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 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.     

New variants in the total synthesis of 14β-hydroxy-17α,R-8α,9β-estradiol derivatives

Two procedures were developed for the synthesis of 17-alkyl-8,9-estra-1,3,5(10)-triene-3,14,17-triols from 3-methoxy-estra-1,3,5(10),8(9),14(15)-pentaene-17-one (1) using photosensitized oxidation by atmospheric oxygen or ionic hydrogenation in the presence of oxygen. It was shown that 17-hexynyl-8,9-estra-1,3,5(10)-triene-3,14,17-triol (23) and its 3-methoxy derivative (26) inhibit K⁺,Na⁺-ATPase, with inhibition degree increasing on introduction of an oxygen-containing substituent into position 17. For the first time steroids were found with ₂-adrenoblocking action.Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 1, pp. 207–212, January, 1993.     

Magnetic sorbent modified by humate for the extraction of alkylphenols,bisphenol A and estradiol

A sorbent has been synthesized from magnetite nanoparticles and a humic acid extracted from sapropel. The sizes of the sorbent nanoparticles and their magnetic core are 218–302 and 14 nm, respectively, the saturation magnetization is 35 emu g^–1. The sorbent provides 87–95% recoveries of alkylphenols, bisphenol A and estradiol with enrichment factors of 1550–1815.