Bioinspired catechol-terminated self-assembled monolayers with enhanced adhesion properties

The role of the catechol moiety in the adhesive properties of mussel proteins and related synthetic materials has been extensively studied in the last years but still remains elusive. Here, a simplified model approach is presented based on a self-assembled monolayer (SAM) of upward-facing catechols thiol-bound to epitaxial gold substrates. The orientation of the catechol moieties is confirmed by spectroscopy, which also showed lack of significant amounts of interfering o-quinones. Local force-distance curves on the SAM measured by atomic force microscopy (AFM) shows an average adhesion force of 45 nN, stronger than that of a reference polydopamine coating, along with higher reproducibility and less statistical dispersion. This is attributed to the superior chemical and topographical homogeneity of the SAM coating. Catechol-terminated SAMs are also obtained on high-roughness gold substrates that show the ability to assemble magnetic nanoparticles, despite their lack of enhanced adhesion at the molecular level. Finally, the influence of the catechol group on the formation and quality of the SAM is explored both theoretically (molecular dynamics simulations) and experimentally using direct-write AFM lithography. Highly packed catechol monolayers with a large density and smaller roughness are studied by AFM force-distance curves. These experiments afford adhesion force values higher and much more monodisperse than those reported for polydopamine-like polymeric materials. These results are unique giving valuable information on the effect of molecular organization on the adhesive properties of interphases. Such information is crucial for the development of improved materials and interphases engineered at the molecular level, by chemical design