title: Collision induced dissociations of non-derivatized and trimethylsilyl-derivatized estradiols: similarities in fragmentation patterns.
abstract: Fragmentation mechanisms of estradiol and trimethylsilyl (TMS)-derivatized estradiol were studied by triple quadrupole tandem mass spectrometry (MSMS) and density functional theory (DFT) at B3LYP/6-311G(d,p) level. Collision induced dissociations (CID) of estradiol give product ions that are associated with the cleavage of B, C and D rings. Characteristic fragments from the cleavage of the aromatic ring A were not identified, and this was confirmed with both labeled estradiol and trimethylsilyl (TMS)-derivatized estradiol. The mechanisms are based on charge-site directed, radical-directed and charge remote fragmentations that are consistent with previous studies of steroids. CID spectra show ion pairs at m/z: 145/146, 157/158, 185/186, 211/213 and 225/226 with significant intensities, suggesting that these pairs are not from isotopic contributions. The mechanisms show similarities with some minor differences in the fragmentation patterns between the non-derivatized and the TMS-derivatized estradiol.
authors: Department of Chemistry and Biochemistry, Spelman College, 350 Spelman Lane, Box 1134, Atlanta, GA, 30314, USA.
authors: Yassin A
authors: YA
authors: Jeilani
authors: Huayang
authors: H
authors: Li
authors: Issifu I
authors: II
authors: Harruna
authors: Khalid R
authors: KR
authors: Alhooshani
authors: Abdulaziz A
authors: AA
authors: Al-Saadi
mesh_terms: D004958:Estradiol / Q000737:chemistry*; D007477:Ions / Q000737:chemistry*; D013058:Mass Spectrometry / Q000379:methods*; D008958:Models, Molecular; D014297:Trimethylsilyl Compounds
chemical_list: D007477:Ions; D014297:Trimethylsilyl Compounds; D004958:Estradiol
keywords: DFT; collision induced dissociation; estradiol; fragmentation mechanism; remote charge fragmentation; steroids; triple quadrupole mass spectrometry