Nonlinear Signal Response in Electrospray Mass Spectrometry: Implications for Quantitation of Arsenobetaine Using Stable Isotope Labeling by Liquid Chromatography and Electrospray Orbitrap Mass Spectrometry

Date

2012-05-01

Author

Ouerdane, Laurent
Meija, Juris
Bakirdere, Sezgin
Yang, Lu
Mester, Zoltan

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Isotope amount ratio measurements by electrospray ionization. mass spectrometry show large systematic biases. Moreover, the signal ratio response can vary nonlinearly with respect to the amount ratio depending on the concentration of the analyte or coeluting matrix components, among other things. Since isotope dilution relies inherently on the linearity of response, accurate quantitation is then more difficult to achieve. In this study, we outline a method to eliminate the quantitation errors due to the effects of the nonlinear signal response. The proposed approach is a hybrid of the method of standard additions and isotope dilution allowing correction for nonlinear trend. As a proof of concept, determination of arsenobetaine content in fish tissue was performed using liquid chromatography coupled with a linear quadrupole ion trap (LTQ) Orbitrap mass spectrometer. The nonlinear isotope dilution method could, in principle, be applied to correct isotope ratio measurement biases in popular relative quantitation methods of biomolecules such as stable isotope labeling by amino acids in cell culture (SILAC), isotope-coded affinity tag (ICAT), or isobaric tags for relative and absolute quantification (iTRAQ).

Subject Keywords

Calibration Curves, Accurate Mass, Identifications, Ions

URI

https://hdl.handle.net/11511/68071

Journal

ANALYTICAL CHEMISTRY

DOI

https://doi.org/10.1021/ac203137n

Collections

Department of Chemistry, Article

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Citation Formats

L. Ouerdane, J. Meija, S. Bakirdere, L. Yang, and Z. Mester, “Nonlinear Signal Response in Electrospray Mass Spectrometry: Implications for Quantitation of Arsenobetaine Using Stable Isotope Labeling by Liquid Chromatography and Electrospray Orbitrap Mass Spectrometry,” ANALYTICAL CHEMISTRY, pp. 3958–3964, 2012, Accessed: 00, 2020. [Online]. Available: https://hdl.handle.net/11511/68071.