Abstract

A new operational mode for an ion cyclotron mobility spectrometry instrument is explored as a possible means of performing high-resolution separations. The approach is based on oscillating fields that are applied to segmented regions of a circular drift tube. Ions with mobilities that are resonant with the frequency of field application are transmitted while nonresonant species are eliminated. An ion mobility spectrum is obtained by scanning the drift field application frequency. The approach is demonstrated by examining mixtures of ions produced by electrospraying the substance P peptide, as well as a mixture of tryptic peptides obtained by enzymatic digestion of cytochrome c. Drift field application frequency scans of substance P peptide ions show that it is possible to separate [M+2H](2+) ions, and compact and elongated forms of [M+3H](3+) ions. The resolution of different ions is related to the number of cycles for the analysis. At high cycle numbers (>50 3/4 or a drift length of 9242.03 cm) values of the resolving power can exceed 300 with a maximum resolving power of ∼400. The ability to tune the resolving power of a mobility-based separation by varying the ion cycle number has substantial analytical utility.

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