Discrimination Between Fructus Gardeniae (ZZ) and Fructus Gardeniae Grandiflorae (SZZ) Based on Fingerprint Coupled with Chemometrics and Quantitative Analysis

Abstract

Fructus Gardeniae, known as Zhi-zi in China, has been used as Chinese herbal medicine and functional health food for thousands of years. Fructus Gardeniae Grandiflorae, named as Shui-zhizi, is a counterfeit herb of Fructus Gardeniae. In order to discriminate these two varieties, based on ultra-high-performance liquid chromatography, an analysis method of fingerprints of Fructus Gardeniae and Fructus Gardeniae Grandiflorae was established. With hierarchical clustering analysis and principal component analysis, they were separated into two groups. Analyzed with partial least squares discriminant analysis, there were differences in chemical compositions between Fructus Gardeniae and Fructus Gardeniae Grandiflorae. Six compounds, crocin I, genipin-1-β-D-gentiobioside and four other unknown compositions were identified as differential marker compositions between them. Furthermore, seven active substances in them were determined simultaneously. Thus, an integral method of ultra-high-performance liquid chromatography fingerprint combined with chemometrics analysis and quantitative assessment was established. It could be utilized in characterization, quality evaluation of Fructus Gardeniae and could be applied for discriminating Fructus Gardeniae from Fructus Gardeniae Grandiflorae.

Comprehensive quality evaluation of different types of Gardeniae Fructus (Zhizi) and Shuizhizi based on LC-MS/MS

“…PCA and OPLS-DA, as commonly used multivariate statistical analysis methods, can achieve sample classification. The content of 13 compounds in 25 batches of Zhizi and Shuizhizi was used for PCA analysis, and the results showed that 19 batches of Zhizi and 6 batches of Shuizhizi could be well distinguished ( Figure 3A ), consistent with prior studies ( Cao et al., 2021a ). In order to further understand which compounds have a significant contribution in distinguishing between Zhizi and Shuizhizi , those compounds datas were used for OPLS-DA analysis ( Figure 3B ).…”

“…In recent years, advanced analytical methods such as ultra-flow liquid chromatography coupled with electrospray ionization triple quadrupole mass spectrometry (UFLC-Q-TRAP-MS/MS) and ultra-performance liquid chromatography (UPLC) have been employed for quantitative analysis and fingerprinting of Zhizi , providing insights into optimal harvesting times and quality evaluations from different regions ( Shan et al., 2019 ; Cao et al., 2021a ; Li et al., 2021 ). Additionally, researchers have utilized ultrahigh-performance liquid chromatography/quadrupole-orbitrap mass spectrometry (UHPLC/Q-Orbitrap MS) and UHPLC-triple quadrupole-linear ion trap mass spectrometry (UHPLC-QTRAP-MS) methods to identify thirteen differential markers and quantify metabolites in Zhizi and Shuizhizi , aiding in their differentiation ( Zhang et al., 2024 ).…”