Hydrofluoroethers (HFEs), Aryl-Based Fluorinated Alkoxides, Diaryl-perfluoropolyalkylethers (PFPAEs) for Theranostics and Extreme Temperature Aerospace Materials

工作性质：形成和稳定全氟烷氧化合物(PFA)历来对合成具有挑战性。然而，在2015年，我们在氢氟醚(HFES)衍生的非金属PFA(CnF2nO-NR4+)方面进行了开创性工作，为此铺平了道路。2019年，我们首次报道了使用氟化银(I)作为一种温和的氟化方法来产生HFES。非金属PFA具有热稳定性，可用于我们在2020年报道的药物和农用化学类似物。我们还展示了PFA在制造称为全氟聚烷基醚(PFPAE)的高性能润滑聚合物中的创新用途。在我们原有工作的基础上，我们提出了两个但又相互关联的研究目标：短期内1)构建形式上无法获得的积木(单体)，长期2)开发从自然生成的矿石氟磷铝(CaF2)逐步衍生的新氟化方案，以同时改进航空航天和医疗材料。为什么以及对谁来说这项研究很重要：从芳基-HFE多聚芳烃中开发封端芳香族的PFPAE单体是下一代工业化学家的有效培训基础，同时也极大地扩展了三个重要行业的材料途径：a)氟聚合物行业正在寻找可以很容易地加入到可生物降解聚合物中的单体，以提高其温度性能，同时保持环境退化。通过我们的技术，我们可以合成芳基-HFE PFA，形成独特的芳香族端基聚合物，适用于保护涂料、表面活性剂和废弃塑料的再利用。B)医疗行业需要更好的诊断和治疗药物输送设备(即治疗药物)，以提供个性化的病人护理和亲脂性药物。使用芳基HFE多聚芳烃，我们可以创建用于患者护理应用的聚合物工具。为了提高产量和降低成本(目前40%的药物含有氟)，亲脂性药物生产中特定的、快速的后期氟化的新方法是可取的。C)航空航天工业正在突破空间探索和火箭运输可重复使用的界限。需要新的材料来满足这些新的需求。一些空间应用需要在没有溶剂、热量和重力的情况下进行化学操作。通过在使用机械力化学过程的生物聚合物共混物中引入芳香族封端的PFPFAE，可以改善极端温度性能。预期成果：在未来5年内，我们将1)开发新型芳香族封端PFPAE单体，使用芳基-HFE PFA用于航空航天材料和慢性疼痛治疗药物的聚合物应用；2)改进聚合物和/或药物的后期氟化方法，以分别提高热性能或亲脂性。总而言之，我们将发展创新的氟化学，以影响基于生物的航空航天材料和医疗监测系统。

NATURE OF THE WORK: Forming and stabilizing perfluoroalkoxides (PFAs) has been historically challenging for synthesis. However in 2015, we paved the way with groundbreaking work in non-metal PFAs (CnF2nO-NR4+) derived from hydrofluoroethers (HFEs). In 2019, we reported the first use of silver(I) fluoride as a mild fluorination method to generate HFEs. Non-metal PFAs are thermally stabile and can be affixed to medicinal and agrochemical analogues reported by us in 2020. We also demonstrated an innovative use of PFAs for manufacturing high performance lubricating polymers known as perfluoropolyalkylethers (PFPAEs). Building upon our original works, we propose research objectives which are two-fold but yet interconnected: in the short-term 1) Construct formally unobtainable building blocks (monomers) and in the long-term 2) Develop new fluorination protocols incrementally derived from the naturally occurring ore, fluorospar (CaF2) to simultaneous improve aerospace and medical materials. WHY AND TO WHOM THE RESEARCH IS IMPORTANT: developing aromatic terminated PFPAE monomers from aryl-HFE PFAs is an effective training ground for the next generation of industry chemists and yet greatly expands material pathways in three important industries: A) The fluoropolymer industry is looking towards monomers which can be readily incorporated into biodegradable polymers to enhance their temperature performance but yet maintain environmental degradation. With our techniques we can synthesize aryl-HFE PFAs to form unique aromatic terminated polymers suitable as protective coatings, surfactants, and in the reuse of discarded plastics. B) The medical industry needs better diagnostic and therapeutic drug delivery devices (i.e. theranostics) for personalized patient care and lipophilic drugs. With aryl-HFE PFAs, we can create polymeric tools for patient care applications. New methods in specified, rapid late-stage fluorination in lipophilic drug manufacturing are desirable for yield improvements and lowering cost (40% of current drugs contain fluorine). C) Aerospace Industry is pushing the boundaries of space exploration and the reusability of rocket transport. New materials are required to handle these newer demands. Some of the space application need chemistries to perform without solvent, heat, and gravity. By introducing aromatic terminated PFPFAEs within biopolymeric blends using mechanochemical processes can improve extreme temperature performance. ANTICIPATED OUTCOMES: In the next 5 years, we will 1) Develop new aromatic terminated PFPAE monomers using aryl-HFE PFAs for polymer applications in aerospace materials and chronic pain theranostics; 2) Improve methodologies in late-stage fluorination of polymers and/or pharmaceuticals for improved thermal performance or lipophilicity, respectfully. In summary, we will develop innovative fluorine chemistries to impact bio-based aerospace materials and medical monitoring systems.