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Ionization Suppression and Recovery in Direct Biofluid Analysis Using Paper Spray Mass Spectrometry

NCJ Number
250018
Journal
Journal of the American Society for Mass Spectrometry Volume: 27 Issue: 4 Dated: April 2016 Pages: 726-734
Author(s)
Date Published
April 2016
Length
9 pages
Annotation
Paper spray mass spectrometry is a method for the direct analysis of biofluid samples in which extraction of analytes from dried biofluid spots and electrospray ionization occur from the paper on which the dried sample is stored. This study examined matrix effects in the analysis of small molecule drugs from urine, plasma, and whole blood.
Abstract

The general method was to spike stable isotope labeled analogs of each analyte into the spray solvent, while the analyte itself was in the dried biofluid. Intensity of the labeled analog is proportional to ionization efficiency; whereas, the ratio of the analyte intensity to the labeled analog in the spray solvent is proportional to recovery. Ion suppression and recovery were found to be compound- and matrix-dependent. Highest levels of ion suppression were obtained for poor ionizers (e.g., analytes lacking basic aliphatic amine groups) in urine and approached -90 percent. Ion suppression was much lower or even absent for good ionizers (analytes with aliphatic amines) in dried blood spots. Recovery was generally highest in urine and lowest in blood. The study also examined the effect of two experimental parameters on ion suppression and recovery: the spray solvent and the sample position (how far away from the paper tip the dried sample was spotted). Finally, the change in ion suppression and analyte elution as a function of time was examined by carrying out a paper spray analysis of dried plasma spots for 5 min by continually replenishing the spray solvent. (Publisher abstract modified)

Date Published: April 1, 2016