pH Switching of Radical Reactivity and Orbital Conversion

自由基反应性的 pH 值转换和轨道转换

• 批准号: DP140101835
• 负责人: Prof Michelle Coote
• 金额: --
• 依托单位: The Australian National University
• 依托单位国家: 澳大利亚
• 项目类别: Discovery Projects
• 财政年份: 2014
• 资助国家: 澳大利亚
• 起止时间: 2014-01-01 至 2013-12-31
• 项目状态: 已结题
• 来源: https://dataportal.arc.gov.au/RGS/Web/Grants/DP140101835
• 关键词: pH; Switching; Radical; Reactivity; Orbital

Radicals are reactive species that have an unpaired electron, which is usually located in the highest occupied orbital. This proposal uses a combination of theory and experiment to design a new class of radical anions whose unpaired electron is not the highest occupied orbital, and whose electronic configuration reverts to the normal aufbau configuration upon protonation. These special radical anions will display unprecedented radical stability that is pH switchable, as well as ferromagnetism and conductivity upon oxidation. This project will exploit these unusual properties in the design of pH-switchable protecting groups for radicals for synthesis and polymerisation, and determine their role in oxidative stress and enzyme kinetics.

自由基是具有未配对电子的活性物种，通常位于最高占据轨道上。该方案采用理论和实验相结合的方法设计了一类新的自由基阴离子，其未配对的电子不是最高占据轨道，其电子构型在质子化后恢复到正常的Aufbau构型。这些特殊的自由基阴离子将表现出前所未有的自由基稳定性，即pH可调，以及氧化时的铁磁性和导电性。该项目将在设计用于合成和聚合的自由基的pH可调保护基团时利用这些不同寻常的特性，并确定它们在氧化应激和酶动力学中的作用。