Collision induced dissociations of non‐derivatized and trimethylsilyl‐derivatized estradiols: similarities in fragmentation patterns |
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| Authors: | Yassin A Jeilani Huayang Li Issifu I Harruna Khalid R Alhooshani Abdulaziz A Al‐Saadi |
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| Institution: | 1. Department of Chemistry and Biochemistry, Spelman College, Atlanta, GA, USA;2. Chemistry Department, Clark Atlanta University, Atlanta, GA, USA;3. Chemistry Department, King Fahd University of Petroleum and Minerals, Dhahran, Saudi Arabia |
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| 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. Copyright © 2015 John Wiley & Sons, Ltd. |
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| Keywords: | estradiol steroids triple quadrupole mass spectrometry fragmentation mechanism remote charge fragmentation collision induced dissociation DFT |
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