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首页> 外文期刊>The European physical journal, D. Atomic, molecular, and optical physics >High-energy collision-activated and electron-transfer dissociation of gas-phase complexes of tryptophan with Na~+, K~+, and Ca~(2+)
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High-energy collision-activated and electron-transfer dissociation of gas-phase complexes of tryptophan with Na~+, K~+, and Ca~(2+)

机译：色氨酸与Na〜+，K〜+和Ca〜（2+）的气相配合物的高能碰撞激活和电子转移解离

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摘要

The structure and reactivity of gas-phase complexes of tryptophan (Trp) with Na~+, K~+, and Ca~(2+) were examined by high-energy collision-activated dissociation (CAD) and electron transfer dissociation (ETD) using alkali metal targets. In the CAD spectra of M~+Trp (M = Na and K), neutral Trp loss was the primary dissociation pathway, and the product ion of collision-induced intracomplex electron transfer from the indole π ring of Trp to the alkali metal ion was observed, indicating a charge-solvated structure in which Trp is non-zwitterionic. The NH_3 loss observed in the CAD spectrum of Ca~(2+)Trp_2 is ascribed to a CZ (mixed charge-solvated/zwitterionic)-type structure, in which one Trp is non-zwitterionic and the other Trp adopts a zwitterionic structure with an NH_3~+ moiety. The H atom and NH_3 losses observed in the ETD spectrum of Ca~(2+)Trp_2 indicate the formation of a hypervalent radical in the complex, R–NH_3, via electron transfer from the alkali metal target to the NH_3~+ group of the CZ-type structure. Ca~(2+) attachment to Trp cluster induces the zwitterionic structure of Trp in the gas phase, and an electron transfer to the zwitterionic Trp forms the hypervalent radical as a reaction intermediate.
机译：色氨酸（Trp）与Na〜+，K〜+和Ca〜（2+）的气相配合物的结构和反应性通过高能碰撞激活解离（CAD）和电子转移解离（ETD）进行了研究使用碱金属靶。在M〜+ Trp（M = Na和K）的CAD光谱中，中性Trp损失是主要的离解途径，碰撞诱导的复杂内电子从Trp的吲哚π环转移到碱金属离子的产物离子为观察到，表明其中Trp为非两性离子的电荷溶解的结构。在Ca〜（2+）Trp_2的CAD光谱中观察到的NH_3损失归因于CZ（混合电荷溶剂化/两性离子）型结构，其中一个Trp为非两性离子，另一个Trp采用具有两性离子的结构NH_3〜+部分。在Ca〜（2+）Trp_2的ETD光谱中观察到的H原子和NH_3的损失表明配合物R–NH_3中的高价自由基是通过电子从碱金属靶向NH_3〜+基团的转移而形成的。 CZ型结构。 Ca〜（2+）与Trp团簇的结合在气相中诱导Trp的两性离子结构，电子转移至两性离子Trp形成高价自由基作为反应中间体。

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