Stanislav A Pshenichnyuk, Nail L Asfandiarov, Rustam G Rakhmeyev, Alexei S Komolov, Oleg E Tereshchenko
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引用次数: 0
摘要
通过解离电子附着(DEA)光谱和密度泛函理论计算,研究了在气相条件下谷氨酸(Glu)对映体的低能(0-14 eV)共振电子相互作用和通过解离电子附着(DEA)产生的碎片种类。与早先利用 DEA 技术研究的一系列氨基酸相反,最丰富的种类与母体分子负离子中一个氢原子的消除无关。除了这种强度较低的闭壳[Glu - H]-片段外,在同一电子能量区域内只检测到[Glu - 19]-和[Glu - 76]-两种质量选择负离子,产率最大值约为 0.9 eV。根据目前的 B3LYP/6-31G(d)计算,该值与 Glu 的最低通常空 π* COOH 分子轨道上的垂直电子附着能量 0.88 eV 非常吻合。虽然在目前的实验条件下无法先验地检测到不对称的 DEA 特性,但 "手性不守恒 "可能与某些衰变通道有关。显而易见,测量到的 L 型和 D 型光谱是相同的,但这些结果对于即将进行的在传统 DEA 技术框架内利用自旋极化电子束作为手性因子的实验具有重要意义。
Electron-driven processes in enantiomeric forms of glutamic acid initiated by low-energy resonance electron attachment.
Low-energy (0-14 eV) resonance electron interaction and fragment species produced by dissociative electron attachment (DEA) for enantiomeric forms of glutamic acid (Glu) are studied under gas-phase conditions by means of DEA spectroscopy and density functional theory calculations. Contrary to a series of amino acids studied earlier employing the DEA technique, the most abundant species are not associated with the elimination of a hydrogen atom from the parent molecular negative ion. Besides this less intense closed-shell [Glu - H]- fragment, only two mass-selected negative ions, [Glu - 19]- and [Glu - 76]-, are detected within the same electron energy region, with the yield maximum observed at around 0.9 eV. This value matches well the energy of vertical electron attachment into the lowest normally empty π* COOH molecular orbital of Glu located at 0.88 eV according to the present B3LYP/6-31G(d) calculations. Although the detection of asymmetric DEA properties a priori is not accessible under the present experimental conditions, "chirality non-conservation" can be associated with some decay channels. Evidently, the measured spectra for the L- and D-forms are found to be identical, the results, nevertheless, being of interest for the forthcoming experiments utilizing spin-polarized electron beam as a chiral factor in the framework of conventional DEA technique.
期刊介绍:
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