片姜黄及其易混伪品中二苯基庚烷类成分的鉴定及化学计量学分析

Identification and Chemometric Analysis of Diarylheptanoids in Wenyujin Rhizoma Concisum and Its Adulterants

关键词:  片姜黄  二苯基庚烷类  UPLC-Q-TOF MS  质谱裂解规律  中药质量控制  

Key words:  Wenyujin Rhizoma Concisum  diarylheptanoids  UPLC-Q-TOF MS  fragmentation pathways  Traditional Chinese Medicines (TCMs) quality control  

摘要:

目的 对片姜黄及其易混伪品（广西莪术根茎切制品、蓬莪术根茎切制品）中的二苯基庚烷类成分进行系统鉴定和质谱裂解规律研究，并通过化学计量学筛选关键质量标志物，实现片姜黄与易混伪品的区分。方法 采用超高效液相色谱-四极杆-飞行时间质谱（UPLC-Q-TOF MS）技术，通过对比对照品、数据库及相关文献，鉴定片姜黄及其易混伪品的二苯基庚烷类成分，并归纳特征碎片及裂解途径；采用聚类热图分析、主成分分析、正交偏最小二乘法-判别分析等化学计量学方法，筛选质量标志物。结果 系统归纳了9类二苯基庚烷类成分的特征裂解途径，从片姜黄及其易混伪品共鉴定出76个二苯基庚烷类化合物，其中片姜黄中65个，广西莪术根茎切制品中65个，蓬莪术根茎切制品中23个；化学计量学分析显示，二苯基庚烷类成分可实现片姜黄及其易混伪品的区分；基于正交偏最小二乘法-判别分析（OPLS-DA）的VIP分析，筛选了姜黄素、去甲氧基姜黄素等化合物作为鉴别片姜黄和广西莪术根茎切制品、蓬莪术根茎切制品的核心质量标志物。结论 系统鉴定和归纳了片姜黄及其易混伪品中的9种二苯基庚烷类成分的特征裂解途径，通过化学计量法筛选出差异性成分，为片姜黄的物质基础研究和质量控制提供了参考依据。

Abstract:

OBJECTIVE A systematic mass spectrometric identification and fragmentation pathways elucidation of diarylheptanoids was conducted in Wenyujin Rhizoma Concisum and its common adulterants (the dryed rhizome slices of Curcuma kwangsiensis S.G Lee et C.F.Liang and Curcuma phaeocaulis Val). Chemometric analysis was employed to screen critical quality markers for distinguishing authentic Rhizoma Wenyujin Concisum from adulterants. METHODS Ultra-high performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry (UPLC-Q-TOF MS) was employed to identify diarylheptanoids in Rhizoma Wenyujin Concisum and its common adulterants (the dryed rhizomes of C. kwangsiensis and C. phaeocaulis) by comparing with reference standards, databases, and literature data. Characteristic fragment ions and fragmentation pathways were systematically summarized. Chemometric analysis, including cluster heatmap analysis, principal component analysis (PCA), and orthogonal partial least squares-discriminant analysis (OPLS-DA), were applied to screen discriminant quality markers. RESULTS The characteristic fragmentation pathways of nine diarylheptanoids were systematically summarized. A total of 76 diarylheptanoids were comprehensively identified in authentic Rhizoma Wenyujin Concisum and its adulterants. Among them, 65 diarylheptanoids were identified in Wenyujin Rhizoma Concisum, 65 in the dryed rhizome slices of C. kwangsiensis rhizomes, and 23 in the dryed rhizome slices of C. phaeocaulis rhizomes. Chemometric analysis demonstrated that diarylheptanoids could effectively discriminate authentic Wenyujin Rhizoma Concisum from its adulterants. Through VIP analysis based on orthogonal partial least squares-discriminant analysis (OPLS-DA), key quality markers including curcumin and demethoxycurcumin were screened as critical biomarkers for distinguishing Wenyujin Rhizoma Concisum from the dryed rhizome slices of C. kwangsiensis and C. phaeocaulis rhizomes. CONCLUSION This study systematically identified and characterized the fragmentation pathways of nine diarylheptanoid subclasses in Wenyujin Rhizoma Concisum and its common adulterants. Through chemometric analysis, discriminant components were successfully screened. This work provides valuable reference for material basis study and quality standards research of Wenyujin Rhizoma Concisum.