Institut für Ionenphysik und Angewandte Physik, Universität Innsbruck, Technikerstrasse 25, A-6020, Innsbruck, Austria.
Center for Biomolecular Sciences Innsbruck, Universität Innsbruck, Technikerstrasse 25, A-6020, Innsbruck, Austria.
Angew Chem Int Ed Engl. 2024 Oct 7;63(41):e202407469. doi: 10.1002/anie.202407469. Epub 2024 Sep 6.
2-Bromo-1-(3,3-dinitroazetidin-1-yl)ethan-1-one (RRx-001) is a hypoxic cell chemotherapeutics with already demonstrated synergism in combined chemo-radiation therapy. The interaction of the compound with secondary low-energy electrons formed in large amounts during the physico-chemical phase of the irradiation may lead to these synergistic effects. The present study focuses on the first step of RRx-001 interaction with low-energy electrons in which a transient anion is formed and fragmented. Combination of two experiments allows us to disentangle the decay of the RRx-001 anion on different timescales. Sole presence of the electron initiates rapid dissociation of NO and HNO neutrals while NO and Br anions are produced both directly and via intermediate complexes. Based on our quantum chemical calculations, we propose that bidirectional state switching between π*(NO) and σ*(C-Br) states explains the experimental spectra. The fast dynamics monitored will impact the condensed phase chemistry of the anion as well.
2-溴-1-(3,3-二硝基氮杂环丁烷-1-基)乙酮（RRx-001）是一种低氧细胞化疗药物，已证明在放化疗联合治疗中具有协同作用。该化合物与辐照物理化学阶段大量形成的次级低能电子相互作用可能导致这些协同效应。本研究集中于 RRx-001 与低能电子相互作用的第一步，其中形成并碎片化瞬态阴离子。两种实验的结合使我们能够在不同的时间尺度上分解 RRx-001 阴离子的衰减。仅存在电子就会引发 NO 和 HNO 中性物的快速离解，而 NO 和 Br 阴离子则通过直接和中间复合物同时产生。基于我们的量子化学计算，我们提出π*(NO)和σ*(C-Br)态之间的双向状态切换解释了实验光谱。监测到的快速动力学将对阴离子的凝聚相化学产生影响。
