Limonene derived lyotropic liquid crystals: synthesis and structure

背景：据估计，2020年生产了9000万吨生物化学品和生物聚合物，而石油化学来源估计将是另外3.3亿吨化学品和聚合物的来源。表面活性剂有着广泛的应用，2018年全球需求量约为1650万吨，年增长率约为3%。溶致液晶是两亲性物质（如表面活性剂）在一定浓度、一定温度和浓度下溶解的物质状态。在全球范围内，柑橘是世界上最大的水果作物，其精油含有许多有用的化合物。其中一种化合物是柠檬烯，占橙子精油含量的85%以上。柠檬烯也可以从废橡胶轮胎的热解中获得，目前正在研究作为喷气燃料添加剂和增塑剂的原料。项目目标：该项目的最初目标是在尽可能坚持绿色化学12条原则的情况下，以柠檬烯为原料合成新型表面活性剂。内环烯烃和外环烯烃的不同反应活性将被利用来产生亲水性（如二醇）和疏水性（如烷基）区域。在合成之后，我们将把水的相图绘制成浓度和温度的函数。我们将利用二维SAXS/WAXS获取结构信息。原子MD模拟将用于使实验趋势合理化。最终，将制备一系列材料-最初使用柠檬烯，但有可能扩展为替代萜类-而观察到的溶性行为的差异将与分子结构有关。

Background: In 2020 it was estimated that were 90 million tonnes of bio-chemicals and biopolymers produced, while petrol chemical sources are estimated to be the source of a further 330 million tonnes of chemicals and polymers. Surfactants have a wide array of applications, with global demand in 2018 of around 16.5 million megatons with an annual growth rate of around 3%. Lyotropic liquid crystals are states of matter in which an amphiphile (e.g. a surfactant) is dissolved at a certain concentration, at a certain temperature and concentration. Globally citrus is the largest fruit crop in the world, and their essential oils contain numerous useful compounds. One such compound is limonene, making up more than 85% of the essential oil content of oranges. Limonene can also obtained from the pyrolysis of waste rubber tyres, and is currently being studied as a feedstock material jet fuel additives and plasticisers. Project Objectives: The initial aim of this project are to synthesise novel surfactants using limonene as a feedstock, adhering to the 12 principles of green chemistry where possible. The differing reactivity of the endo- and exo-cyclic olefins will be exploited to produce hydrophilic (e.g. diol) and hydrophobic (e.g. alkyl) regions. Following synthesis, we will map the phase diagram with water as a function of concentration and temperature. We will utilise 2D SAXS/WAXS to obtain structural information. Atomistic MD simulations will be utilised to rationalise experimental trends. Ultimately, a family of materials will be prepared - initially using limonene but with the possibility of expanding to alternate terpenoids - and the differences in observed lyotropic behaviour will be related back to molecular structure.