Quantitative and confirmative performance of liquid chromatography coupled to high-resolution mass spectrometry compared to tandem mass spectrometry
Article first published online: 14 MAR 2011
Copyright © 2011 John Wiley & Sons, Ltd.
Rapid Communications in Mass Spectrometry
Volume 25, Issue 7, pages 979–992, 15 April 2011
How to Cite
Kaufmann, A., Butcher, P., Maden, K., Walker, S. and Widmer, M. (2011), Quantitative and confirmative performance of liquid chromatography coupled to high-resolution mass spectrometry compared to tandem mass spectrometry. Rapid Commun. Mass Spectrom., 25: 979–992. doi: 10.1002/rcm.4952
- Issue published online: 17 MAR 2011
- Article first published online: 14 MAR 2011
- Manuscript Accepted: 22 JAN 2011
- Manuscript Revised: 17 JAN 2011
- Manuscript Received: 11 NOV 2010
The quantitative and confirmative performance of two different mass spectrometry (MS) techniques (high-resolution MS and tandem MS) was critically compared. Evaluated was a new extraction and clean-up protocol which was developed to cover more than 100 different veterinary drugs at trace levels in a number of animal tissues and honey matrices. Both detection techniques, high-resolution mass spectrometry (HRMS) (single-stage Orbitrap instrument operated at 50 000 full width at half maximum) and tandem mass spectrometry (MS/MS) (quadrupole technology) were used to validate the method according to the EU Commission Decision 2002/657/EEC. Equal or even a slightly better quantitative performance was observed for the HRMS-based approach. Sensitivity is higher for unit mass resolution MS/MS if only a subset of the 100 compounds has to be monitored.
Confirmation of suspected positive findings can be done by evaluating the intensity ratio between different MS/MS transitions, or by accurate mass based product ion traces (no precursor selection applied). MS/MS relies on compound-specific optimized transitions; hence the second, confirmatory transition generally shows relatively high ion abundance (fragmentation efficacy). This is often not the case in single-stage HRMS, since a generic (not compound-optimized) collision energy is applied. Hence, confirmation of analytes present at low levels is superior when performed by MS/MS. Slightly better precision, but poorer accuracy (fortified matrix extracts versus pure standard solution) of ion ratios were observed when comparing data obtained by HRMS versus MS/MS. Copyright © 2011 John Wiley & Sons, Ltd.