Identification of Citri Reticulatae Pericarpium (Chenpi) From Different Cultivars via LC – MS / MS and UPLC Coupled With Multivariate Chemometrics Analysis

ABSTRACT Citri Reticulatae Pericarpium (CP), derived from the peel of Citrus reticulata Blanco and its cultivated varieties, is widely used and has substantial commercial value. However, notable differences in origin, quality, and price are observed among various CP cultivars. To ensure effective quality control and safe clinical use, a reliable and efficient method for distinguishing these cultivars is urgently needed. This study aimed to investigate the chemical profile differences among seven CP cultivars and to establish a rapid and accurate multi‐component quantitative method using ultra‐high‐performance liquid chromatography (UPLC) for their differentiation. Multivariate statistical analyses, including PCA, OPLS‐DA, and HCA, were employed to distinguish the seven cultivars. LC–MS/MS analysis identified 53 compounds, including 48 flavonoids, and nine representative flavonoids were selected for quantitative determination. The developed UPLC‐based method exhibited high specificity, linearity, precision, repeatability, stability, and accuracy. PCA revealed that C. reticulata “Chachi” (GCP), C. reticulata “Succosa” (BDZ), C. reticulata “Tankan” (JG), and C. reticulata “Unshiu” (WZMG) formed distinct clusters, indicating substantial differences in flavonoid composition. In contrast, C. reticulata “Kinokuni” (NFMJ), C. reticulata “Ponkan” (PG), and C. reticulata “Dahongpao” (DHP) grouped together but were further differentiated by PCA and OPLS‐DA, consistent with the HCA results. Hesperetin was quantified exclusively in GCP, suggesting its potential as a cultivar‐specific marker. Although the overall chemical profiles of the seven CP cultivars were similar, their flavonoid contents varied significantly. The combined UPLC quantification and multivariate analyses provide an effective approach for distinguishing major CP cultivars and offer new insights for quality control and future research.