Succinimidyl Carbonate-Based Amine-Reactive Polymer Brushes: Facile Fabrication of Functional Interfaces

• Published in: ACS applied polymer materials Vol. 3; no. 5; pp. 2507 - 2517
• Main Authors: Gevrek, Tugce Nihal, Degirmenci, Aysun, Sanyal, Rana, Klok, Harm-Anton, Sanyal, Amitav
• Format: Journal Article
• Language: English
• Published: American Chemical Society 14.05.2021
• Subjects: polymeric coatings; biofunctionalization; succinimidyl carbonate; carbamate formation; polymer brushes; amine conjugation
• ISSN: 2637-6105; 2637-6105
• DOI: 10.1021/acsapm.1c00107

Polymeric coatings that can undergo effective functionalization with ligands and (bio)­molecules necessary for intended applications are widely employed to engineer functional interfaces. Herein, amine-reactive polymer brushes are fabricated using a succinimidyl group-activated carbonate monomer, and their facile post-polymerization functionalization is demonstrated through ligand-mediated protein immobilization and detection. Copolymer brushes containing varying amounts of the reactive monomer and an ethylene glycol-based methacrylate comonomer were obtained using surface-mediated reversible addition fragmentation chain transfer polymerization. Post-polymerization functionalization of the thus-obtained copolymer brushes with a fluorine-containing amine, namely, 4-(trifluoromethyl)­benzylamine, demonstrated highly efficient functionalization at ambient temperature. To demonstrate possible applications, polymer brushes functionalized with a bioactive ligand, namely, biotin, were used to detect the target protein, streptavidin. The biotin–streptavidin interaction on brushes could also be employed to conjugate protein-coated quantum dots. Importantly, comparison of the attachment of 4-(trifluoromethyl)­benzylamine on activated carbonate group-containing brushes with reaction of the same molecule on traditional active ester-based brushes demonstrated higher extent of conjugation to carbonate brushes. Finally, orthogonal functionalization of the copolymer brushes with an amino-functionalized molecule and a maleimide-containing fluorescent dye in spatial control using microcontact printing was demonstrated. One can envision that the facile fabrication and efficient functionalization of succinimidyl carbonate-based amine-reactive brushes afford an attractive platform for applications using functional interfaces for diagnostic purposes.