The (un)certainty of selectivity in liquid chromatography tandem mass spectrometry.
We developed a procedure to determine the "identification power" of an LC-MS/MS method operated in the MRM acquisition mode, which is related to its selectivity. The probability of any compound showing the same precursor ion, product ions, and retention time as the compound of interest is used as a measure of selectivity. This is calculated based upon empirical models constructed from three very large compound databases. Based upon the final probability estimation, additional measures to assure unambiguous identification can be taken, like the selection of different or additional product ions. The reported procedure in combination with criteria for relative ion abundances results in a powerful technique to determine the (un)certainty of the selectivity of any LC-MS/MS analysis and thus the risk of false positive results. Furthermore, the procedure is very useful as a tool to validate method selectivity.
RIKILT, Wageningen University and Research Centre, Akkermaalsbos 2, 6708WB, P.O. Box 230, 6700AE Wageningen, The Netherlands. bjorn.berendsen@wur.nl
Bjorn J A
BJ
Berendsen
Linda A M
LA
Stolker
Michel W F
MW
Nielen
D002853:Chromatography, Liquid / Q000379:methods* / Q000592:standards*; D016208:Databases, Factual; D007477:Ions / Q000737:chemistry; D008970:Molecular Weight; D004364:Pharmaceutical Preparations / Q000737:chemistry; D015203:Reproducibility of Results; D012680:Sensitivity and Specificity; D053719:Tandem Mass Spectrometry / Q000379:methods* / Q000592:standards*; D035501:Uncertainty
D007477:Ions; D004364:Pharmaceutical Preparations