Collision cross section (CCS) measurement by ion cyclotron resonance mass spectrometry with short-time Fourier transform.

RATIONALE: The collision cross section (CCS) is an important shape parameter which is often used in molecular structure investigation. In Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS), the CCS affects the ion signal damping shape due to the effect of ion-neutral collisions. It is potential to obtain ion CCS values from FTICR-MS with the help of a proper ion-collision model.

METHODS: We have developed a rapid method to obtain the ion damping profile and CCS for mixtures by only one FTICR-MS measurement. The method utilizes short-time Fourier transform (STFT) to process FTICR-MS time domain signals. The STFT-processed result is a three-dimensional (3D) spectrum which has an additional time axis in addition to the conventional mass-to-charge ratio and intensity domains. The damping profile of each ion can be recognized from the 3D spectrum.

RESULTS: After extracting the decay profile of a specified ion, all the three ion-neutral collision models were tested in curve fitting. The hard-sphere model was proven to be suitable for our experimental setup. A linear relationship was observed between the CCS value and hard-sphere model parameters. Therefore, the CCS values of all the peaks were obtained through the addition of internal model compounds and linear calibration.

CONCLUSIONS: The proposed method was successfully applied to determine the CCSs of fatty acids and polyalanines in a petroleum gas oil matrix. This technique can be used for simultaneous measurement of cross sections for many ions in congested spectra.