Shotgun chemome characterization of Artemisia rupestris L. Using direct infusion-MS/MSALL

In comparison of liquid chromatography, direct infusion is a superior choice to achieve high-throughput measurements. The specificity and selectivity of tandem mass spectrometry (MS/MS) actually result in a so-called MS separation potential when chemical characterization of herbal medicines. Here, a MS/MSᴬᴸᴸ program was introduced to promote DI–MS/MS to be an eligible tool for shotgun chemome characterization of Artemisia rupestris L. that is currently drawing worldwide interests because of the promising antiviral activity. After MS¹ spectral acquisition for the crude extract, the gas phase fractionation concept enabled the precursor ion cohort sequentially entered the collision cell with a stepped unit mass window (step-size as 1 Da) to generate MS² spectra, thus generating a unique property integrating the advantages of both data-dependent and data-independent acquisition manners. Even though being free of chromatographic separation, spectrometric separations were accomplished for by MS/MSᴬᴸᴸ program unless the components shared identical nominal molecular weights. Extensive efforts such as the correlations of MS¹ signals with MS² spectra, structural annotations of fragment ion species, information retrieval in some accessible databases, and referring to the literature data, were devoted for chemical characterization, and as a result, 44 compounds, in total, were structurally identified from 50% aqueous methanol exact of A. rupestris, including 8 caffeoyl quinic acid derivatives, 13 flavonoids, 15 monomeric and dimeric sesquiterpenoids, 4 fatty acids, 2 penylpropanoids, along with 2 other compounds. However, isomers were assigned as an isomeric mixture because their precursor ions always co-existed in a single mass window. Above all, DI–MS/MSᴬᴸᴸ provides an alternative tool for chemome characterization of herbal medicines, in particular when the great measurement workload for a large sample cohort, attributing to the high-throughput advantage.