Efficient injection of low‐mass ions into high magnetic field Fourier transform ion cyclotron resonance mass spectrometers

RATIONALE: Low-mass cut-off restrictions for injecting ions from external ion sources into high magnetic fields impose limitations for wide mass range analyses with Fourier transform ion cyclotron resonance (FTICR) instruments. Radio-frequency (RF)-only quadrupole ion guides (QIGs) with higher frequencies can be used to overcome low-mass cut-off in FTICR instruments. METHODS: RF signals (1.0 MHz to 10.0 MHz) were applied to QIGs to transfer externally generated ions from either electron ionization (EI) or electrospray ionization (ESI) sources into ICR cells of 9.4 T FTICR mass spectrometers. Efficiencies of QIGs were evaluated using externally generated ions from: EI of acetone, air, and perfluorotributylamine mixture, EI of gas chromatography (GC)-separated components of a standard sample mixture, and ESI of complex mixtures such as petroleum and fulvic acid samples. RESULTS: We were able to transfer ions with m/z as low as 26 from an external EI source into the ICR cell of a 9.4 T FTICR mass spectrometer and extend the operational low-mass range for ESI-FTICR analyses. High mass resolving power and mass measurement accuracy of GC/FTICR mass spectrometry were utilized to discriminate between oxygenated and non-oxygenated compounds in a 'Grob' sample. Ion losses based on SIMION ion trajectory predictions were consistent with experimental findings. CONCLUSIONS: We demonstrated that the use of high-frequency QIGs can extend the operational lower m/z range for both external EI- and ESI-FTICR mass spectrometers. By considering both ICR and Mathieu equations of motions to describe ion trajectories, theoretical ion ejection thresholds (consistent with our experimental findings) could be predicted.