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Thiolactone chemistry has garnered significant attention as a powerful post-polymerization modification (PPM) route to mutlifunctional polymeric materials. Here, we apply this versatile chemistry to the fabrication of ultrathin, multifunctional polymer surfaces via aminolysis and thiol-mediated double modifications of thiolactone-containing polymer brushes. Polymer brush surfaces were synthesized via microwave-assisted surface-initiated polymerization of dl -homocysteine thiolactone acrylamide. Aminolysis and thiol-Michael double modifications of the thiolactone-functional brush were explored using both sequential and one-pot reactions with bromobenzyl amine and 1 H ,1 H -perfluoro- N -decyl acrylate. X-ray photoelectron spectroscopy and argon gas cluster ion sputter depth profiling enabled quantitative comparison of the sequential and one-pot PPM routes with regard to conversion and spatial distribution of functional groups immobilized throughout thickness of the brush. While one-pot conditions proved to be more effective in immobilizing the amine and acrylate within the brush, the sequential reaction enabled the fabrication of multifunctional, micropatterned brush surfaces using reactive microcontact printing. 

Post-polymerization modification (PPM) has been broadly employed to achieve functional polymer brush surfaces via immobilization of functional moieties on the brush using efficient organic tranformations. Here, we demonstrate the amine-anhydride reaction as a modular PPM route to functional brush surfaces using poly(styrene–maleic anhydride) (pSMA) copolymer brushes as a platform. The amine-anhydride reaction on pSMA surfaces proceeds to high conversions, with rapid kinetics, under ambient reaction conditions, and exploits a readily available library of functional amines. Using cystamine as a modifier, a convenient route to thiol-functionalized brushes was developed that enables sequential PPM modifications with a large library of alkenes using both base-catalyzed thiol-Michael and radical-mediated thiol–ene reactions. The high fidelity PPM reactions were demonstrated via the development of multifunctional, micropatterned brush surfaces.