Zirconium(IV) coordination-mediated rapid and versatile post-modification of polydopamine coating as stationary phase for open-tubular capillary electrochromatography

In recent years, mussel-inspired polydopamine (PDA)-based materials have attracted significant attention in the field of open-tubular capillary electrochromatography (OT-CEC) owing to their diverse and appealing properties. However, previously established functionalized PDA coating-based CEC stationary phases predominantly relied on the latent reactivity of PDA with amine/thiol-containing molecules, limiting the types of applicable modifiers and requiring time-consuming reaction processes. Herein, we presented a versatile and efficient method for the facile and rapid fabrication of diverse functionalized PDA coatings as OT-CEC stationary phases through a Zr(IV) coordination-mediated post-modification strategy. Different kinds of modifiers, including octadecylamine (ODA), lauric acid (LA), and perfluorooctanoic acid (PFOA), were rapidly and robustly grafted onto the PDA coating, verified through multiple characterization techniques. The influences of preparation parameters on the grafting efficiency of the functionalized PDA coating were systematically investigated. Utilizing the Zr(IV)-mediated ODA-, LA- and PFOA-functionalized PDA-based OT-CEC columns, we achieved high-efficiency baseline separation of a series of neutral analytes with excellent repeatability, good stability, and long lifetime. Given the strong universality of the Zr(IV) coordination-mediated post-modification approach, our study provides an effective pathway for advancing the development of a wider range of functional PDA-based chromatographic stationary phases.