Neutral Loss Ion Mapping Experiment Combined with Precursor Mass List and Dynamic Exclusion for Screening Unstable Malonyl Glucoside Conjugates

Abstract

Abstract. Malonates are one type of the acylation conjugates and found abundantly in ginseng and soybean. Malonyl conjugates of ginsenosides and isoflavone glycosides were often considered as the characteristic components to evaluate various species and different forms of ginseng and soybean products because of their thermal instability. Another famous isoflavonoid-rich leguminous traditional Chinese medicine (TCM), named Puerarin lobata (Gegen), has also been reported to contain malonyl daidzin and malonyl genistin. However, the conjugates were found to present in very low amount and particularly unstable in the negative ion mode scan using LTQ Orbitrap mass spectrometry with electrospray ionization (ESI). In order to screen and characterize the malonyl conjugates in Gegen, a specific method was designed and developed combining neutral loss ion mapping (NLIM) experiment and precursor mass list (PL) triggered data dependent acquisition (DDA). Along with the activation of dynamic exclusion (DE), the method was proven to be specific and efficient for searching the malonate derivatives from Gegen. Two samples were examined by the established method. A total of 66 compounds were found, and 43 of them were malonates of isoflavone glycoside. Very few compounds were reported previously in Gegen. The results are helpful to understand the constituents of Gegen with more insight. The study not only provided a method for analyzing the malonyl conjugates from complex matrices but also explored a way to trace other low amount components in TCMs.

Can Statistical Evaluation Tools for Chromatographic Method Development Assist in the Natural Products Workflow? A Case Study on Selected Species of the Plant Family Malpighiaceae

“…Malonylated flavonoid glycosides were also observed in the phenolic cluster, specifically present in B. laevifolia ( m / z 565.1213 [M + H] + ) and A. septentrionalis ( m / z 521.1296 [M + H] + ), in which both present a neutral loss of 248 Da corresponding to a hexose (162 Da) bonded to a malonyl (86 Da) group . The malonylated flavonoid glycoside at m / z 565.1213 [M + H] + has been previously described for Pyrus spp., , berry plants, , Ambrosia artemisiifolia , Fagonia cretica , and Phyteuma orbiculare ; however, to the best of our knowledge, the one at m / z 521.1296 [M + H] + (C 24 H 25 O 13 ) has not been reported to date.…”

“…The mass spectra were acquired in both the positive and negative modes, separately, in a mass range of 50−1600 Da using the data-dependent acquisition mode (DDA) to obtain MS and MS/ MS data. The parameters used for data acquisition were as follows: capillary voltage of 3.0 kV, cone and desolvation gas flow of 50 and 800 L h −1 , respectively, source temperature of 100 °C, and desolvation temperature of 650 °C with sampling cone and source offset at 40 Heritage and Associated Traditional Knowledge (SISGEN), no. A6FDC2E.…”

“…This study is the first report of this subclass of compounds for the family Malpighiaceae, besides being the first chemical study on the genus Ptilochaeta. This subclass of compounds, containing p-coumaric acid and methoxycaffeic 40 The malonylated flavonoid glycoside at m/z 565.1213 [M + H] + has been previously described for Pyrus spp., 41,42 berry plants, 43,44 Ambrosia artemisiifolia, 45 Fagonia cretica, 46 and Phyteuma orbiculare; 47 however, to the best of our knowledge, the one at m/z 521.1296 [M + H] + (C 24 H 25 O 13 ) has not been reported to date. This study is the first evidence of this subclass of compounds in the family Malpighiaceae.…”

Phenolic Characterization, Antioxidant Activity, and Enzyme Inhibitory Properties of Berberis thunbergii DC. Leaves: A Valuable Source of Phenolic Acids

“…Compound 26 , with M + ion at m/z 551, suffered the neutral loss of 248 Da (malonyl + glucoside), yielding the anthocyanidin named delphinidin at m/z 303, and it was characterized as delphinidin malonyl glucose [23]. Delphinidin was also reported in B. lycium Royle and B. microphylla [24,25], being the most representative anthocyanidin in various species of Berberis [26].…”

Systematic Qualitative and Quantitative Analyses of Wenxin Granule via Ultra-High Performance Liquid Chromatography Coupled with Ion Mobility Quadrupole Time-of-Flight Mass Spectrometry and Triple Quadrupole–Linear Ion Trap Mass Spectrometry

“…However, when facing a complex matrix, DDA techniques often have low coverage for the components of interest. This issue can be partially solved by adding the precursor ions list (PIL) containing the target masses or the exclusion list (EL) containing the meaningless masses [ 19 , 20 ]. It is very impressive that ion mobility mass spectrometry (IM-MS) has been increasingly applied in TCM analysis recently, which can enable the additional separation of the gas-phase ions according to their charge, size, and shape, leading to more confident characterization of the chemical components of TCM compounds [ 21 ].…”