We report on the role of the chemical structure of polyphenol pendant groups in linear antioxidant polymers in their assembly and chain intermixing within layer-by-layer (LbL) films, as well as in the antioxidant performance of interfacial assemblies. When assembled with poly(ethylene oxide) (PEO) within hydrogen-bonded films, the antioxidant polymers—poly(3,4-dihydroxybenzyl methacrylamide) (P2HMA) and poly(3,4,5-trihydroxybenzyl methacrylamide) (P3HMA)—which contain catechol- and gallol-like moieties, respectively, generated films with drastically different structure and functionality. Specifically, while catechol-based P2HMA deposited within LbL films linearly with a low increment of mass increase per step, the growth of P3HMA/PEO films was strongly exponential. Dramatic differences in chain intermixing and layering in these films are revealed by the application of neutron reflectometry using deuterated PEO, dPEO, to create marker layers. Differences in film structure strongly affected film antioxidant performance, as demonstrated by the radical scavenging assay. While assembled P3HMA was fully available for scavenging 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS^•+) radical cations, in assembled P2HMA, radical scavenging was restricted to the top ∼35 nm of the LbL film, highlighting the effect of LbL film structure on antioxidant performance.

中文翻译：

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线性合成多酚的层状氢键合抗氧化膜

我们报告了线性抗氧化剂聚合物中的多酚侧基在组装和层间（LbL）膜内的链混合以及界面组装的抗氧化性能方面的作用。当在氢键薄膜中与聚环氧乙烷（PEO）组装时，抗氧化剂聚合物-聚（3,4-二羟基苄基甲基丙烯酰胺）（P2HMA）和聚（3,4,5-三羟基苄基甲基丙烯酰胺）（P3HMA）分别包含邻苯二酚和类似没食子醇的部分，生成的膜的结构和功能截然不同。具体而言，虽然基于邻苯二酚的P2HMA线性沉积在LbL膜中，且每步质量增加的增量很小，但P3HMA / PEO膜的生长却呈强指数增长。通过使用氘化PEO，dPEO形成标记层的中子反射仪的应用，揭示了这些膜中链的混合和分层的显着差异。自由基清除试验证明，薄膜结构的差异会严重影响薄膜的抗氧化性能。组装后，P3HMA完全可用于清除2,2'-叠氮基双（3-乙基苯并噻唑啉-6-磺酸）（ABTS）^•+）自由基阳离子，在组装的P2HMA中，自由基清除仅限于LbL膜的顶部〜35 nm，突出了LbL膜结构对抗氧化性能的影响。