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Electrospray collision‐induced dissociation of testosterone and testosterone hydroxy analogs
Author(s) -
Williams T. M.,
Kind A. J.,
Houghton E.,
Hill D. W.
Publication year - 1999
Publication title -
journal of mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 1076-5174
DOI - 10.1002/(sici)1096-9888(199903)34:3<206::aid-jms785>3.0.co;2-1
Subject(s) - chemistry , mass spectrometry , electrospray ionization , mass spectrum , fragmentation (computing) , ion , dissociation (chemistry) , collision induced dissociation , chromatography , ionization , analytical chemistry (journal) , electrospray , tandem mass spectrometry , organic chemistry , computer science , operating system
Complications with the gas chromatographic analysis of steroidsprompted the use of alternative techniques for their identification.High‐performance liquid chromatography/mass spectrometrywith atmospheric pressure ionization allowed the collection of datafor structural identification of these compounds. The objective ofthis study was to investigate the up‐frontcollision‐induced dissociation (UFCID) electrosprayionization (ESI) mass spectra of testosterone andmonohydroxylated testosterones. The positive ion UFCID ESI massspectrum of testosterone showed three significant ions at m / z 97, 109 and 123. The relative abundance of theseions in the UFCID ESI mass spectra of monohydroxylated testosteronesvaried with the position of the hydroxy group. Statistical dataallowed the prediction of hydroxy group position on testosterone byevaluation of the relative abundance of the m / z 97,109, 121 and 123 ions. Data from the ESI mass spectral analysis oftestosterone in a deuterated solvent and from the analysis ofcholestenone and4‐androstene‐3β,17β‐diol indicatedthat the initial ionization of testosterone occurred at the3‐one position. CID parent ion monitoring analyses of the m / z 97, 109 and 123 ions indicated that each resultedfrom different fragmentation mechanisms and originated directly fromthe [M+H] + parent ion. The elementalcomposition of these fragment ions is proposed based on evidencegathered from the CID analysis of the pseudo‐molecular ions of[1,2‐ 2 H 2 ]‐,[2,2,4,6,6‐ 2 H 5 ]‐,[6,7‐ 2 H 2 ]‐,[7‐ 2 H]‐, [19,19,19‐ 2 H 3 ]‐ and [3,4‐ 13 C 2 ]testosterone. The structure and a possiblemechanism of formation of the m / z 109 and 123 ionsis presented. The results of this study advance the understanding ofthe mechanisms of collision‐induced fragmentation of ions.Copyright © 1999 John Wiley & Sons, Ltd.