Mass spectrometry analysis of saponins

Abstract

Saponins are amphiphilic molecules of pharmaceutical interest and most of their biological activities (i.e., cytotoxic, hemolytic, fungicide, etc.) are associated to their membranolytic properties. These molecules are secondary metabolites present in numerous plants and in some marine animals, such as sea cucumbers and starfishes. Structurally, all saponins correspond to the combination of a hydrophilic glycan, consisting of sugar chain(s), linked to a hydrophobic triterpenoidic or steroidic aglycone, named the sapogenin. Saponins present a high structural diversity and their structural characterization remains extremely challenging. Ideally, saponin structures are best established using nuclear magnetic resonance experiments conducted on isolated molecules. However, the extreme structural diversity of saponins makes them challenging from a structural analysis point of view since, most of the time, saponin extracts consist in a huge number of congeners presenting only subtle structural differences. In the present review, we wish to offer an overview of the literature related to the development of mass spectrometry for the study of saponins. This review will demonstrate that most of the past and current mass spectrometry methods, including electron, electrospray and matrix‐assisted laser desorption/ionization ionizations, gas/liquid chromatography coupled to (tandem) mass spectrometry, collision‐induced dissociation including MS3 experiments, multiple reaction monitoring based quantification, ion mobility experiments, and so forth, have been used for saponin investigations with great success on enriched extracts but also directly on tissues using imaging methods.

Microwave-Assisted Desulfation of the Hemolytic Saponins Extracted from Holothuria scabra Viscera

“…State-of-the-art Mass Spectrometry (MS) methods, including Matrix-assisted Laser Desorption/Ionization experiments (MALDI) [47], Liquid Chromatography separation (LC-MS) [48], accurate mass measurements (HRMS-High Resolution MS) [49], and Collisioninduced Dissociation experiments (CID or MSMS analysis) [50], will be used to afford the most accurate description of the saponin molecules present in the native and modified extracts. MS is now largely recognized as the standard method for saponin analysis [51]. Selectively removing the sulfate group of the H. scabra saponins could contribute to validate the hypothetical role of the sulfate group present on these defensive chemicals.…”

Impact of the Hydrolysis and Methanolysis of Bidesmosidic Chenopodium quinoa Saponins on Their Hemolytic Activity

“…The characterization of the saponins contained in the NE is achieved using the mass spectrometry (MS) protocol developed in our laboratory [ 46 ], combining MALDI-MS, accurate mass measurements (HRMS) and LC-MS (MS) experiments. The saponin identification is based on reference studies by Madl et al [ 37 ], Kuljanabhagavad et al [ 39 ] and Colson et al [ 40 ].…”

Saponins as Natural Emulsifiers for Nanoemulsions

“…Given this context, the most commonly employed technique is liquid chromatography (high-performance liquid chromatography, HPLC, or ultraperformance liquid chromatography, UPLC). However, due to the complexity of saponins, this analysis can be combined with diode array detection (HPLC-DAD), electrospray ionization tandem mass spectrometry with evaporative light scattering detector (HPLC-ELSD-ESI-MS), or quadrupole time-of-flight mass spectrometry (UPLC-QToF/MS). , According to Savarino et al, mass spectrometry methods have, nowadays, achieved the maturity to allow the identification of saponins in plant extracts, even though saponins usually occur as multicomponent mixtures with compounds of similar structure. The nuclear magnetic resonance (NMR) spectroscopy technique (1D and 2D) has also been reported to establish saponin structures. , The appropriate chemical characterization of saponins and saponin-rich extracts can also play a key role to determine the composition–properties relationship, helping to evaluate their suitability toward final applications.…”