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

使用新型全氟烷基官能化树枝状两亲物和染料间隔基作为光学探针进行超分子结构的高分辨率结构表征和稳定

• 批准号: 317551446
• 负责人: Privatdozent Dr. Christoph Böttcher
• 金额: --
• 依托单位: Abteilung Organische Chemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2016
• 资助国家: 德国
• 起止时间: 2015-12-31 至 2019-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/317551446?language=en
• 关键词: resolution; structure; characterisation; stabilisation; supramolecular

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.

超分子组装体可以使用低温透射电子显微镜（cryo-TEM）在纳米尺度上表征其准天然状态，但只有在极少数情况下才能精确测定分子组织。然而，如果利用特定的花青染料作为两亲性自组装系统的集成组件，它们的光学特性在聚集时以特定方式改变（例如通过形成H-和J-聚集体），可以用于补充确定纳米级框架内的分子排列。因此，在分子水平上了解自组织过程的关键参数是可用的。根据这些发现，我们提出了一种新型两亲性分子，以便（a）表征其自组装结构，（b）产生光稳定的超分子聚集体，以及（c）建立能够自我发出有效负载释放信号的诊断转运蛋白。我们的方法结合了不同代（G1-G3）的树枝状聚甘油头基的特殊性质和花青染料探针的光学性质。此外，还将引入烷基链和氟化烷基链，并通过光谱学和直接成像技术，特别是冷冻-TEM或冷冻电子断层扫描来表征它们的结构形成特性。疏水效应、树枝状头基的方向性、染料体系的聚集趋势以及氟化链的区室化效应（微相分离）的综合功效旨在创建特别稳定且结构明确的超微结构，由于其增强的光稳定性和光学特性，这些超微结构可用作专门的转运蛋白。

项目成果

Stereochemistry‐Controlled Supramolecular Architectures of New Tetrahydroxy‐Functionalised Amphiphilic Carbocyanine Dyes

• DOI: 10.1002/chem.201905745
• 发表时间: 2020-02
• 期刊: Chemistry (Weinheim an Der Bergstrasse, Germany)
• 作者: B. Schade;A. Singh;Virginia Wycisk;J. L. Cuéllar-Camacho;H. Berlepsch;R. Haag;C. Böttcher