Isotopic effect on ion mobility and separation of isotopomers by high-field ion mobility spectrometry.
Distinguishing and separating isotopic molecular variants is important across many scientific fields. However, discerning such variants, especially those producing no net mass difference, has been challenging. For example, single-stage mass spectrometry is broadly employed to analyze isotopes but is blind to isotopic isomers (isotopomers) and, except at very high resolution, species of the same nominal mass (isobars). Here, we report separation of isotopic ions, including isotopomers and isobars, using ion mobility spectrometry (IMS), specifically, the field asymmetric waveform IMS (FAIMS). The effect is not based on the different reduced masses of ion-gas molecule pairs previously theorized to cause isotopic separations in conventional IMS, but appears related to the details of energetic ion-molecule collisions in strong electric fields. The observed separation qualitatively depends on the gas composition and may be improved using gas mixtures. Isotopic shifts depend on the position of the labeled site, which allows its localization and contains information about the ion geometry, potentially enabling a new approach to molecular structure characterization.
Shvartsburg
Alexandre A
AA
Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, P.O. Box 999, Richland, Washington 99352, USA.
Clemmer
David E
DE
Smith
Richard D
RD
D000465:Algorithms; D002247:Carbon Isotopes / Q000737:chemistry; D005740:Gases / Q000737:chemistry; D007477:Ions / Q000737:chemistry*; D009587:Nitrogen Isotopes / Q000737:chemistry; D013057:Spectrum Analysis / Q000379:methods*
D002247:Carbon Isotopes; D005740:Gases; D007477:Ions; D009587:Nitrogen Isotopes
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