Juha T Kokkonen | PubMed Health

PubMed2004

Analysis of anabolic steroids by partial filling micellar electrokinetic capillary chromatography and electrospray mass spectrometry.

A partial filling micellar electrokinetic capillary chromatography (PF-MEKC) separation of six anabolic androgenic steroids (androstenedione, metandienone, fluoxymesterone, methyltestosterone, 17-epimetandienone and testosterone) is introduced. The method utilises a mixed micellar solution consisting of sodium dodecyl sulphate (SDS) and sodium taurocholate. The analytes are detected with a photodiode array detector at 247 nm wavelength. Methyltestosterone is used as internal standard. The detection limits were 39 microg/L for androstenedione, 40 microg/L for testosterone, 45 microg/L for fluoxymesterone, 45-90 microg/L for 17-epimetandienone, 59 microg/L for methyltestosterone and 90 microg/L for metandienone. Linear correlation between concentration (0.1-5.0 mg/L) and detector response was obtained with r2 of 0.994 for fluoxymesterone, 0.998 for 17-epimetandienone and 0.999 for androstenedione, metandienone and testosterone. In addition, ionisation of the investigated compounds in electrospray mass spectrometry (ESI-MS) was studied in positive ion mode. The most intense signal (100%) was the protonated molecular ion [M + H]+, except for 17-epimetandienone, which gave its strongest signal at m/z corresponding to [M - H2O + H]+. Finally, separation and identification of fluoxymesterone, androstenedione and testosterone by PF-MEKC-ESI-MS is described. This is the first use of PF-MEKC and PF-MEKC-ESI-MS assays for anabolic androgenic steroids.

Anabolic Agents↗

PubMed2002

Computing positional isotopomer distributions from tandem mass spectrometric data.

The isotopomer distributions of metabolites are invaluable pieces of information in the computation of the flux distribution in a metabolic network. We describe the use of tandem mass spectrometry with the daughter ion scanning technique in the discovery of positional isotopomer distributions (PID). This technique increases the possibilities of mass spectrometry since given the same fragment ions, it uncovers more information than the full scanning mode. The mathematics of the new technique is slightly more complicated than the techniques needed by full scanning mode methods. Our experiments, however, show that in practice the inadequacy of the fragmentation of amino acids in the tandem mass spectrometer does not allow uncovering the PID exactly even if the daughter ion scanning is used. The computational techniques have been implemented in a MATLAB application called PIDC (Positional Isotopomer Distribution Calculator).

Alanine↗