Molecular Electrochemistry as Enabling Technology in Inorganic and Bioinorganic Chemistry

2019年诺贝尔化学奖因开发锂离子电池(Li-ion)而获得的奖项戏剧性地表明，对最平淡无奇的主题的基础研究可能会改变世界。锂离子电池有许多不同的类型，但都依赖于离子嵌入到层状过渡金属氧化物和硫化物中的知识，这些主题在应用于可靠的轻型充电电池之前已经研究了几十年。这项拟议的研究的一个主要主题涉及富硫氮分子化学的密切细节。这肯定与另一项主要的储能技术有关，即钠硫电池(关于这类电池中三硫自由基阴离子S3的行为)。然而，这一提议未来更有可能应用于分子电子学的微型传感器和探测器。 这项研究提案的另一个主要主题涉及高活性有机磷化合物的化学合成。这些药物将用于开发含有稀有金属Ru的新化合物，并测试它们在细胞中的生物活性，这些化合物有可能取代老化的铂类化疗药物，癌症对这些药物的免疫力已经提高。最初关于铂化合物的工作完全出人意料地来自于使用所谓的惰性铂电极来研究电场对细菌的影响。该提案的一个主要主题是使用分子电化学作为一种使能技术来指导化学合成，提供对涉及电子转移(或氧化还原)反应及其诱导的基本过程的机械性见解。 这里提出的工作往往需要远离日常生活的环境。工作是在各种惰性气室中进行的。使用高能X射线衍射在分子水平上测量结构。电气工作采用专门的电路，对施加的电压和小电流的准确测量提供高度控制。通过物质与不同频率的电磁辐射的相互作用，光谱学被进一步用于分析物质。磁共振光谱学使用无线电或微波频率对在均匀磁环境中保存的样品进行分析。所有这些技术都需要安装复杂的多用户仪器。最后，与我的培训理念一致，所要求的大部分资金将用于为年轻的HQP提供适度的津贴，他们正在通过几年的全日制研究经验来加强他们的理科教育，这最终将为加拿大经济带来许多回报。基础研究经费的进一步增加将改善这些年轻人的报酬，他们正在接受培训，成为知识社会中富有成效的成员。

As was dramatically shown by the award of the 2019 Nobel Prize in Chemistry for the development of lithium-ion batteries (Li-ion), basic research on the most prosaic topics can have world altering outcomes. There are many different Li-ion battery types, but all depend on a knowledge of the intercalation of ions into layered transition-metal oxides and sulfides, topics that were studied for decades before the application to reliable light-weight rechargeable batteries was conceived. A major theme of the proposed research involves the intimate details of the chemistry of sulfur-nitrogen rich molecules. There is certainly a link to another major technology for energy storage, namely the sodium-sulfur battery (regarding behaviour of the trisulfur radical anion S3- in such batteries). However, the more likely future application of this proposal is to miniaturized sensors and detectors for molecular electronics. Another major theme of this research proposal relates to the chemical synthesis of highly reactive organophosphorus compounds. These will be used to develop new chemical compounds with the rare metal ruthenium and testing their biological activity in cells, which have the potential to replace ageing platinum-based chemotherapies to which cancers have developed increased immunity. The original work on platinum compounds came entirely unexpectedly from the use of supposedly inert platinum electrodes to study the effects of electric fields on bacteria. An overarching theme of this proposal is the use of molecular electrochemistry as an enabling technology to guide chemical synthesis, provide mechanistic insights into the basic processes involved in, and induced by, electron-transfer (or redox') reactions. The work proposed here often requires environments far-removed from daily life. Work is done in inert-atmosphere chambers of various kinds. Structures are measured at the molecular level using high-energy X-ray diffraction. Electrical work employs specialized circuitry that provides high degrees of control on the applied voltages and on the accurate measurement of small currents. Spectroscopy is further used to analyze matter by its interactions with varying frequencies of electromagnetic radiation. Magnetic resonance spectroscopy uses radio or microwave frequencies on samples held in homogeneous magnetic environments. All these techniques require sophisticated installations of multi-user instrumentation. Finally, in alignment with my training philosophy most of the requested funding goes to provide modest stipends for young HQP who are augmenting their BSc education by several years of full- time research experience, which ultimately has many returns to the Canadian economy. Further increases in fundamental research funding will improve the remuneration of these young people who are being trained to be productive members of the knowledge society.