Development of novel supramolecular alignment media based on 1,3,5-benzenetricarboxamides (BTAs)

基于1,3,5-苯三甲酰胺（BTA）的新型超分子排列介质的开发

• 批准号: 402363279
• 负责人: Professorin Dr. Christina Marie Thiele
• 金额: --
• 依托单位: Arbeitskreis Thiele
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2018
• 资助国家: 德国
• 起止时间: 2017-12-31 至 2022-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/402363279?language=en
• 关键词: Development; novel; supramolecular; alignment; media

In recent years residual dipolar couplings became more and more important in protein as well as organic structure elucidation. Alignment media play a key role in this respect: Dipolar couplings are anisotropic NMR interactions, which are not observable under isotropic conditions. Thus, NMR experiments for the observation of anisotropic NMR interactions are usually conducted either in liquid crystals or in anisotropically swollen gels. Most systems used so far have in common, that they are based on classic polymeric materials. This leads to significant challenges as far as a complicated and/or time consuming preparation and purification is concerned. To provide a solution for this problem we have developed the first lyotropic liquid crystals based on supramolecular polymers in organic solvents, which can be used as alignment media. The 1,3,5-benzene tricarboxamides (BTAS) used for this purpose are monomeric compounds of low molecular weight, which self-assemble in solution to large stacks (due to hydrogen bonding and pi-pi-stacking). These stacks behave – in the broader sense – analogously to classic polymeric chains, including their form anisotropy which is necessary for the establishment of a liquid crystalline behavior.A formidable challenge in the application of supramolecular polymers as alignment media is the dynamic nature of the underlying self-association process: disturbing effects of the solvent, the analyte or of impurities can have a negative impact on the self-association process and thus on the alignment medium obtained. This can even lead to the break-down of anisotropic properties. One starting point to alleviate these difficulties is the structure of the BTA used. It contains a core, which is mainly responsible for the self-assembly and a substituent, which can – in principle - be chosen freely. Starting points for a clever choice of substituents are provided by the literature. The aim of this research project is thus the preparation and testing of known, as well as the development of novel substituted BTAs for the use as alignment media in organic solvents to establish a versatile alternative to the known polymer-based systems.

近年来，残留的偶极耦合在蛋白质以及有机结构阐明中变得越来越重要。对齐介质在这方面起着关键作用：偶极耦合是各向异性NMR相互作用，在各向同性条件下无法观察到。这是针对观察各向异性NMR相互作用的NMR实验通常在液晶或各向异性肿胀凝胶中进行。到目前为止，大多数使用的系统具有共同的共同点，它们基于经典的聚合物材料。就复杂和/或耗时的准备和净化而言，这导致了重大挑战。为了解决此问题的解决方案，我们开发了基于有机溶液中超分子聚合物的第一个溶作液晶体，可以用作对齐培养基。为此目的，用于此目的的1,3,5-苯苯三羧化酰胺（BTA）是低分子量的单体化合物，它们可以在溶液中自组装（由于氢键键合和PI-PI堆积）。这些堆栈在更广泛的含义上与经典聚合物链相似，包括它们的各向异性，这对于建立液晶晶体行为是必不可少的。在应用超分子聚合物时，可实现的巨大挑战是对准介质，因为对齐媒体是对基础的动态性质的动态性质，因此是底层自我效应的动态性质：扰乱溶液的效果，对分析的效果，分析或分析的效果，分析效果，分析效果或构成分析的效果。获得的比对介质。这甚至可以导致各向异性特性的分解。减轻这些困难的一个起点是使用的BTA的结构。它包含一个核心，主要负责自组装和取代基，从原则上讲可以自由选择。文献提供了巧妙选择取代基的起点。因此，该研究项目的目的是对已知的替代BTA进行制备和测试，并开发了在有机溶液中用作对齐介质的使用，以建立基于已知聚合物的系统的多功能替代品。