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首页> 外文期刊>The Analyst: The Analytical Journal of the Royal Society of Chemistry: A Monthly International Publication Dealing with All Branches of Analytical Chemistry >Microheterogeneity within conformational states of ubiquitin revealed by high resolution trapped ion mobility spectrometry
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Microheterogeneity within conformational states of ubiquitin revealed by high resolution trapped ion mobility spectrometry

机译：高分辨率捕获离子迁移谱法揭示泛素构象状态内的微异质性

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摘要

The present work employs trapped ion mobility spectrometry (TIMS) for the analysis of ubiquitin ions known to display a multitude of previously unresolved interchangeable conformations upon electrospray ionization. The conformational distributions of ubiquitin [M + 6H](6+) through [M + 13H](13+) ions observed by TIMS are nearly identical to numerous drift tube ion mobility spectrometry studies reported in the literature. At an experimental resolving power up to similar to 300, many of the congested conformations within the well-known compact, partially folded, and elongated [M + 7H](7+) states are separated. Minimizing the voltages (RF and DC) in the entrance funnel results in exclusive observation of compact [M + 7H](7+) conformers. However, under these conditions, the mobility-dependent pseudopotential coefficient may discriminate against ions having larger collision cross sections-a universal effect for all RF ion guides, funnels, and traps operating in the presence of a gas. The data presented underscore the complications associated with direct comparison of collision cross section values that represent an ensemble average of multiple underlying conformations. As illustrated herein, the microheterogeneity within a particular conformational family and the relative state-to-state abundance can be altered by solvent memory, energetic, and kinetic effects.
机译：本工作采用捕获离子迁移谱法（TIMS）来分析泛素离子，已知该泛素离子在电喷雾电离时会显示出许多先前未解析的可互换构象。通过TIMS观察到的泛素[M + 6H]（6+）到[M + 13H]（13+）离子的构象分布与文献中报道的大量漂移管离子迁移谱研究几乎相同。在高达300的实验分辨力下，众所周知的紧密，部分折叠和拉长的[M + 7H]（7+）状态下的许多拥挤构象被分离。最小化进入漏斗中的电压（RF和DC）会导致仅观察紧凑的[M + 7H]（7+）构象异构体。但是，在这些条件下，与迁移率有关的假电位系数可能会与具有较大碰撞横截面的离子区分开来-对所有在气体存在下运行的RF离子导管，漏斗和阱的普遍影响。呈现的数据强调了与直接比较碰撞横截面值相关的复杂性，这些碰撞横截面值表示多个基础构象的整体平均值。如本文所述，特定构象族内的微异质性和相对状态间的丰度可以通过溶剂记忆，能量和动力学效应来改变。

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