Identification of Efficacy-Associated Markers to Discriminate Flos Chrysanthemum and Flos Chrysanthemi Indici Based on Fingerprint–Activity Relationship Modeling: A Combined Evaluation over Chemical Consistence and Quality Consistence

Abstract

Monitoring the quality consistency of traditional Chinese medicines, or herbal medicines (HMs), is the basis of assuring the efficacy and safety of HMs during clinical applications. The purpose of this work was to characterize the difference in hydrophilic antioxidants and related bioactivities between Flos Chrysanthemum (JH) and its wild relatives (Chrysanthemum indicum L.; YJH) based on the establishment of fingerprint–efficacy relationship modeling. The concentrations of the total phenolics and flavonoids of JH samples were shown to be generally higher than those of YJH, but the concentration distribution ranges of YJH were significantly greater compared to JH samples, possibly related to environmental stress factors leading to the concentration fluctuations of phytochemicals during the growth and flowering of Chrysanthemum cultivars. Correspondingly, the total antioxidant capabilities of JH were greatly higher than those of YJH samples, as revealed by chemical assays, including DPPH and ABTS radical scavenging activities and FRAP assays. In addition, cellular-based antioxidant activities confirmed the results of chemical assays, suggesting that the differences in antioxidant activities among the different types of Chrysanthemums were obvious. The extracts from YJH and JH samples showed significant α-glucosidase inhibitory activity and lipase-inhibitory activity, implying the modulatory effects on lipid and glucose metabolisms, which were also confirmed by an untargeted cell-based metabolomics approach. The selected common peaks by similarity analysis contributed to the discrimination of YJH and JH samples, and the modeling of the fingerprint–bioactivity relationship identified neochlorogenic acid, isochlorogenic acid A, and linarin as efficacy-associated chemical markers. These results have demonstrated that integrating HPLC fingerprints and the analysis of similarity indexes coupled with antioxidant activities and enzyme-inhibitory activities provides a rapid and effective approach to monitoring the quality consistency of YJH/JH samples.

Separation, identification, and fingerprinting of antioxidant components in persimmon (Diospyros kaki) leaves by offline two‐dimensional liquid chromatography with electrochemical detection and tandem mass spectrometry

“…In comparison with the fractions obtained from 1 D-LC (Figure S1) and the standard solution, 33 peaks were identified. They were gallic acid (1), (E)GC-(E)GC/GC (5), protocatechuic acid (6), (E)GC-(E)C isomer (7), neochlorogenic acid (8), (E)GC-(E)C ( 9), catechin (10), chlorogenic acid/2×(E)GC-(E)C ( 12), p-coumaric acid isomer (13), procyanidin B2 (14), EGCG (15), p-coumaric acid (17), orientin (18), myricetin-O-hexoside (20,21), hyperoside (22), isoquercitrin (23), methyl rhamnoflavone In fingerprint studies, similarity is often used to compare the proximity and differences between chromatograms. Cosine Algorithm is a commonly used method for simi- larity evaluation [38].…”

“…The chemical composition of medicinal and edible plants is complex, generally containing compounds such as flavonoids, phenols, terpenoids, saponins, etc., which have a variety of pharmacological effects, even from multiple active ingredients acting through multiple targets [11]. Fingerprinting technology is considered a powerful tool for quality control [12,13]. High-performance liquid chromatography (HPLC) and ultra-HPLC (UHPLC) are the most commonly used methods for generating fingerprints.…”