Dynamic Nitroxide Functional Materials.

A substrate-independent and versatile coating platform for (spatially resolved) surface functionalization, based on nitroxide radical coupling (NRC) reactions and the formation of thermo-labile alkoxyamine functional groups, was introduced. Nitroxide-decorated poly(glycidyl methacrylate) (PGMA) microspheres, obtained through bioinspired copolymer surface deposition using dopamine and a nitroxide functional dopamine derivative as monomers, were conjugated with small functional groups in a rewritable process. Reversible coding of the nitroxide functional microspheres by NRC and decoding through thermal alkoxyamine fission were monitored and characterized by electron paramagnetic resonance (EPR) spectroscopy and X-ray photoelectron spectroscopy (XPS). In addition, this nitroxide coating system was exploited in "grafting-to" polymer surface ligations of poly(methyl methacrylate) (PMMA) and poly(2,2,2-trifluoroethyl methacrylate) (PTFEMA) in spatially confined areas. Polymer strands terminated with an Irgacure 2959 (2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone) photoinitiator were obtained through chain-transfer polymerization, and subsequently coupled to nitroxide-immobilized poly(dopamine) (PDA)-coated silicon substrates by using rapid photoclick NRC reactions. Light-driven polymer surface coding was visualized by time-of-flight secondary ion mass spectrometry (ToF-SIMS) and XPS imaging.

Engineering Nitroxide Functional Surfaces Using Bioinspired Adhesion.

We pioneer a versatile surface modification strategy based on mussel-inspired oxidative catecholamine polymerization for the design of nitroxide-containing thin polymer films. A 3,4-dihydroxy-l-phenylalanine (l-DOPA) monomer equipped with a 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-derived oxidation-labile hydroxylamine functional group is employed as a universal coating agent to generate polymer scaffolds with persistent radical character. Various types of materials including silicon, titanium, ceramic alumina, and inert poly(tetrafluoroethylene) (PTFE) were successfully coated with poly(DOPA-TEMPO) thin films in a one-step dip-coating procedure under aerobic, slightly alkaline (pH 8.5) conditions. Steadily growing polymer films (∼1.1 nm h-1) were monitored by ellipsometry, and their thicknesses were critically compared with those obtained from atomic force microscopic cross-sectional profiles. The heterogeneous composition of surface-adherent nitroxide scaffolds examined by X-ray photoelectron spectroscopy was correlated to that examined by in-solution polymer analysis via high-resolution electrospray ionization mass spectrometry, revealing oligomeric structures with up to six repeating units, mainly composed of covalently linked dihydroxyindole along the polymer backbone. Critically, the reversible redox-active character of the nitroxide-containing polymer scaffolds was investigated by cyclic voltammetric measurements, revealing a convenient and facile access route to electrochemically active nitroxide polymer coatings with potential application in electronic devices such as organic radical batteries.