Functionalization of Reactive Polymeric Coatings via Diels–Alder Reaction Using Microcontact Printing

The fabrication of polymeric thin films amenable to facile functionalization by reactive μCP via a Diels–Alder reaction is described. Precursor copolymers containing FuMA, PEGMA, and TMSMA are prepared using ATRP. Surface‐tethered thin films of these polymers are obtained on oxidized silicon and glass substrates and patterned with maleimide‐appended dye molecules by simple μCP to demonstrate efficient functionalization via Diels–Alder reaction. Printing of biotin‐based ligands is carried out to demonstrate directed immobilization of the enzyme streptavidin. Due to the thermoreversible nature of the Diels–Alder reaction, these surfaces can be used as rewritable platforms. This is demonstrated by sequential write–erase–rewrite protocols via μCP of a maleimide‐containing fluorescent dye.