IMMM, Institut des Molécules et Matériaux du Mans UMR CNRS 6283, Université du Mans - UFR Sciences et Techniques, Avenue Olivier Messiaen, 72085 Le Mans, France.
IMMM, Institut des Molécules et Matériaux du Mans UMR CNRS 6283, Université du Mans - UFR Sciences et Techniques, Avenue Olivier Messiaen, 72085 Le Mans, France; A. Chełkowski Institute of Physics, University of Silesia in Katowice, 75 Pułku Piechoty 1A, Chorzów, Poland.
Colloids Surf B Biointerfaces. 2021 Jan;197:111427. doi: 10.1016/j.colsurfb.2020.111427. Epub 2020 Oct 20.
We describe a bottom-up surface functionalization to design hybrid molecular coatings that tether biomembranes using wet chemistry. First, a monolayer was formed by immersion in a NH-Ar-SOH solution, allowing aryldiazonium salt radicals to spontaneously bind to it via strong C bonding. After formation of the air-stable and dense molecular monolayer (-Ar-SOH), a subsequent activation was used to form highly reactive -Ar-SOCl groups nearly perpendicular to the monolayer. These can bind commercial surfactants, PEGylated oligomers and other inexpensive molecules via their -OH, -COOH, or -NH chain end-moieties, to build hybrid coatings. Metal and oxidized chromium, semi-conductor n-doped silicon (111), are the substrates tested for this protocol and the aromatic organic monolayers formed at their surface are characterized by X-ray photoelectron spectroscopy (XPS). XPS reveals unambiguously the presence of C-Cr and C-Si bonds, ensuring robustness of the coatings. Functional sulfur groups (-SOH) cover up to 6.5×10 mol cm of the silicon interface and 4.7×10 mol cm of the oxidized chromium interface. These surface concentrations are comparable to the classic values obtained when the prefunctionalisation is driven by electrochemistry on conductors. Tethered lipid membranes formed on these coatings were analyzed by neutron reflectivity at the interface of functionalized n-doped silicon substrates after immersion in a solution of lipid vesicles and subsequent fusion. Results indicate a rather compact hybrid coating of Brij anchor-harpoon molecules that maintain a single lipid bilayer above the substrate, on top of a hydrated PEO cushion.
我们描述了一种自下而上的表面功能化方法，通过湿化学将生物膜固定在混合分子涂层上。首先，通过浸入 NH-Ar-SOH 溶液中形成单层，允许芳基重氮盐自由基通过强 C 键自发结合到它上面。在形成稳定的空气致密分子单层（-Ar-SOH）之后，随后的激活用于形成几乎垂直于单层的高反应性 -Ar-SOCl 基团。这些基团可以通过其 -OH、-COOH 或 -NH 链末端部分与商业表面活性剂、PEG 化低聚物和其他廉价分子结合，构建混合涂层。金属和氧化铬、半导体 n 掺杂硅（111）是该方案测试的基底，在其表面形成的芳基有机单层通过 X 射线光电子能谱（XPS）进行表征。XPS 明确揭示了 C-Cr 和 C-Si 键的存在，确保了涂层的坚固性。功能硫基团（-SOH）覆盖了高达 6.5×10 mol cm 的硅界面和 4.7×10 mol cm 的氧化铬界面。这些表面浓度与经典值相当，当预功能化由导体上的电化学驱动时，可获得该经典值。将脂质囊泡溶液浸入功能化 n 掺杂硅基底的界面后，通过中子反射法分析了这些涂层上形成的脂质膜。结果表明，Brij 锚钩分子的混合涂层相当紧凑，它在水合 PEO 缓冲层之上保持了单层脂质双层，位于基底上方。
