Use of ion mobility mass spectrometry to enhance cumulative analytical specificity and separation to profile 6‐C/8‐C‐glycosylflavone critical isomer pairs and known–unknowns in medicinal plants. Issue 4 (19th March 2019)

• Record Type: Journal Article
• Authors: McCullagh, Michael; Pereira, Cintia Alessandra Matiucci; Yariwake, Janete Harumi
• Is Part Of: Phytochemical analysis. Volume 30:Issue 4(2019)
• Page Start: 424
• Page End: 436
• Publication Date: 2019-03-19
• Subjects: authentication profiling -- known−unknowns -- CCS -- C‐glycosylflavone isomers -- ion mobility mass spectrometry; Plants -- Analysis -- Periodicals; Plants -- chemistry -- Periodicals; 572.2
• DOI: 10.1002/pca.2825
• Languages: English
• ISSNs: 0958-0344

Abstract

Abstract: Introduction: Plant medicine/herbal extracts are typically complex, encompassing a wide range of flavonoid diversity and biological benefits. Combined with a lack of standards; species authentication profiling is a challenge. A non‐targeted screening strategy using two‐dimensional (2D) separation and specificity of ultra‐high‐performance liquid chromatography ion mobility collision‐induced dissociation mass spectrometry (UHPLC‐IM‐CID‐MS) has been investigated, to identify the 6 ‐C and 8 ‐C ‐glycosylflavone isomer orientin/isoorientin and vitexin/isovitexin pairs in Passiflora species. Utilising available standards and "known–unknowns" a reference CCS (collision cross‐section) speciation finger print for Passiflora extracts could be generated to illustrate species profiling. Material and Methods: SPE was performed to extract flavonoids of interest from powdered and ground Passiflora leaf. Chromatographic separation was achieved via UHPLC and analysis performed using positive/negative ion electrospray coupled with linear T‐wave IM‐MS (calibrated to perform accurate mass and CCS measurements). Results: Comparative phytochemical screening of Passiflora alata, P. edulis, P. incarnata and P. caerulea leaf extracts has generated CCS, CID IM product ion spectra, 2D separation with UHPLC‐IM‐MS, enabling the unequivocal identification of flavone C‐glycosides in complex extracts. A phytochemical reference CCS library was generated comprised of "knowns" and "known–unknowns". Isomers have been differentiated using a CCS metric enabling novel CCS specific isomeric quantitation of co‐eluting isomers. Conclusions: The screening approach illustrated has the potential to play an important role in the profiling of medicinal plants to determine phytochemical make‐up and improve consumer safety through generation of highly specific speciation profiles. Abstract : Natural product plant matrices are typically complex, encompassing a wide range of flavonoid diversity. Passiflora leaf extracts have been analysed using UHPLC‐IM‐MS 2D separation and specificity. CCS values have been determined to differentiate isomeric marker critical pairs. Chromatographically coeluting isomeric product ion spectra have been deconvoluted. In addition cumulative specificity incorporating CCS has been used to produce a highly specific "known‐unkown" speciation fingerprint and the combination of CCS with 2D separation has enabled novel isomeric quantitation.