*3.8. HPLC-HRMS/MS Analysis*

The HRMS analysis was carried out on MaXis 4G instrument (Bruker Daltonics, Bremen, Germany) coupled to an Ultimate 3000 HPLC (Thermo Fisher Scientific, Bremen, Germany). HPLC-method was applied as follows: the spectrometer using a gradient (solvent A: 0.1% formic acid (FA) in H2O, and solvent B: 0.06% formic acid in acetonitrile), a gradient of 10–100% B in 45 min, 100% B for an additional 10 min, using a flow rate of 0.3 mL/min; 5 μL injection volume and UV detector (UV/VIS) wavelength monitoring at 210, 254, 280, and 360 nm. The separation was carried out on a Nucleoshell 2.7 μm 150 × 2 mm column (Macherey-Nagel, Düren, Germany), and the range for MS acquisition was *m/z* 100–1800. A capillary voltage of 4500 V, nebulizer gas pressure (nitrogen) of 2 (1.6) bar, ion source temperature of 200 ◦C, the dry gas flow of 9 (7) l/min source temperature, and spectral rates of 3 Hz for MS1 and 10 Hz for MS<sup>2</sup> were used. For acquiring MS/MS fragmentation, the ten most intense ions per MS1 were selected for subsequent collisioninduced dissociation (CID) with stepped CID energy applied. The employed parameters for tandem MS were applied as previously detailed by Garg et al. in 2015 [123]. Sodium formate was used as an internal calibrant and Hexakis (2,2-difluoroethoxy) phosphazene (Apollo Scientific Ltd., Stockport, UK) as the lock mass. Data processing was performed using Bruker Daltonics Data Analysis 4.1(Bremen, Germany).
