Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Prospect 47, 119991 Moscow, Russia.
Int J Mol Sci. 2021 Jul 16;22(14):7637. doi: 10.3390/ijms22147637.
The processes involving the capture of free radicals were explored by performing DFT molecular dynamics simulations and modeling of reaction energy profiles. We describe the idea of a radical recognition assay, where not only the presence of a radical but also the nature/reactivity of a radical may be assessed. The idea is to utilize a set of radical-sensitive molecules as tunable sensors, followed by insight into the studied radical species based on the observed reactivity/selectivity. We utilize this approach for selective recognition of common radicals-alkyl, phenyl, and iodine. By matching quantum chemical calculations with experimental data, we show that components of a system react differently with the studied radicals. Possible radical generation processes were studied involving model reactions under UV light and metal-catalyzed conditions.
通过进行 DFT 分子动力学模拟和反应能量曲线模拟，探索了自由基捕获过程。我们描述了自由基识别测定的想法，其中不仅可以评估自由基的存在，还可以评估自由基的性质/反应性。该想法是利用一组自由基敏感分子作为可调谐传感器，然后根据观察到的反应性/选择性深入了解所研究的自由基种类。我们将这种方法用于选择性识别常见自由基-烷基、苯基和碘。通过将量子化学计算与实验数据相匹配，我们表明系统的组成部分与所研究的自由基反应不同。研究了涉及模型反应在紫外光和金属催化条件下的可能自由基生成过程。
