Energy-Dependent Collision-Induced Dissociation of Lithiated Polytetrahydrofuran: Effect of the Size on the Fragmentation Properties

Ákos Kuki, Lajos Nagy, Antony Memboeuf, László Drahos, Károly Vékey, Miklós Zsuga, Sándor Kéki

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Abstract

The fragmentation properties of singly and doubly lithiated polytetrahydrofuran (PTHF) were studied using energy-dependent collision-induced dissociation. The product ion spectrum of [PTHF + Li]+ showed the formation of three different series corresponding to product ions with hydroxyl, aldehyde and vinyl end-groups. Interestingly, besides these series, two additional, non-lithiated product ions C4H9O+ and C4H7+ were identified in the MS/MS spectra. The MS/MS of the doubly lithiated PTHF ([PTHF + 2Li]2+) with a number of repeat units ranging from 8 to 27 showed the formation of product ions similar to those of the singly lithiated series, however, doubly lithiated product ions and product ions formed by the loss of one Li+-ion from the precursor ion also appeared with significant abundances. Analysis of the breakdown curves for the singly and doubly charged PTHF indicated that the series A ions are formed most probably together with the series B ions, while members of the series C ions appeared at significantly higher collision energies. The fragmentation properties of [PTHF + Li]+ and [PTHF + 2Li]2+ were also interpreted using the survival yield method. It was found that the collision energy/voltage necessary to obtain 50% fragmentation (CV50) was dependent linearly on the number of the repeat units, i.e., on the size, or the number of degrees of freedom (DOF).

Original languageEnglish
Pages (from-to)1753-1761
Number of pages9
JournalJournal of the American Society for Mass Spectrometry
Volume21
Issue number10
DOIs
Publication statusPublished - okt. 1 2010

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ASJC Scopus subject areas

  • Structural Biology
  • Spectroscopy

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