Improved Performance of Protected Catecholic Polysiloxanes for Bioinspired Wet Adhesion to Surface Oxides

A facile synthetic strategy for introducing catecholic moieties into polymeric materials based on a readily available precursor (eugenol) and efficient chemistries [tris-(pentafluorophenyl)borane-catalyzed silation and thiol-ene coupling] is reported. Silyl protection is shown to be critical for the oxidative stability of catecholic moieties during synthesis and processing, which allows functionalized polysiloxane derivatives to be fabricated into 3D microstructures as well as 2D patterned surfaces. Deprotection gives stable catechol surfaces whose adhesion to a variety of oxide surfaces can be precisely tuned by the level of catechol incorporation. The advantage of silyl protection for catechol-functionalized polysiloxanes is demonstrated and represents a promising and versatile new platform for underwater surface treatments.