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Metal-mediated formation of gas-phase amino acid radical cations

机译:金属介导的气相氨基酸自由基阳离子的形成

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摘要

The results from an investigation of the collision-induced dissociation ( CID) of the ternary complexes [Cu-II(terpy)(AA)](2+) are presented (terpy)2,2':6',2''- terpyridine; AA) one of the twenty common amino acids). These complexes show a rich gas-phase chemistry, which depends on the identity of the amino acid. For the histidine-, lysine- and tryptophan-containing complexes, oxidative dissociation of the amino acid is observed, yielding the amino acid radical cation. The results of further mass selection and CID of these amino acid radical cations are presented. The CID of the series [Fe-III( salen)( AA)](+) ( where salen) N, N'-ethylenebis( salicylideneaminato)) is also examined. These complexes undergo loss of the neutral amino acid in all cases, although the radical cation of arginine is also produced and its subsequent fragmentation examined. B3-LYP/6-31G(d) computations were carried out to test aspects of the proposed fragmentation mechanism of the histidine and arginine radical cations.
机译:研究了三元配合物[Cu-II(terpy)(AA)](2+)的碰撞诱导解离(CID),结果显示为(terpy)2,2':6',2''-特吡啶AA)二十种常见氨基酸之一。这些配合物显示出丰富的气相化学,这取决于氨基酸的身份。对于含组氨酸,赖氨酸和色氨酸的复合物,观察到氨基酸的氧化解离,产生氨基酸自由基阳离子。给出了进一步的质量选择和这些氨基酸自由基阳离子的CID的结果。还检查了[Fe-III(salen)(AA)](+)系列的CID(其中salen)是N,N'-亚乙基双(水杨基亚胺)。在所有情况下,这些复合物都会损失中性氨基酸,尽管还会生成精氨酸的自由基阳离子并检查其随后的断裂情况。进行了B3-LYP / 6-31G(d)计算,以测试所建议的组氨酸和精氨酸自由基阳离子断裂机理的各个方面。

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