Traveling Wave Ion Mobility-Derived Collision Cross Section Database for Plant Specialized Metabolites: An Application to Ventilago harmandiana Pierre

The combination of ion mobility mass spectrometry (IM -MS) and chromatography is a valuable tool for identifying compounds in natural products. In this study, using an ultra-performance liquid chromatography system coupled to a high-resolution quadrupole/traveling wave ion mobility spectrometry/time-of-flight MS (UPLC-TWIMS-QTOF), we have established and validated a comprehensive TWCCSN2 and MS database for 112 plant specialized metabolites. The database included 15 compounds that were isolated and purified in-house and are not commercially available. We obtained accurate m/z, retention times, fragment ions, and TWIMS-derived CCS (TWCCSN2) values for 207 adducts (ESI+ and ESI-). The database included novel 158 TWCCSN2 values from 79 specialized metabolites. In the presence of plant matrix, the CCS measurement was reproducible and robust. Finally, we demonstrated the application of the database to extend the metabolite coverage of Ventilago harmandiana Pierre. In addition to pyranonaphthoquinones, a group of known specialized metabolites in V. harmandiana, we identified flavonoids, xanthone, naphthofuran, and protocatechuic acid for the first time through targeted analysis. Interestingly, further investigation using IM-MS of unknown features suggested the presence of organonitrogen compounds and lipid and lipid-like molecules, which is also reported for the first time. Data are available on the MassIVE (https://massive.ucsd.edu, data set identifier MSV000090213).

Automated summary

The combination of ion mobility mass spectrometry and chromatography is a powerful tool for identifying compounds in natural products. In this study, a comprehensive database for plant specialized metabolites was established and validated using an ultra-performance liquid chromatography system coupled with a high-resolution quadrupole/traveling wave ion mobility spectrometry/time-of-flight mass spectrometry. The database included both commercially available compounds and those that were isolated and purified in-house, providing accurate information on molecular weight, retention times, fragment ions, and ion mobility-derived collision cross section values. The database was successfully applied to extend the metabolite coverage of Ventilago harmandiana Pierre.