Abstract
Environmental conditions can alter olfactory scent and chemical communication among biological species. In particular, odorant molecules interact with aerosols. Thermodynamics variables governing the adsorption from air to water surface of bombykol, the most studied pheromone, and of three derivative molecules, bombykal, bombykoic acid, and bombykyle acetate, are computed by steered and un-biased molecular dynamics in order to compare the role of their polar head group on adsorption on aqueous aerosols. When adsorbed, the molecule center of mass stands at about 1.2 Å from the interface and oscillates on the same length scale, trapped in an energy well. Gibbs energy of adsorption and desorption time of bombykol are found to be 9.2 kBT and 59 µs, respectively. The following ordering between the molecules is observed, reading from the more to the least adsorbed: bombykoic acid [Formula: see text] bombykol [Formula: see text] bombykoic acetate [Formula: see text] bombykal. It originates from a complex interplay of entropy and enthalpy. The entropy and enthalpy of adsorption are discussed in the light of structural arrangement, H-bonding, and hydrophilic tail positioning of the molecules at the interface. Our results show that, when dispersed in the air, pheromones adsorb on aqueous aerosols. However, the individual residence time is quite short on pure water surfaces. Aerosols can, therefore, only have a decisive influence on chemical communication through collective effects or through their chemical composition that is generally more complex than that of a pure water surface.