Conformational studies of Gram-negative bacterial quorum sensing acyl homoserine lactone (AHL) molecules: The importance of the n → π* interaction

Goar Sánchez-Sanz, Irish Centre of High-End Computing
Darren Crowe, Technological University Dublin
Alan Nicholson, Technological University Dublin
Adrienne Fleming, Technological University Dublin
Ed Carey, Technological University Dublin
Fintan Kelleher, Technological University Dublin

Document Type Article

Biophysical Chemistry

Abstract

A 1H NMR study shows the presence of intermolecular hydrogen bonds for AHLs in CDCl3 solution. A detailed computational study of the structure of AHLs and the relative stability between the extended conformations (X) and those showing n → π* interactions (np) have been carried out by means of DFT calculations. Solvent effects have been shown to be very important when stabilising np conformations, particularly with polar solvents. This was shown by the shortening of C⋯O intramolecular distances and the increase in the relative energies favouring the np conformation with the dielectric constant of the solvent. The charge transfer between the O donor and the acceptor carbonyl group, assessed by second order perturbation energies, E(2), also shows an increase in the E(2) values with the dielectric constant of the solvent.