Supramolecular self-assembly is of paramount importance for the development of novel functional materials with molecular-level feature control. In particular, the interest in creating well-defined stratified multilayers through simple methods using readily available building blocks is motivated by a multitude of research activities in the field of “nanoarchitectonics” as well as evolving technological applications. Herein, we report on the facile preparation and application of highly organized stacked multilayers via layer-by-layer assembly of lipid-like surfactants and polyelectrolytes. Polyelectrolyte multilayers with high degree of stratification of the internal structure were constructed through consecutive assembly of polyallylamine and dodecyl phosphate, a lipid-like surfactant that act as a structure-directing agent. We show that multilayers form well-defined lamellar hydrophilic/hydrophobic domains oriented parallel to the substrate. More important, X-ray reflectivity characterization conclusively revealed the presence of Bragg peaks up to fourth order, evidencing the highly stratified structure of the multilayer. Additionally, hydrophobic lamellar domains were used as hosts for ferrocene in order to create an electrochemically active film displaying spatially-addressed redox units. Stacked multilayers were then assembled integrating redox-tagged polyallylamine and glucose oxidase into the stratified hydrophilic domains. Bioelectrocatalysis and “redox wiring” in the presence of glucose was demonstrated to occur inside the stratified multilayer.

中文翻译：

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高度组织层叠多层经由层-层脂质如表面活性剂和聚电解质的组装。（生物）电化学纳米建筑的分层超分子结构†

超分子自组装对于开发具有分子水平特征控制的新型功能材料至关重要。尤其是，人们对利用“纳米建筑学”领域中的众多研究活动以及不断发展的技术应用，通过使用容易获得的构件通过简单的方法来创建清晰分层的多层结构感兴趣。在此，我们对浅显的编制报告和高度组织化的堆叠多层的应用通过类脂质表面活性剂和聚电解质的逐层组装。通过连续组装聚烯丙胺和十二烷基磷酸酯（一种充当结构导向剂的类脂质表面活性剂），可以构建内部结构高度分层的聚电解质多层膜。我们显示多层形成平行于底物定向的明确定义的层状亲水/疏水域。更重要的是，X射线反射率表征最终表明存在布拉格峰直至四阶，这证明了多层的高度分层结构。另外，疏水性层状结构域被用作二茂铁的主体，以产生显示空间寻址的氧化还原单元的电化学活性膜。然后组装堆叠的多层，将氧化还原标记的聚烯丙胺和葡萄糖氧化酶整合到分层的亲水域中。葡萄糖存在下，生物电催化和“氧化还原布线”被证明发生在分层的多层结构内部。