Building‐Block Diversity in Polydopamine Underpins a Multifunctional Eumelanin‐Type Platform Tunable Through a Quinone Control Point

Abstract Rational approaches to engineering polydopamine films with tailored properties for surface coating and functionalization are currently challenged by the lack of detailed information about the polymer structure and the mechanism of buildup. Using an integrated chemical and spectroscopic approach enables the demonstration of: a) a three‐component structure of polydopamine, comprising uncyclized (catecholamine) and cyclized (indole) units, as well as novel pyrrolecarboxylic acid moieties; b) remarkable variations in the relative proportions of the cyclized and uncyclized units with starting dopamine concentration; c) the occurrence of oligomer components up to the tetramer level; d) the covalent incorporation of Tris buffer; and e) the role of dopamine quinone as a crucial control point for directing the buildup pathways and tuning the properties. The importance of the uncyclized amine‐containing units in polydopamine adhesion is also highlighted. The proper selection of substrate concentration and buffer is thus proposed as a practical means of tailoring polydopamine functionality via control of competing pathways downstream of dopamine quinone.