Abstract
Two-dimensional mass spectrometry (2D MS) is a data-independent tandem mass spectrometry technique in which precursor and fragment ion species can be correlated without the need for prior ion isolation. The behavior of phase in 2D Fourier transform mass spectrometry is investigated with respect to the calculation of phase-corrected absorption-mode 2D mass spectra. 2D MS datasets have a phase that is defined differently in each dimension. In both dimensions, the phase behavior of precursor and fragment ions is found to be different. The dependence of the phase for both precursor and fragment ion signals on various parameters (e.g., modulation frequency, shape of the fragmentation zone) is discussed. Experimental data confirms the theoretical calculations of the phase in each dimension. Understanding the phase relationships in a 2D mass spectrum is beneficial to the development of possible algorithms for phase correction, which may improve both the signal-to-noise ratio and the resolving power of peaks in 2D mass spectra.
Highlights
Two-dimensional mass spectrometry (2D MS) is a dataindependent tandem mass spectrometry technique in which precursor and fragment ion species can be correlated without the need for prior ion isolation [1]
Two precursor ions can be assigned in the spectrum MH33+ and MH22+ of substance P, as well as fragments that are characteristic of electron capture dissociation (ECD)
The middle column shows the evolution of the intensity of the MH22+ precursor ion, the left column shows the evolution of the intensity of the c5 fragment, and the right column shows the evolution of the intensity of the c7 fragment
Summary
Two-dimensional mass spectrometry (2D MS) is a dataindependent tandem mass spectrometry technique in which precursor and fragment ion species can be correlated without the need for prior ion isolation [1]. The fragmentation patterns of all ions from a complex sample can be mapped in a. M. A. van Agthoven et al.: Phases in 2DMS single 2D mass spectrum from one experiment. The experiment time and sample consumption are independent of sample complexity. Because there is no ion isolation and the ion signals are multiplexed, the signal-to-noise improves with the resolving power for more accurate precursor-fragment ion correlation. Using isotopic distributions of fragment ions, the correlation between precursor and fragment ions can be achieved through their m/z ratio and their charge state [2]
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