Modelling cetrimonium micelles as 4-OH cinnamate carriers targeting a hydrated iron oxide surface

Molecular interactions between 4-OH-cinnamate and cetrimonium in solution result in improved adsorption of the cinnamate on mild steel, developing a protective mechanism against the diffusion of corrosive chloride to the oxide surface. Fundamental understanding of this mechanism should allow new design routes for the development of eco-friendly corrosion inhibitors.

Via classic molecular dynamics, simulations were carried out for cetrimonium and 4-OH-cinnamate in aqueous solutions at different ionic strengths and the results were validated with experimental SAXS data. Self-aggregation of cetrimonium 4-OH-cinnamate on a hydrated hematite surface was then simulated and results were compared with cryo-TEM imaging for the same compound. Finally, the effect of the adsorbed aggregates on chloride diffusion to the oxide surface was modelled.

Simulations showed the encapsulation of 4-OH-cinnamate into cetrimonium micelles, consistent with experiments. The newly formed micelles adsorb onto a hydrated iron oxide surface by forming hydrogen bonds between their carboxylate outer-shell groups and the surface hydroxyls. As the adsorbate concentrations increase, there is a morphological transition from spherical to wormlike adsorbed aggregates. The wormlike structure can block chloride ions, demonstrating a synergistic inhibitory mechanism between both cetrimonium and 4-OH-cinnamate. Encapsulation and delivery of active compounds to certain targets, such as carcinogenic tumors, have been well studied in biochemistry research, we demonstrate that the same mechanism can be applied to the design of efficient corrosion inhibitors, optimizing their delivery to the metal surface.