Preparation of Functional Alternating Polymer Brushes and Their Orthogonal Surface Modification through Microcontact Printing

Chemistry. 2017 May 2;23(25):6042-6047. doi: 10.1002/chem.201603565. Epub 2016 Oct 31.

Abstract

This paper reports microcontact printing (μCP) to immobilize an alkoxyamine initiator (regulator) on glass and silicon substrates and subsequent surface-initiated alternating nitroxide-mediated copolymerization (siNMP) of hexafluoroisopropyl acrylate (HFIPA) and 7-octenylvinyl ether (OVE). The resulting patterned polymer brushes are analyzed by using atomic force microscopy (AFM). In addition, site-specific post-functionalization of the alternating polymer brushes by applying two orthogonal surface reactions is achieved with thiols and amines through μCP. The versatility of this post-polymerization modification approach is demonstrated by site-selective immobilization of small organic molecules, fluorophores, and ligands providing a binary bioactive surface. The successful side-by-side orthogonal immobilization is verified by using X-ray photoelectron spectroscopy (XPS) and fluorescence microscopy.

Keywords: alternating copolymers; microcontact printing; polymerization; polymers; surface functionalization.