High resolution structure characterisation and stabilisation of supramolecular architectures using novel perfluoralkyl functionalised dendron-amphiphiles with dye spacers as optical probes

使用低温透射电子显微镜（cryo-TEM）可以在纳米尺度上表征其准天然状态的超分子组装，但只有在极少数情况下才能精确确定分子组织。如果利用特定的菁染料作为两亲性自组装系统的组成部分，它们的光学性质，在聚集时以特定的方式改变（例如，通过形成H-和j -聚集体），可以用于纳米级框架内分子排列的互补测定。因此，在分子水平上理解自组织过程的关键参数是可用的。在这些发现的基础上，我们提出了一种新型的两亲性分子，以便(a)表征它们的自组装结构，(b)产生光稳定的超分子聚集体，以及(c)建立能够自我发送有效载荷释放信号的诊断转运体。我们的方法结合了不同世代（G1-G3）树突状聚甘油头群的特殊性质和花菁染料探针的光学性质。此外，烷基链以及氟化烷基链将被介绍，它们的结构形成特性将通过光谱和直接成像技术，特别是低温透射电镜或低温电子断层扫描进行表征。疏水效应、树突头基团的定向特性、染料系统的聚集倾向以及氟化链的区隔化效应（微相分离）的综合功效旨在创造特别稳定和结构明确的超微结构，由于其增强的光稳定性和光学特性，这些超微结构适用于专门的转运体。

Supramolecular assemblies can be characterised in their quasi native state on the nano scale using cryogenic transmission electron microscopy (cryo-TEM), but an exact determination of the molecular organisation is achieved in only rare cases. If utilising particular cyanine dyes as an integrated component of an amphiphilic self-assembling systems, their optical properties, which alter in a specific way upon aggregation (e.g. by the formation of H- and J-aggregates), can, however, be used for a complementary determination of the molecular arrangement within the nanoscopic framework. Consequently, crucial parameters for an understanding of the self-organisation process on the molecular level are available.On the basis of these findings, we propose a new type of amphiphilic molecules in order to (a) characterise their self-assembled architectures, (b) produce photostable supramolecular aggregates, and (c) establish diagnostic transporters which are capable of self-signalling the release of their payloads. Our approach combines the particular properties of dendritic polyglycerol head groups of differing generations (G1-G3) and the optical properties of cyanine dye probes. In addition, alkyl chains as well as fluorinated alkyl chains will be introduced and their structure forming properties be characterised by spectroscopy and direct imaging techniques, in particular Cryo-TEM or Cryo-Electron Tomography. The combined efficacy of the hydrophobic effect, directional properties of dendritic head groups, the aggregation tendency of dye systems, as well as compartimentalisation effect (microphase separation) of fluorinated chains aims at the creation of particularly stable and structurally defined ultrastructures, which are applicable as specialised transporters due to their enhanced photostability and optical properties.