Structural characterization of polyethers using matrix-assisted laser desorption/ionization quadrupole ion trap time-of-flight mass spectrometry

Eur. J. Mass Spectrom. 12, 181–187 (2006)
DOI: 10.1255/ejms.809

Structural characterization of polyethers using matrix-assisted laser desorption/ionization quadrupole ion trap time-of-flight mass spectrometry

Shoji Okuno,^a Masato Kiuchi^a and Ryuichi Arakawa^a,b,*
^aNational Institute of Advanced Industrial Science and Technology (AIST), 1-8-31 Midorigaoka, Ikeda, Osaka 563-8577, Japan
^b,*Department of Applied Chemistry, Kansai University (3-3-35 Yamatecho, Suita, Osaka 564-8680, Japan. E-mail: arak@ipcku.kansai-u.ac.jp

ABSTRACT:

Fragmentation of polyethers, such as poly(ethylene glycol) (PEG), poly(propylene glycol) and poly(tetramethylene glycol) was analyzed by matrix-assisted laser desorption/ionization tandem mass spectrometry (MALDI-MS/MS) using a quadrupole ion trap time-of-flight mass spectrometer (QIT-ToF). The Li adduct ion provided more abundant fragments than the Na and K adduct ions in the MS/MS spectra. A previous study had demonstrated four series fragments of hydroxyl-, vinyl- and formyl-terminated ions, as well as distonic cations, in high-energy fast atom bombardment MS/MS and MALDI collision-induced dissociation measurements of poly(ethylene glycol). In the present study, the low-energy MS/MS measurements using MALDI-QIT-ToF, showed hydroxyl-, vinyl- and formyl-terminated fragments with or without other fragment groups, but not distonic cations. The fragmentation depended on the types of polyethers examined. MS/MS measurements using MALDI- QIT-ToF are expected to allow structural characterization of unknown components of polyethers.

Keywords: polyether, matrix-assisted laser desorption/ionization, ion trap ToF, tandem mass spectrometry

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