Observations and Applications of Dissociative Electron Transfer Reactions in Selected Molecular Systems

解离电子转移（DET）是化学、生物和环境体系中许多分子反应的基础。在过去的十年中，申请人（Lu）专注于各种分子系统中弱束缚电子的DET反应的研究，并发现了它们在各种主题中的关键作用，从环境重要的卤代分子的反应和电离辐射诱导的DNA损伤到抗癌药物的活化。这个更新的建议描述了一个连续的计划，研究弱束缚电子在选定的分子系统的环境和生物意义的DET反应。该计划的目标是获得电离辐射下卤代分子在水溶液中的DET反应的实时观测，并探索其环境和生物医学应用。然而，该提案仅关注物理科学的研究挑战。 分子反应的实时观察对于理解从化学和生物学到环境和医学科学的不同领域的许多过程和结果非常重要。在分子尺度上监测反应可以导致识别控制反应的分子途径;一旦识别了途径，就可以预测、修改和控制反应。飞秒时间分辨激光光谱（fs-TRLS）是一种非常强大的实时观测分子反应的技术。该研究将联合收割机fs-TRLS与DNA损伤试验相结合，研究生物学效应。具体来说，我们将演示如何拟议的DET反应的卤化分子与电离辐射产生的弱束缚电子发生在真实的时间，并确定其反应效率。 该计划建立在创新的研究策略和申请人在分子系统中新型反应机制的最新进展之上。它处于环境物理学和化学，生物物理学，生物化学，生物物理学，飞秒化学和飞秒生物学的前沿，并以坚实的先前研究为基础。这些结果有望为卤代分子的反应机制及其对重要环境和生物过程（如臭氧消耗和DNA损伤）的影响提供深入的了解。该项目还可能最终导致在环境保护和修复以及人类健康方面的重要应用。

Dissociative electron transfer (DET) underlies many molecular reactions in chemical, biological and environmental systems. Over the past decade, the applicant (Lu) has focused on research on DET reactions of weakly-bound electrons in various molecular systems, and discovered their crucial roles in a variety of topics, ranging from the reactions of environmentally important halogenated molecules and ionizing-radiation induced DNA damage to the activation of anticancer drugs. This renewal proposal describes a continuous program to study DET reactions of weakly-bound electrons in selected molecular systems of environmental and biological significance. The objectives of this program are to obtain real-time observations of the DET reactions of halogenated molecules in aqueous solutions under ionizing radiation and to explore their environmental and biomedical applications. This proposal however will only focus on research challenges in the physical sciences. Real-time observations of molecular reactions are important to understand many processes and outcomes in diverse fields from chemistry and biology, to environmental and medical sciences. The monitoring of the reactions on the molecular scale can lead to the identification of molecular pathways controlling the reactions; once the pathways are identified, the reactions can be predicted, modified and controlled. Femtosecond time-resolved laser spectroscopy (fs-TRLS) is a tremendously powerful technique for real-time observations of molecular reactions. The proposed research will combine fs-TRLS with DNA damage assays to study the biological effects. Specifically, we will demonstrate how the proposed DET reactions of halogenated molecules with weakly-bound electrons produced by ionizing radiation occur in real time, and determine their reaction efficiencies. This program is built on an innovative research strategy and the Applicant's recent advances on a novel reaction mechanism in molecular systems. It is at the cutting edge of environmental physics and chemistry, biophysics, biochemistry, photophysics, femtochemistry and femtobiology, and is grounded in solid previous studies. The results are expected to provide a deep understanding of the reaction mechanisms of halogenated molecules and their effects on important environmental and biological processes such as ozone depletion and DNA damage. This project may also ultimately lead to important applications in environmental protection and remediation, and human health.