V-Shaped Molecular Configuration of Wax Esters of Jojoba Oil in a Langmuir Film Model

The aim of the present work was to understand the interfacial properties of a complex mixture of wax esters (WEs) obtained from Jojoba oil (JO). Previously, on the basis of molecular area measurements, a hairpin structure was proposed as the hypothetical configuration of WEs, allowing their organization as compressible monolayers at the air–water interface. In the present work, we contributed with further experimental evidence by combining surface pressure (π), surface potential (ΔV), and PM-IRRAS measurements of JO monolayers and molecular dynamic simulations (MD) on a modified JO model. WEs were self-assembled in Langmuir films. Compression isotherms exhibited πlift-offat 100 Å2/molecule mean molecular area (Alift-off) and a collapse point at πc≈ 2.2 mN/m and Ac≈ 77 Å2/molecule. The ΔVprofile reflected two dipolar reorganizations, with one of them at A> Alift-offdue to the release of loosely bound water molecules and another one at Ac< A< Alift-offpossibly due to reorientations of a more tightly bound water population. This was consistent with the maximal SP value that was calculated according to a model that considered two populations of oriented water and was very close to the experimental value. The orientation of the ester group that was assumed in that calculation was coherent with the PM-IRRAS behavior of the carbonyl group with the C═O oriented toward the water and the C–O oriented parallel to the surface and was in accordance with their orientational angles (∼45 and ∼90°, respectively) determined by MD simulations. Taken together, the present results confirm a V shape rather than a hairpin configuration of WEs at the air–water interface.