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

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 associa...

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Bibliographic Details
Published in:Journal of mass spectrometry. 2015-02, Vol.50 (2), p.308-315
Main Authors: Jeilani, Yassin A., Li, Huayang, Harruna, Issifu I., Alhooshani, Khalid R., Al-Saadi, Abdulaziz A.
Format: Article
Language:English
Subjects:
Analogies
Cleavage
collision induced dissociation
DFT
estradiol
Estradiol - chemistry
Fragmentation
fragmentation mechanism
Ion pairs
Ions - chemistry
Mass spectrometry
Mass Spectrometry - methods
Models, Molecular
remote charge fragmentation
Sex hormones
Spectra
Steroids
Trimethylsilyl Compounds
triple quadrupole mass spectrometry
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Summary: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.
ISSN:1076-5174
1096-9888
DOI:10.1002/jms.3529