The IMSCal approach to determine collision cross section of multiply charged anions in traveling wave ion mobility spectrometry

The need for appropriate standards to calibrate ion arrival times in traveling wave ion mobility (TWIM) remains an issue for collision cross section (CCS) measurements, particularly in the case of multiply charged anions due to the scarcity of calibrants in the negative ion mode. In order to circumvent constraints raised for standards in the conventional power law calibration, the new approach recently implemented in the IMSCal software (Anal. Chem. 93 (2021) 3542-3550) has been evaluated here to derive CCS of multiply charged anions measured by TWIM. The mathematical model developed in IMSCal to describe ion motion in the TWIM cell was trained with different combinations of phosphoric acid clusters and deprotonated polyalanine standards and performance of so-obtained calibrations was evaluated for multiply deprotonated oligothymidine 10mers used as control analytes. Although optimal composition of the calibrant set could not be fully rationalized, one mandatory condition for best CCS accuracy is to include standards of different charge states to properly model the effects of radial distribution of ions in the TWIM cell. Further improvement of calibration robustness requires that one of these charge states equals that of the analytes to account for the effects of velocity relaxation also incorporated in the IMSCal model. Doing so, experimental CCS values could be readily obtained with relative error below & PLUSMN;5% for anions of charge state up to 6-.

Automated summary

The need for appropriate standards to calibrate ion arrival times in traveling wave ion mobility (TWIM) for collision cross section (CCS) measurements, especially for multiply charged anions, is addressed by a new approach implemented in the IMSCal software. The approach involves training a mathematical model with different combinations of phosphoric acid clusters and deprotonated polyalanine standards to derive CCS values for TWIM-measured multiply charged anions. The inclusion of standards with different charge states, as well as matching the charge state of the analytes, is crucial for accurate CCS determination.