Unexpected linear ion trap collision-induced dissociation and Fourier transform ion cyclotron resonance infrared multi-photon dissociation fragmentation of a hydrated C-glycoside of 5-fluorouridine formed by the action of the pseudouridine synthases RluA and TruB

As part of the investigation of the pseudouridine synthases, 5‐fluorouridine in RNA was employed as a mechanistic probe. The hydrated, rearranged product of 5‐fluorouridine was isolated as part of a dinucleotide and found to undergo unusual fragmentation during mass spectrometry, with the facile los...

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Bibliographic Details
Published in:Rapid communications in mass spectrometry 2011-09, Vol.25 (18), p.2627-2632
Main Authors: Miracco, Edward J., Bogdanov, Bogdan, Mueller, Eugene G.
Format: Article
Language:English
Subjects:
Bonding
Cyclotron resonance
Fourier transforms
Fragmentation
Hydro-Lyases - genetics
Hydro-Lyases - metabolism
Infrared
Intramolecular Transferases - genetics
Intramolecular Transferases - metabolism
Mass spectrometry
Mathematical analysis
Molecular Structure
Monosaccharides - chemistry
Monosaccharides - metabolism
Pseudouridine - chemistry
Pseudouridine - metabolism
Pyrimidines
RNA - chemistry
RNA - metabolism
Spectroscopy, Fourier Transform Infrared
Uridine - analogs & derivatives
Uridine - chemistry
Uridine - metabolism
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Summary:As part of the investigation of the pseudouridine synthases, 5‐fluorouridine in RNA was employed as a mechanistic probe. The hydrated, rearranged product of 5‐fluorouridine was isolated as part of a dinucleotide and found to undergo unusual fragmentation during mass spectrometry, with the facile loss of HNCO from the product pyrimidine ring favored over phosphodiester bond rupture. Although the loss of HNCO from uridine and pseudouridine is well established, the pericyclic process leading to their fragmentation cannot operate with the saturated pyrimidine ring in the product of 5‐fluorouridine. Based on the MSn results and calculations reported here, a new mechanism relying on the peculiar disposition of the functional groups of the product pyrimidine ring is proposed to account for the unusually facile fragmentation. Copyright © 2011 John Wiley & Sons, Ltd.
ISSN:0951-4198
1097-0231
1097-0231
DOI:10.1002/rcm.5162