Peak width‐mass correlation in CID MS/MS of isomeric oligosaccharides using traveling‐wave ion mobility mass spectrometry

Abstract Isomeric oligosaccharides γ‐cyclodextrin (γ‐CD), glucosyl‐βCD (Glc 1 ‐βCD) and maltosyl‐αCD (Glc 2 ‐αCD) were analyzed by traveling‐wave ion mobility (twIM) mass spectrometry (MS). Their formation of multicharged multimers differed from each other. The ion mobility‐mass spectrometry was useful in the self‐assembling and complex formation analyses of CD isomers. The drift times of the isomers and their product ions with the same mass were almost the same in collision‐induced dissociation (CID) MS/MS. In contrast, the ion mobility peak widths were sensitive to structural differences of the isomeric product ions. The twIM peak width (ms ‐ µs) of the product ions [M − Glc n + H] + ( n = 0 ∼ 6) of γ‐CD correlated linearly with their masses (Da); the large and/or long chain product ions had wider peak widths, which were much wider than those from the general diffusion effect. This was a novel and useful ‘trend line’ to discriminate between the three isomers. Plots of [M − Glc 2 ∼ 6 + H] + of Glc 1 ‐βCD and [M − Glc 3 ∼ 6 + H] + of Glc 2 ‐αCD product ions' plots were on the same trend line as γ‐CD. The plots of [M − Glc 1 + H] + of Glc 1 ‐βCD and [M − Glc 1, 2 + H] + of Glc 2 ‐αCD strayed from the γ‐CD line; their peak widths were narrower than those of γ‐CD. These results indicated that product ions from the chemical species of Glc 1 ‐β CD and Glc 2 ‐αCD retained their CD structure. Analyses of the IM peak widths enable us to elucidate the structures of the product ions. Copyright © 2009 John Wiley & Sons, Ltd.