Unexpected linear ion trap collision-induced dissociation and Fourier transform ion cyclotron resonance infrared multi-photon dissociation fragmentation of a hydrated C-glycoside of 5-fluorouridine formed by the action of the pseudouridine synthases RluA
Unexpected linear ion trap collision-induced dissociation and Fourier transform ion cyclotron resonance infrared multi-photon dissociation fragmentation of a hydrated C-glycoside of 5-fluorouridine formed by the action of the pseudouridine synthases RluA
复制标题
由假尿苷合酶 RluA 的作用形成的 5-氟尿苷水合 C-糖苷的意外线性离子阱碰撞诱导解离和傅里叶变换离子回旋共振红外多光子解离碎片
DOI：
10.1002/rcm.5162
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发表时间：
2011
期刊：
影响因子：
--
通讯作者：
Mueller,EugeneG
中科院分区：
文献类型：
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作者：
Miracco,EdwardJ;Bogdanov,Bogdan;Mueller,EugeneG
作为对假性尿苷合成酶研究的一部分，RNA中的5-氟尿苷被用作机械探针。5-氟尿苷的水合重排产物被分离出来，作为二核苷酸的一部分，并在质谱学过程中经历了不寻常的碎裂，产物嘧啶环上的HNCO容易丢失，而不是磷酸二酯键的断裂。虽然尿苷和假尿苷中HNCO的损失已被证实，但导致它们裂解的周环过程不能与5-氟尿苷产物中饱和的嘧啶环起作用。基于本文报道的MSn结果和计算，提出了一种依赖于产物嘧啶环上官能团的特殊配置的新机制来解释异常容易的碎裂。版权所有©2011 John Wiley&Sons，Ltd.
As part of the investigation of the pseudouridine synthases, 5‐fluorouridine in RNA was employed as a mechanistic probe. The hydrated, rearranged product of 5‐fluorouridine was isolated as part of a dinucleotide and found to undergo unusual fragmentation during mass spectrometry, with the facile loss of HNCO from the product pyrimidine ring favored over phosphodiester bond rupture. Although the loss of HNCO from uridine and pseudouridine is well established, the pericyclic process leading to their fragmentation cannot operate with the saturated pyrimidine ring in the product of 5‐fluorouridine. Based on the MSnresults and calculations reported here, a new mechanism relying on the peculiar disposition of the functional groups of the product pyrimidine ring is proposed to account for the unusually facile fragmentation. Copyright © 2011 John Wiley & Sons, Ltd.