Institut des Sciences Moléculaires d'Orsay



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Accueil > Équipes scientifiques > Structure et dynamique des systèmes complexes isolés photoexcités (SYSIPHE) > CHIralité et spectroscoPIE (CHIPIE) > Vibrational Circular Dichroism

Vibrational Circular Dichroism

par Zehnacker-Rentien Anne - 31 juillet 2018 (modifié le 25 mars 2020)

Our recent VCD studies include cyclic dipeptides in the solid phase, like diketopiperazine peptides and those derived of cis or trans 2-aminocyclobutane-1-carboxylic acids (ACBCs).
The cyclo LL diphenylalanine is organised as dimers in the solid state, which are bound by a double hydrogen bridge. This is however not the case for the LD dipeptides for which dispersion between the aromatic rings is the major interaction in the solid phase.
Solid-state cyclo LL diphenylalanine
Solid-state cyclo LL diphenylalanine
Formation of cyclo LD diphenylalanine in the solid phase by thermal peptide bond formation in the linear LD diphenylalanine parent leads to the formation of a new chiral phase resulting from the synchronisation of the transient chirality of the -otherwise not chiral- subunit.
cis or trans ACBC derivatives have been studied in the solid phase. While the VCD spectrum of the cis derivative is described by that of the monomer in the solid phase, that of the trans requires inclusion of at least a tetramer. A dramatic enhancement in the VCD intensity of the trans derivative relative to the cis is observed.
VCD spectrum and structure of trans and cis ACBC derivatives
VCD spectrum and structure of trans and cis ACBC derivatives
We are also inteerested in the description of VCD spectra for molecules in strong interaction with their solvent. The “Cluster-in-the bulk” description of the influence of hydrogen bond formation on VCD spectra allows proposing a computationally affordable strategy for the calculation of VCD spectra of flexible chiral molecules in strong interaction with their environment. It was compared for 1-indanol insolution in DMSO to time-dependent methods resting on first-principles molecular dynamics (MD) simulations that fully account for anharmonicity, temperature and environment effects.
Experimental and simulated VCD spectra of 1-indanol
Experimental and simulated VCD spectra of 1-indanol

This example emphasizes one of the questions raised by the description of the effects of the environment (solvation,hydrogen bond, formation of clusters or supramolecular entities) and their influence on the shape of the VCD spectra. This study is conducted in the frame of the ANR project Dichroprobe, in collaboration with Carine Clavaguera (LCP Orsay), Rodolphe Vuilleumier (Laboratoire PASTEUR ENS Paris), Florent Calvo (IPG Grenoble)


Effect of puckering motion and hydrogen bond formation on the vibrational circular dichroism spectrum of a flexible molecule : the case of (S)-1-indanol
K. Le Barbu-Debus, A. Scherrer, A. Bouchet, D. Sebastiani, R. Vuilleumier, and A. Zehnacker
Phys. Chem. Chem. Phys., 2018, vol 20, 14635-14646

Solid-state synthesis of cyclo LD-diphenylalanine : A chiral phase built from achiral subunits
A. Perez-Mellor, K. Le Barbu-Debus, and A. Zehnacker
Chirality, 2020, 1-12

Vibrational circular dichroism as a probe of solid-state organisation of derivatives of cyclic beta-amino acids : Cis- and trans-2-aminocyclobutane-1-carboxylic acid
V. Declerck, A. Perez-Mellor, R. Guillot, DJ. Aitken, M. Mons, and A. Zehnacker
Chirality, 2019, vol 31, 547-560