High-Definition Ion Mobility/Mass Spectrometry with Structural Isotopic Shifts for Nominally Isobaric Isotopologues
High-Definition Ion Mobility/Mass Spectrometry with Structural Isotopic Shifts for Nominally Isobaric Isotopologues
复制标题
具有结构同位素位移的高清晰度离子淌度/质谱，用于标称同量异位同位素体
DOI：
10.1021/acs.jpca.3c01792
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发表时间：
2023
期刊：
影响因子：
--
通讯作者：
Shvartsburg, Alexandre A.
中科院分区：
文献类型：
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作者：
Pathak, Pratima;Shvartsburg, Alexandre A.
我们已经报道了不同离子结构的同位素包络膜在不同离子分离中的应用。然而，这种区分异构体的新方法受到混合所有名义等压同位素的单位质量分辨率的限制。本文将高分辨率FAIMS与超高分辨率（Orbitrap）质谱直接耦合，并利用所得到的平台探索同位素精细结构的FAIMS光谱。在N2/ co2缓冲液中，15n和13c（被6mda分割）的卤化苯胺同位素物的峰移明显不同，比13c、37Cl或81br的峰移相差1或2 Da。FAIMS空间在不同元素同位素取代上的位移是相互正交的，并且与潜在的分离是正交的，形成指纹多维矩阵和跨气体成分的三维轨迹，冗余地描绘了所考虑的所有异构体。这项工作中相互关联的仪器和方法升级将结构同位素转移方法提升到一个新的水平。
We had reported the isotopic envelopes in differential IMS (FAIMS) separations depending on the ion structure. However, this new approach to distinguish isomers was constrained by the unit-mass resolution commingling all nominally isobaric isotopologues. Here, we directly couple high-definition FAIMS to ultrahigh-resolution (Orbitrap) MS and employ the resulting platform to explore the FAIMS spectra for isotopic fine structure. The peak shifts therein for isotopologues of halogenated anilines with15N and13C (split by 6 mDa) in N2/CO2buffers dramatically differ, more than for the13C,37Cl, or81Br species apart by 1 or 2 Da. The shifts in FAIMS space upon different elemental isotopic substitutions are orthogonal mutually and to the underlying separations, forming fingerprint multidimensional matrices and 3-D trajectories across gas compositions that redundantly delineate all isomers considered. The interlocking instrumental and methodological upgrades in this work take the structural isotopic shift approach to the next level.