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Probing Long-lived Radical Intermediates in Electron Capture Dissociation with a Double Resonance Experiment

机译:用双共振实验探测电子捕获解离中的长期自由基中间体

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Despite its growing application in the field of proteomics, the mechanism of electron capture dissociation (ECD)1 is still not thoroughly understood. Recent calculations and experiments suggested that in addition to a rapid, possibly non-ergodic primary cleavage, ECD generates a metastable radical cation as one of the product species.~(2-4) ECD of cyclic peptides showed extensive secondary sidechain and backbone cleavages, which was postulated to be the result of free radical cascade.2 Radical rearrangement was also observed in ECD of linear peptides in the form of H/D scrambling.4 The presence of reaction intermediates can sometimes be revealed via double resonance (DR) experiments,5 where resonant ejection of an intermediate during the dissociation event will modulate the peak intensity of all secondary ions derived from it.
机译:尽管在蛋白质组学领域的应用越来越多,但电子捕获解离(ECD)1的机制仍然没有彻底理解。最近的计算和实验表明,除了快速,可能是非遍历初级切割之外,ECD还产生亚稳的自由基阳离子作为产物物种之一。〜(2-4)环状肽的ECD显示出广泛的继发性旁司和骨干裂解,假设其假设是自由基级联的结果.2在H / D扰扰的形式的线性肽的ECD中也观察到自由基重排.4反应中间体的存在有时会通过双共振(DR)实验揭示,如图5所示,在解离事件期间中间体的共振喷射将调节衍生自衍生的所有副离子的峰强度。

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