Desorption chemical ionization tandem mass spectrometry of polyprenyl and dolichyl phosphates
(1996) Journal of the American society for mass spectrometry — Vol. 7, n° 9, p. 958-964 (1996)
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- Abstract
- Negative-ion desorption chemical ionization (DCI) tandem mass spectrometry was applied to the analysis of nanomole quantities of semisynthetic polyisoprenyl phosphates, the chain length of which ranged from 7 to 20 isoprene units. The DCI spectrum of all the compounds tested show the presence of independently generated ions [M - HPO3 - H](-), [M - H3PO2 - H](-) and [M - H3PO4 - H](-) resulting from the loss of a part of or the entire phosphate group of a polyisoprenyl-P. In tandem mass spectrometry, the [M - H3PO4 - H](-) fragment produces series of ions 68 mass units apart, indicative of the polyisoprenoid nature of a compound. Studies with deuterated and alpha-saturated polyisoprenyl phosphates demonstrated that fragmentations of the [M - H3PO4 - H](-) ion proceed from both ends (alpha and omega) of a polyisoprenoid chain and may occur at either allylic (A) or vinylic (V) sites. Fragments of masses equal to [n x 68 - 1] and [n x 68 - 13] (where n is the number of isoprene units and 3 I n is less than the total number of isoprene residues within a polyisoprenoid chain) comprise the alpha A and omega V series, respectively, and represent the most abundant ions in tandem mass spectra of the [M - H3PO4 - H](-) fragment of polyprenyl phosphates. alpha-Saturated dolichyl phosphates can be distinguished easily from corresponding polyprenyl phosphates not only on the basis of a 2-u shift of the [M - H3PO4 - H](-) ion and the alpha series of fragments, but also because of the presence of an additional (A + 14) series of ions 14 u heavier than fragments resulting from the allylic cleavages of an alpha-saturated polyisoprenoid chain. Possible mechanisms of the collision-induced dissociation reactions of polyprenyl phosphates are discussed.
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Wolucka, BA., Rozenberg, R., de Hoffmann, E., & Chojnacki, T. (1996). Desorption chemical ionization tandem mass spectrometry of polyprenyl and dolichyl phosphates. Journal of the American society for mass spectrometry, 7(9), 958-964. https://doi.org/10.1016/1044-0305(96)80514-9 (Original work published 1996)