Sidebands in Fourier transform ion cyclotron resonance mass spectra

Sidebands in mass spectra are an intrinsic feature of Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Appearance of the sidebands there is detrimental for the analytical performance, especially in case of complex mixtures analyzed at high resolution. Yet, the sidebands have a practical potential as well. Specifically, they can be applied for fine tuning of ICR cells and were previously employed to improve mass measurement accuracy for small molecules and atoms in fundamental physics experiments. Moreover, experimental characteristics of sidebands allow evaluating the theory of the ICR signal, which provides the metrological basis in FT-ICR MS. Here, we revisit the sidebands phenomenon in the conventional FT-ICR MS, specifically applied to macromolecules. We extend the previous reports on sidebands by examining the appearance of sidebands as functions of ICR cell trapping potentials, resolution, and number of charges for the first three harmonics of the reduced cyclotron frequency. Next, we develop an analytical model of sidebands that contributes to the existing theory of the ICR signal by showing the origin of sidebands to be the result of the broadband amplitude-phase modulation occurring in the ICR signal. Finally, we evaluate the theory of the ICR signal on the basis of the obtained experimental sidebands. Further progress in the theory of the ICR signal shall outline the way for further improvements in FT-ICR MS performance.

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► Sidebands of reduced cyclotron frequency harmonics in experimental FT-ICR spectra.
► Evaluation of the existing theory of ICR signal on the basis of the experimental data.
► An analytical model showing the physical origin of sidebands in FT-ICR spectra.
► Sidebands as a result of broadband amplitude-phase modulation occurring in ICR signal.