Collision induced dissociations of non-derivatized and trimethylsilyl-derivatized estradiols: similarities in fragmentation patterns.

Autor: Jeilani YA; Department of Chemistry and Biochemistry, Spelman College, 350 Spelman Lane, Box 1134, Atlanta, GA, 30314, USA., Li H, Harruna II, Alhooshani KR, Al-Saadi AA
Jazyk: angličtina
Zdroj: Journal of mass spectrometry : JMS [J Mass Spectrom] 2015 Feb; Vol. 50 (2), pp. 308-15.
DOI: 10.1002/jms.3529
Abstrakt: 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.
(Copyright © 2015 John Wiley & Sons, Ltd.)
Databáze: MEDLINE
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