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.

中文翻译：

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使用生物启发的黏合剂工程化一氧化二氮功能表面

我们开创了基于贻贝启发的氧化儿茶酚胺聚合的多功能表面改性策略，用于设计含氮氧化物的聚合物薄膜。配备有2,2,6,6-四甲基哌啶-1-氧基（TEMPO）衍生的对氧化不稳定的羟胺官能团的3,4-二羟基-1-苯丙氨酸（1- DOPA）单体用作通用涂层剂生成具有持久自由基特性的聚合物支架。在有氧，弱碱性（pH 8.5）下，通过一步浸涂法成功地将聚（DOPA-TEMPO）薄膜涂覆到包括硅，钛，陶瓷氧化铝和惰性聚四氟乙烯（PTFE）在内的各种类型的材料上） 条件。稳定生长的聚合物膜（〜1.1 nm h ^–1）通过椭圆偏振法进行监测，并将其厚度与从原子力显微镜横截面轮廓获得的厚度进行严格比较。通过X射线光电子能谱检查的表面粘附氮氧化物支架的异质组成与通过高分辨率电喷雾电离质谱通过溶液中聚合物分析的结果相关联，揭示了具有最多六个重复单元的寡聚结构，主要由共价键组成沿聚合物主链连接二羟基吲哚。至关重要的是，通过循环伏安法测量了含氮氧化物的聚合物支架的可逆氧化还原活性，