Effect of Substituents in Mussel-inspired Surface Primers on their Oxidation and Priming Efficiency

Marine mussels contain an abundant catechol moiety, 3,4-dihydroxyphenylalanine (DOPA), in their interfacial foot proteins. DOPA contributes to both surface adhesion and bridging between the surface and overhead proteins (surface priming) by taking advantage of the unique redox properties of catechol. Inspired by the mussel surface priming mechanism, herein we synthesized a series of DOPA-mimetic analogs – a bifunctional group molecule, consisting of a catechol group and an acrylic group at the opposite ends. The surface primers with differently substituted (−COOH, −CH₃) alkyl chains in the middle spacer were synthesized. Time-dependent oxidation and redox potentials of the surface primers were studied in an oxidizing environment to gain a better understanding of the mussel‘s redox chemistry. The thickness and degree of priming of the surface primers on silicon-based substrates were analyzed by ellipsometry and UV/Vis absorption spectroscopy. The post-reactivity of the acrylic groups of the primed layer was first visualized through a reaction with an acrylic group-reactive dye.