Sweet and bitter tastes are known to be mediated by G-protein-coupled receptors. The relationship between the chemical structure of gustable molecules and their molecular organization in saliva (aqueous solution) near the surface of the tongue provides a useful tool for elucidating the mechanism of chemoreception. The interactions between stimulus and membrane receptors occur in an anisotropic system. They might be influenced by the molecular packing of gustable molecules within an aqueous solvent (saliva) close to the receptor protein. To investigate the molecular organization of a sweet molecule (sucrose), a bitter molecule (caffeine), and their mixture in an aqueous phase near a "wall," a hydrophobic phase, we modeled this using an air/liquid interface as an anisotropic system. The experimental (tensiometry and ellipsometry) data unambiguously show that caffeine molecules form an adsorption layer, whereas sucrose induces a desorption layer at the air/water interface. The adsorption of caffeine molecules at the air/water interface gradually increases with the volume concentration and is delayed when sucrose is added to the solution. Spectroscopic ellipsometry data show that caffeine in the adsorption layer has optical properties practically identical to those of the molecule in solution. The results are interpreted in terms of molecular association of caffeine with itself at the interface with and without sucrose in the subphase, using the theory of ideal gases. (C) 2004 Elsevier Inc. All rights reserved.