Rapid Dereplication of Bioactive Compounds in Plant and Food Extracts Using Liquid Chromatography–Electrospray–Tandem Mass Spectrometry

High-throughput screening and identification of common phytochemicals are crucial for lead optimization, drug development and investigation of metabolic pathways in complex herbal extracts. The available databases contain a huge number of compounds, making it challenging and time-consuming to dereplicate valuable compounds. Therefore, the current study aimed to develop an in-house mass spectral library for the rapid dereplication of 31 commonly occurring natural products from different classes using liquid chromatography-electrospray ionization-tandem mass spectrometry (LC-ESI-MS/MS). A total of 31 standards were grouped into two different pools, and each pool was analysed under uniformly optimized conditions in positive ionization mode. A pooling strategy on the basis of log <i>P</i> values and exact masses was adopted to minimize the co-elution and the presence of isomers in the same pool. The MS/MS features of each compound were acquired using [M + H]⁺ and/or [M + Na]⁺ adducts at 25.5-62 eV range as average collision energy and 10, 20, 30 and 40 eV as individual collision energies. The names, molecular formulae, exact masses with <5 ppm error, MS and MS/MS features of analysed reference compounds were used to construct the MS/MS library. The developed MS/MS library was efficiently used for the rapid dereplication and validation of 31 compounds in 15 different food and plant sample extracts. The MS data of 31 reference standards have been submitted to the MetaboLights online database (MTBLS9587). The developed library will be beneficial for the rapid dereplication of biologically valuable compounds in a variety of herbal formulations and food samples.