Simultaneous quantitative analysis of ten bioactive flavonoids in Citri Reticulatae Pericarpium Viride (Qing Pi) by ultrahigh‐performance liquid chromatography and high‐resolution mass spectrometry combined with chemometric methods

Abstract

Introduction: Citri Reticulatae Pericarpium Viride (Qing Pi in Chinese) is a clinically effective Chinese herb, which contains biologically valuable flavonoids. Qing Pi is divided into two commodity specifications, Si Hua Qing Pi (SHQP) and Ge Qing Pi (GQP), based on the harvesting time. The flavonoid contents in Qing Pi from different origins and commodity specifications may vary significantly, which will affect their therapeutic functions. Thus, it is crucial to set up a reliable and comprehensive quality evaluation method for flavonoid analysis in Qing Pi.Objectives: We aimed to establish a rapid and sensitive ultrahigh-performance liquid chromatography method coupled with diode-array detection and high-resolution mass spectrometry (UPLC-DAD-HRMS) for identification and quantification of ten flavonoids in Qing Pi. Chemometric methods were further applied to distinguish Qing Pi of different origins and specifications.Methodology: An UPLC-DAD-HRMS method was developed for the simultaneous separation and quantification of ten flavonoids in 46 batches of Qing Pi samples from different sources in China. Chemometric approaches were applied to discriminate Qing Pi from different origins and commodity specifications.Results: The chemometric procedures (i.e., hierarchical clustering analysis and principal component analysis) were employed to identify the differences of Qing Pi samples with different origins and commodity specifications. The results showed that the contents of ten flavonoids in Qing Pi samples of different origins were significantly different, and the same results were found out between SHQP and GQP. Conclusions:This study provides a chemical basis for quality control of Qing Pi.

Rapid profiling of potential antitumor polymethoxylated flavonoids in natural products by integrating cell biospecific extraction with neutral loss/diagnostic ion filtering‐based high‐performance liquid chromatography–quadrupole time‐of‐flight tandem mass spectrometry

“…Thus, coeluting with standards, compounds 10 and 11 were unequivocally assigned as tetramethyl‐ O ‐isoscutellarein and tetramethyl‐ O ‐scutellarein 41 . Similarly, compounds 12 and 13 can be identified as nobiletin and 3,5,6,7,8,3′,4′‐heptamethoxyflavone by comparing their HPLC‐QTOF‐MS/MS spectra with those of standards 31 . Compounds 4 , 6 , 9 , and 15 were isomeric compounds with parent ions at m / z 389.1257 ([M + H] + , C 20 H 21 O 8 , 16 Da greater than that of compound 5 ), indicating the presence of one hydroxyl group and five methoxy groups.…”

“…Compound 16 generated characteristic fragment ions at m / z 241.0719 ([ 1,3 A] + ) and 135.0447 ([ 0,2 B] + ), suggesting that the A‐ring contained four methoxy groups and that the B‐ring contained only one methoxy group. By comparing their retention times and fragmentation patterns with standards, compounds 5 , 7 , and 16 were unequivocally confirmed as isosinensetin, sinensetin, and tangeretin 31,41 . Compound 3 showed an [M + H] + ion at m / z 403.1411 (C 21 H 23 O 8 , 30 Da greater than that of 5 ) and a [ 1,3 A] + ion at 211.0627 (the same as that of 5 ), indicating the existence of an additional methoxy group on the B‐ring.…”

“…Citri Reticulatae Pericarpium Viride (CRPV, Qing Pi in Chinese, the immature fruit of C. reticulata Blanco and its cultivars) has been widely used in traditional Chinese medicine to regulate qi, soothe the liver, resolve stagnation, and promote digestion. 30 Investigations on CRPV have received little attention, and most of them have focused on the quantification and discrimination of the main flavonoids, [31][32][33][34] identification of volatile oils, 35 and pharmacological evaluation of crude extracts. 36 Thus, to broaden the clinical application of CRPV, further comprehensive study of its antitumor PMFs is essential.…”

Analyses of Physical and Chemical Compositions of Different Medicinal Specifications of CRPV by Use of Multiple Instrumental Techniques Combined with Multivariate Statistical Analysis

“…and alkaloids (synephrine, N-methyltyraminehydrochloride) are significantly different. While GQP has higher narirutin and hesperidin contents than SHQP, it has comparatively lower contents of nobiletin and tangeretin [ 28 , 29 , 30 ]. Understanding the pharmacodynamic material basis of the two CRPV types would help in guiding their rational clinical use.…”

Study on Closely Related Citrus CMMs based on Chemometrics and Prediction of Components-Targets-Diseases Network by Ingenuity Pathway Analysis

“…AFI is often used to eliminate phlegm and dissipate stagnant qi, while AF relieves gastrointestinal indigestion in a gentle yet effective manner [ 3 , 4 ]. CRPV is mostly used to promote the flow of liver qi, while CRP is commonly utilized to strengthen the spleen and dispel phlegm [ 5 , 6 ]. However, the different chemical features in the four decoction pieces have not been systematically reported, which is not beneficial for understanding the different clinical applications.…”