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Naji, M. |
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Motta, Antonella |
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Aletan, Dirar |
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Mohamed, Tarek |
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Ertürk, Emre |
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Taccardi, Nicola |
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Kononenko, Denys |
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Petrov, R. H. | Madrid |
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Alshaaer, Mazen | Brussels |
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Bih, L. |
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Casati, R. |
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Muller, Hermance |
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Kočí, Jan | Prague |
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Šuljagić, Marija |
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Kalteremidou, Kalliopi-Artemi | Brussels |
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Azam, Siraj |
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Ospanova, Alyiya |
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Blanpain, Bart |
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Ali, M. A. |
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Popa, V. |
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Rančić, M. |
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Ollier, Nadège |
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Azevedo, Nuno Monteiro |
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Landes, Michael |
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Rignanese, Gian-Marco |
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Woehlk, Hendrik
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article
Engineering nitroxide functional surfaces using bioinspired adhesion
Abstract
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<sup>–1</sup>) 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.