Laboratory of Chemical Biology, Department of Biomedical Engineering and Institute for Complex Molecular Systems, Eindhoven University of, Technology, P.O. Box 513, 5600MB, Eindhoven, The Netherlands.
SyMO-Chem B.V., Den Dolech 2, 5612AZ, Eindhoven, The Netherlands.
Chemistry. 2018 May 28;24(30):7734-7741. doi: 10.1002/chem.201801022. Epub 2018 May 3.
Interest in bay-substituted perylene-3,4:9,10-tetracarboxylic diimides (PDIs) for solution-based applications is growing due to their improved solubility and altered optical and electronic properties compared to unsubstituted PDIs. Synthetic routes to 1,12-bay-substituted PDIs have been very demanding due to issues with steric hindrance and poor regioselectivity. Here we report a simple one-step regioselective and high yielding synthesis of a 1,12-dihydroxylated PDI derivative that can subsequently be alkylated in a straightforward fashion to produce nonplanar 1,12-dialkoxy PDIs. These PDIs show a large Stokes shift, which is specifically useful for bioimaging applications. A particular cationic PDI gemini-type surfactant has been developed that forms nonfluorescent self-assembled particles in water ("off state"), which exerts a high fluorescence upon incorporation into lipophilic bilayers ("on state"). Therefore, this probe is appealing as a highly sensitive fluorescent labelling marker with a low background signal for imaging artificial and cellular membranes.
由于取代的苯并[1,2-b:4,5-b']二噻吩-4,8-二酮（BSBDT）具有比未取代的 PDIs 更高的溶解度和不同的光学和电子性质，因此人们对其在基于溶液的应用中的兴趣日益增加。由于空间位阻和区域选择性差等问题，1,12-取代的 PDIs 的合成路线非常苛刻。在这里，我们报告了一种简单的一步区域选择性和高产率合成 1,12-二羟基 PDIs 衍生物的方法，该衍生物随后可以以直接的方式进行烷基化，以生成非平面的 1,12-二烷氧基 PDIs。这些 PDIs 显示出较大的斯托克斯位移，这对于生物成像应用特别有用。已经开发出一种特殊的阳离子 PDIs 双子型表面活性剂，它在水中形成非荧光自组装颗粒（“关闭状态”），而在掺入亲脂性双层时会发出强荧光（“打开状态”）。因此，该探针作为一种具有低背景信号的高灵敏度荧光标记物，非常适合用于人工和细胞膜成像。
