Dimension-Enhanced Ultra-High Performance Liquid Chromatography/Ion Mobility-Quadrupole Time-of-Flight Mass Spectrometry Combined with Intelligent Peak Annotation for the Rapid Characterization of the Multiple Components from Seeds of Descurainia sophia

Abstract

The complex composition of herbal metabolites necessitates the development of powerful analytical techniques aimed to identify the bioactive components. The seeds of Descurainia sophia (SDS) are utilized in China as a cough and asthma relieving agent. Herein, a dimension-enhanced integral approach, by combining ultra-high performance liquid chromatography/ion mobility-quadrupole time-of-flight mass spectrometry (UHPLC/IM-QTOF-MS) and intelligent peak annotation, was developed to rapidly characterize the multicomponents from SDS. Good chromatographic separation was achieved within 38 min on a UPLC CSH C18 (2.1 × 100 mm, 1.7 μm) column which was eluted by 0.1% formic acid in water (water phase) and acetonitrile (organic phase). Collision-induced dissociation-MS 2 data were acquired by the data-independent high-definition MS E (HDMS E ) in both the negative and positive electrospray ionization modes. A major components knockout strategy was applied to improve the characterization of those minor ingredients by enhancing the injection volume. Moreover, a self-built chemistry library was established, which could be matched by the UNIFI software enabling automatic peak annotation of the obtained HDMS E data. As a result of applying the intelligent peak annotation workflows and further confirmation process, a total of 53 compounds were identified or tentatively characterized from the SDS, including 29 flavonoids, one uridine derivative, four glucosides, one lignin, one phenolic compound, and 17 others. Notably, four-dimensional information related to the structure (e.g., retention time, collision cross section, MS 1 and MS 2 data) was obtained for each component by the developed integral approach, and the results would greatly benefit the quality control of SDS. KEYWORDSDescurainia sophia; multicomponent characterization; ultra-high performance liquid chromatography; ion mobility/quadrupole time-of-flight mass spectrometry; high-definition MS E ; flavonoid

An efficient approach addressing the chemical complexity of Jiawei Fangji Huangqi decoction by integrating ultra‐high‐performance liquid chromatography/ion mobility‐quadrupole time‐of‐flight mass spectrometry and intelligent data processing workflows

“…In total, 134 flavonoids (comprising 31.16% of the total number of compounds) were provisionally identified in the JFH decoction. Flavonoids are known to be one of the main classes of active ingredients in AR [17], GRR [18], PS [19], and DSLS [16]. The negative fragmentation pathways of the flavonoids, regardless of the subclass, involved typical neutral loss (NL) of the sugar moiety to generate a deprotonated aglycone moiety ([A − H] − ); the preferred NL of CO 2 (43.98 Da), CO (27.99 Da), H 2 O (18.01 Da), or CH 2 O (30.01 Da); the radical cleavage of •CH 3 (for compounds containing –OCH 3 ); and retro ‐Diels–Alder (RDA) reactions [20].…”

“…In total, 134 flavonoids (comprising 31.16% of the total number of compounds) were provisionally identified in the JFH decoction. Flavonoids are known to be one of the main classes of active ingredients in AR [17], GRR [18], PS [19], and DSLS [16] ). Accordingly, compound 215# was identified as a formononetin isomer [21].…”

Rapid Profiling and Characterization of the Multicomponents from the Root and Rhizome of Salvia miltiorrhiza by Ultra-High Performance Liquid Chromatography/Ion Mobility-Quadrupole Time-of-Flight Mass Spectrometry in Combination with Computational Peak Annotation Workflows

“…The Vion IM-QTOF platform is a benchtop high-resolution mass spectrometer facilitating the ion mobility separation and convenient determination of the CCS values, by which dimension-enhanced multicomponent characterization can be achieved [17,18,[31][32][33][34]. Key ion source parameters, including the capillary voltage, cone voltage, and RCE, in the negative mode were optimized in sequence, aimed to improve the sensitivity of Vion IM-QTOF for the multicomponent characterization from S. miltiorrhiza.…”

“…Post-data acquisition processing, such as the development of different mass defect filtering vehicles [11,12], precursor ion list (PIL) [13], dynamic exclusion [14], or multiple reaction monitoring (MRM) [15], can be utilized to improve the coverage of DDA. DIA strategies recently receive more applications due to its highest coverage without the loss of MS information [16], such as MS E or high-definition MS E (HDMS E ) [17,18], sequential window acquisition of all theoretical spectra (SWATH) [19], or all ion fragmentation (AIF) [20]). But matching between the precursor ions and the product ions is inevitable prior to interpreting the DIA-MS 2 data [21], which can be performed by developing in-house data processing algorithms (such as MS-DIAL or MS-FINDER [22]) or by using the mature commercial deconvolution software (such as UNIFI TM from Waters).…”

Software Assisted Multi-Tiered Mass Spectrometry Identification of Compounds in Traditional Chinese Medicine: Dalbergia odorifera as an Example

“…The low-throughput plus tedious isolation process of this method confines its application for a holistic and fast analysis of TCM components. In the past decades, due to its unprecedented selectivity and sensitivity, liquid chromatography–tandem mass spectrometry (LC–MS), especially multistage high-resolution MS (HRMS), has become increasingly popular and a most widely used technique for the separation and identification of TCM components [ 5 , 6 , 7 ]. In addition to the masses of the targets, HRMS/MS can convey certain structural information through abundant spectral fragments, which are critical for metabolites identification.…”