational SFG spectroscopy reveals that bacterial adhesion can alter the conformation of grafted "brush" chains on SAM

Understanding bacterial adhesion on a surface is a crucial step to design new materials with improved properties or to control biofilm formation and eradication. Sum Frequency Generation (SFG) vibrational spectroscopy has been employed to study in situ the conformational response of a self-assembled monolayer (SAM) of octadecanethiol (ODT) on a gold film to the adhesion of hydrophilic and hydrophobic ovococcoid model bacteria. The present work highlights vibrational SFG spectroscopy as a powerful and unique non-invasive biophysical technique to probe and control bacteria interaction with ordered surfaces. Indeed, the SFG vibrational spectral changes reveal different ODT SAM conformations in air and upon exposure to aqueous solution or bacterial adhesion. Furthermore, this effect depends on the bacterial cell surface properties. The SFG spectral modeling demonstrates that hydrophobic bacteria flatten the ODT SAM alkyl chain terminal part, whereas the hydrophilic ones raise this ODT SAM terminal part. Microorganism-induced alteration of grafted chains can thus affect the desired interfacial functionality, a result that should be considered for the design of new reactive materials.