Muftakhov Mars V, Shchukin Pavel V
Institute of Molecule and Crystal Physics - Subdivision of the Ufa Federal Research Centre of the Russian Academy of Sciences, IMCP UFRC RAS, Prospekt Oktyabrya 151, 450075, Ufa, Russia.
Rapid Commun Mass Spectrom. 2019 Mar 15;33(5):482-490. doi: 10.1002/rcm.8354.
Charge transfer via DNA plays an important role in physical and chemical processes in biological systems, and is used in biomolecular electronics. The present study considers the resonant interaction of free electrons with nucleosides, which is important for an understanding of the processes of electron transport in DNA.
Resonant electron capture negative ion mass spectrometry was used to study the processes of low-energy electron attachment to two uracil nucleosides, uridine and deoxyuridine, while density functional theory (DFT) calculations were used to analyze the energy aspects of ion formation and decay.
Short-lived molecular ions, formed via mechanisms of π* shape resonances, were found in the energy region below 5 eV. The fragmentation channels of these resonances and the structures of the charged and neutral products formed were determined.
These results suggest that the formation of some fragment negative ions occurs through intramolecular charge transfer.
通过DNA进行的电荷转移在生物系统的物理和化学过程中起着重要作用，并被应用于生物分子电子学。本研究考虑了自由电子与核苷的共振相互作用，这对于理解DNA中的电子传输过程很重要。
采用共振电子捕获负离子质谱法研究低能电子与两种尿嘧啶核苷（尿苷和脱氧尿苷）的附着过程，同时使用密度泛函理论（DFT）计算来分析离子形成和衰变的能量方面。
在低于5 eV的能量区域发现了通过π*形状共振机制形成的短寿命分子离子。确定了这些共振的碎裂通道以及形成的带电和中性产物的结构。
这些结果表明，一些碎片负离子的形成是通过分子内电荷转移发生的。
