In-depth exploration of spermidines in Goji berry: the identification and semi-quantitation of spermidines by liquid chromatography-tandem mass spectrometry with feature-based molecular network and high performance liquid chromatography

In this study, 164 compounds, including 43 spermidines and 5 spermines, were identified from Lycium barbarum (Zhongning, China) by liquid chromatography-tandem mass spectrometry (LC-MS/MS) coupled with feature-based molecular network (FBMN). The high performance liquid chromatography (HPLC) fingerprint of Goji berry was established, and 16 common peaks were assigned, 13 of which corresponded to spermidines derivatives. Fingerprint similarities of 23 batches ranged from 0.742 to 0.933 relative to the reference chromatogram. Using the self-purified N¹-N¹⁰-dihydrocaffeoyl-caffeoyl-spermidine-di-glucoside as reference standard, an HPLC quantitative method for 1 spermidine and semi-quantitative method for 15 spermidines in Goji berry was developed and validated (linear range: 4.68–574.53 μg/mL, correlation coefficient ( R ² ): 0.9990, recovery rate: 96.4%–101.3%, relative standard deviation (RSD): 1.57%). The total content of 16 spermidines across 23 batches ranged from 2.08 to 4.98 mg/g. These methods are applicable to the quality assessment, offering an analytical framework for the characterization of spermidine type constituents in Goji berry.