title: Molecular and supramolecular chirality in gemini-tartrate amphiphiles studied by electronic and vibrational circular dichroisms.
abstract: This contribution presents an application of electronic circular dichroism (ECD) and vibrational circular dichroism (VCD) to study the molecular and supramolecular chirality in assemblies of gemini-tartrate amphiphiles. Nonchiral dicationic n-2-n amphiphiles (n = 14-20) can self-organize into right- or left-handed structures upon interacting with chiral tartrate counterions. Micellar solutions can also be obtained for shorter alkyl chains (n = 12). First, the conformation of tartrate counterions has been investigated in various environments (micellar solutions and chiral ribbons). ECD and VCD spectra recorded in micellar solutions are independent from the solvent and from the nature of the cations (sodium, cetyl-trimethylammonium, or dimeric surfactant 12-2-12) used and are representative of the anticonformation of the tartrate dianions. On the other hand, drastic changes in the ECD and VCD spectra have been observed in multilayered chiral assemblies of 16-2-16 tartrate. These strong spectral modifications are associated with the chiral arrangement of the tartrate molecules at the surface of the bilayers. Moreover, chirality transfer from counterions to achiral amphiphiles has been clearly evidenced by VCD since circular dichroism has been observed on vibrations related to alkyl chains and gemini headgroups. Finally, ECD and VCD experiments were performed varying the enantiomeric excess of the tartrate. The ECD and VCD intensities do not vary linearly with the enantiomeric excess of the anion and different behaviors have been observed from the two spectroscopic methods: ECD intensities are correlated to the pitch of the ribbons, whereas the VCD intensities are correlated to the dimension of the chiral ribbons.
authors.affiliation: Institut Européen de Chimie et Biologie (IECB), Université de Bordeaux (CNRS UMR5248), Pessac Cedex 33607, France.
authors.forename: Aurélie
authors.initials: A
authors.lastname: Brizard
authors.forename: Damien
authors.initials: D
authors.lastname: Berthier
authors.forename: Carole
authors.initials: C
authors.lastname: Aimé
authors.forename: Thierry
authors.initials: T
authors.lastname: Buffeteau
authors.forename: Dominique
authors.initials: D
authors.lastname: Cavagnat
authors.forename: Laurent
authors.initials: L
authors.lastname: Ducasse
authors.forename: Ivan
authors.initials: I
authors.lastname: Huc
authors.forename: Reiko
authors.initials: R
authors.lastname: Oda