Characterization and quantitative analysis with GC/TOFMS comparing enhanced separation with tandem-column stop-flow GC and spectral deconvolution of overlapping peaks.

Abstract

Time-of-flight mass spectrometry is unique in that ion abundance ratios are constant over the chromatographic peak profile provided that the peak contains only one component. This provides the means for the automated finding and spectral deconvolution of overlapping chromatographic peaks from completely unknown mixtures if the mass spectra for the overlapping components are sufficiently unique. This can greatly reduce the chromatographic resolution requirements, which allows for very rapid quantitative analysis as well as for high-speed mixture characterization. High-speed GC with stop-flow operation of a series-coupled column ensemble can be used to completely separate some component pairs that coelute from the column ensemble, thus eliminating the need for spectral deconvolution of those mixture components. This provides two options for high-speed qualitative and quantitative analysis, using either the mass spectra from deconvoluted overlapping peaks or the mass spectra from the completely separated peaks obtained with stop-flow operation of the tandem column ensemble. These options are compared with respect to the similarity for spectral matching with a library and to peak area linearity with concentration, calibration plot correlation coefficients, and shot-to-shot reproducibility.