Multistimuli Responsive Reversible Cross-Linking–Decross-Linking of Concentrated Polymer Brushes

Poly(furfuryl methacrylate) (PFMA) brushes were cross-linked using bismaleimide cross-linkers via the Diels-Alder (DA) reaction at 70 °C, generating cross-linked PFMA brushes (PFMA brush gels). The cross-linked PFMA brushes were decross-linked at 110 °C via the retro-Diels-Alder (rDA) reaction, offering the temperature-responsive reversible PFMA brush gels. The wettability of the brush was tunable by cross-linking and decross-linking. The use of a disulfide containing bismaleimide as a cross-linker gave the S-S bond at the cross-linking point. The S-S bond was cleaved upon thermal or photo stimulus and regenerated through oxidative stimulus, offering another reversible decross-linking/cross-linking pathway of the PFMA brush gel. The use of photo stimulus together with photomasks further offered patterned brushes with the cross-linked and decross-linked domains. The combination of the DA/rDA reactions and the reversible S-S bond cleavage provided multistimuli-responsive brush gels for switching the surface properties in unique manners. The reversible cross-linking, multiresponsiveness, access to patterned structures, and metal-free synthetic procedure are attractive features in the present approach for creating smart functional surfaces.