Functionalisation of Natural Deep Eutectic Solvents (NADES) by Means of Self-Assembly

天然深层次有机溶剂（NADES），由于其通常的生物友好特性，是一类有趣的溶剂，可以通过选择其组分在很大程度上调节其溶剂性质。它们可以通过在其中形成自组装聚集体而进行官能化，从而对于许多潜在应用更具吸引力。通过这样做，可以控制诸如增溶或流变性质的性质。然而，到目前为止，NADES通常在物理化学方面的特征很差，其中许多具有高粘度。因此，本提案的第一个目标是通过对各种NADES的相行为进行彻底和系统的研究来改变这一点，重点是开发低粘度系统，因为高粘度通常会阻碍其实际应用。 对于最有趣的NADES，我们将研究一系列（生物）表面活性剂，具有不同的头基胶束结构（主要通过光，X射线和中子散射）和胶束形成的热力学（ITC，CMC），目的是识别和量化表面活性剂分子基序的亲溶剂性和疏溶剂性。对于这些表面活性剂体系，我们还将确定典型油和活性剂的增溶特性，因为这通常是采用表面活性剂的关键方面。在下一步中，将研究由两亲性共聚物进行的自组装，这将导致更大规模的结构化。由于聚合物在NADES中的溶解度还鲜为人知，首先我们必须确定不同聚合物的溶解度，将其分为可溶性（A）和不溶性（B）均聚物。在此基础上，我们将合成AB型和BAB型两亲性嵌段共聚物，并研究它们在NADES中的自组装性质，特别关注所形成的结构。BAB型共聚物应充当NADES的流变改性剂，并允许通过自组装和网络形成来控制其粘度。 用于自组装研究的低粘度NADES也将在其纳米结构方面进行研究，特别是采用中子衍射实验（这与澳大利亚合作伙伴密切合作），因为根据其组成，它们可能在流体状态下具有或多或少明显的内部结构。该项目的一个关键目标是确定NADES流体纳米结构与其促进自组装的能力之间的关系，以及自组装聚集体的结构如何与NADES的纳米结构相关。 总之，该项目将提供在不同的低粘度NADES中自组装的基本原理，基于该原理，可以在NADES中针对低和高Mw两亲物进行定制的自组装，并且该原理适用于给定NADES的分子结构。

Natural Deep Eutectic Solvents (NADES), due to their generally biofriendly character, are an interesting class of solvents that can be tuned largely with respect to their solvent properties by choice of their components. They can be made even more attractive for many potential applications by functionalisation via formation of self-assembled aggregates in them. By doing so one can control properties like solubilisation or rheological properties. However, so far NADES are often poorly characterised in physico-chemical terms and many of them suffer from high viscosity. Therefore, the first objective of this proposal is to change this by a thorough and systematic investigation of the phase behaviour of a large variety of NADES with a focus on developing low-viscous systems, as high viscosity is often preventing their practical application. For the most interesting NADES we will study for a range of (bio)surfactants, with different head groups micelle structure (mainly by light, x-ray, and neutron scattering) and thermodynamics of micelle formation (ITC, cmc), with the aim of identifying and quantifying solvophilic and solvophobic properties of the molecular motifs of the surfactants. For these surfactant systems we will also determine the solubilisation properties for typical oils and active agents, as this is typically a key aspect to employing surfactants. In a next step, self-assembly by amphiphilic copolymers is to be studied that leads to larger scale structuring. As polymer solubility in NADES is little known yet, first we will have to determine the solubility of different polymers to group them into soluble (A) and insoluble (B) homopolymers. Based on that knowledge amphiphilic block copolymers of AB and BAB type will be synthesized and their self-assembly properties in NADES will be studied, with a particular focus on the structures formed. The BAB-type copolymers should function as rheological modifiers for NADES and allow controlling their viscosity by self-assembly and network formation. The low viscous NADES employed for the self-assembly studies, will also become studied with respect to their nanostructure, in particular employing neutron diffraction experiments (this in close cooperation with the Australian partners), as depending on their composition, they may possess a more or less pronounced internal structure in the fluid state. A key objective of the project then will be to determine relations between the NADES fluid nanostructure and their ability to promote self-assembly, and how the structure of the self-assembled aggregates may be related to the nanostructure of the NADES. In summary, this project shall deliver the basic principles of self-assembly in different low viscous NADES, based on which tailored self-assembly in NADES for low and high Mw amphiphiles can be done, and which is adapted to the molecular structure of a given NADES.