title: 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.
abstract: 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 MS(n) 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.
authors: University of Delaware, Department of Chemistry and Biochemistry, Newark, DE 19716, USA.
authors: Edward J
authors: EJ
authors: Miracco
authors: Bogdan
authors: B
authors: Bogdanov
authors: Eugene G
authors: EG
authors: Mueller
mesh_terms: D006027:Glycosides; D006836:Hydro-Lyases / Q000235:genetics / Q000378:metabolism*; D019751:Intramolecular Transferases / Q000235:genetics / Q000378:metabolism*; D015394:Molecular Structure; D009005:Monosaccharides / Q000737:chemistry* / Q000378:metabolism; D011560:Pseudouridine / Q000737:chemistry / Q000378:metabolism; D012313:RNA / Q000737:chemistry / Q000378:metabolism; D017550:Spectroscopy, Fourier Transform Infrared; D014529:Uridine / Q000031:analogs & derivatives* / Q000737:chemistry / Q000378:metabolism
chemical_list: C438934:C-glycoside; D006027:Glycosides; D009005:Monosaccharides; D011560:Pseudouridine; C001943:5-fluorouridine; D012313:RNA; D006836:Hydro-Lyases; C022479:pseudouridylate synthetase; D019751:Intramolecular Transferases; C096995:pseudouridine synthases; D014529:Uridine
references: Mol Cell. 2006 Nov 17;24(4):535-45
references: 17188032
references: J Am Soc Mass Spectrom. 2006 Oct;17(10):1335-1341
references: 16872831
references: J Biol Chem. 1960 May;235:1488-98
references: 13811056
references: J Am Soc Mass Spectrom. 2007 Aug;18(8):1477-92
references: 17583534
references: Rapid Commun Mass Spectrom. 2001;15(1):8-14
references: 11135418
references: Biochemistry. 2011 Jan 25;50(3):426-36
references: 21142053
references: Cell. 2001 Dec 28;107(7):929-39
references: 11779468
references: Biochem Biophys Res Commun. 1969 May 8;35(3):383-8
references: 5788495
references: J Am Chem Soc. 2011 Aug 10;133(31):11826-9
references: 21744792
references: J Biol Chem. 1999 Aug 6;274(32):22225-30
references: 10428788
references: J Am Soc Mass Spectrom. 2010 May;21(5):681-93
references: 20189827
references: J Antibiot (Tokyo). 1975 Sep;28(9):668-75
references: 810468
references: Proc Natl Acad Sci U S A. 1999 Dec 7;96(25):14270-5
references: 10588695
references: J Am Chem Soc. 1965 Oct 20;87(20):4569-76
references: 5845072
references: RNA. 2004 Feb;10(2):192-9
references: 14730018
references: J Am Chem Soc. 2004 Oct 13;126(40):12758-9
references: 15469254
references: Rapid Commun Mass Spectrom. 2005;19(21):3075-85
references: 16206154
references: Biochemistry. 1999 Oct 5;38(40):13106-11
references: 10529181
references: J Am Soc Mass Spectrom. 1992 Jan;3(1):60-70
references: 24242838
references: Biochemistry. 2006 Oct 3;45(39):12029-38
references: 17002302