A novel strategy to rapidly explore potential chemical markers for the discrimination between raw and processed Radix Rehmanniae by UHPLC-TOFMS with multivariate statistical analysis.

In traditional Chinese medicine, raw and processed herbs are used to treat different diseases. Suitable chemical markers are crucial for the discrimination between raw and processed herbs. In this study, a novel strategy using UHPLC-TOFMS coupled with multivariate statistical analysis to rapidly explore potential chemical markers was proposed and validated. Using Radix Rehmanniae as a model herb, batches of raw and processed samples were determined by UHPLC-TOFMS. The datasets of t(R)-m/z pair, ion intensity and sample code were subjected to principal component analysis (PCA) and orthogonal partial least squared discriminant analysis (OPLS-DA) to holistically compare the difference between raw and processed samples. Once a clear cluster was found, extended statistics was performed to generate S-plot, in which the variables (t(R)-m/z pair) contributing most to the difference were clearly indicated as points at the two ends of "S", and the components that correlate to these ions should be the processing-induced transformed components. These transformed components could be regarded as the potential chemical markers that can be used to distinguish between raw and processed herbs. The identity of the potential markers can be identified by comparing the mass/UV spectra and retention time with that of reference compounds and/or tentatively assigned by matching empirical molecular formula with that of the known compounds published. Using this proposed strategy, leonuride or its isomer and 5-(alpha-d-glucopyranosyl-(1-6)-alpha-d-glucopyranosyloxymethyl)-2-furancarboxaldehyde were rapidly explored as the most characteristic markers of raw and processed Radix Rehmanniae, respectively. This newly proposed strategy can not only be used to explore chemical markers but also to investigate the chemical transforming mechanisms underlying traditional herb processing.

Li SL ，Song JZ ，Qiao CF ，Zhou Y ，Qian K ，Lee KH ，Xu HX ... -  《-》

UPLC-PDA-TOFMS based chemical profiling approach to rapidly evaluate chemical consistency between traditional and dispensing granule decoctions of traditional medicine combinatorial formulae.

In the present study, an ultra performance liquid chromatography coupled with photo-diode array detector and time-of-flight mass spectrometry (UPLC-PDA-TOFMS) based chemical profiling approach to rapidly evaluate chemical consistency between traditional and dispensing granule decoctions of traditional medicine combinatorial formulae was proposed and validated using San-Huang-Xie-Xin-Tang (SHXXT) as a model combinatorial formula. Two different kinds of decoctions, namely traditional decoction: water extract of mixed three constituent herbs of SHXXT, and dispensing granules decoction: mixed water extract of each individual herbs of SHXXT, were prepared. Batches of these two kinds of decoction samples were subjected to UPLC-PDA-TOFMS analysis, the datasets of t(R)-m/z pairs, ion intensities and sample codes were processed with supervised orthogonal partial least squared discriminant analysis (OPLS-DA) to holistically compare the difference between these two kinds of decoction samples. Once a clear classification trend was found in score plot, further statistics was performed to generate S-plot, in which the variables (t(R)-m/z pair) contributing most to the difference were clearly depicted as points at the two ends of "S", and the components that correlate to these ions were regarded as the most changed components during decocting of combinatorial formula. The identities of the changed components can be identified by comparing the mass/UV spectra and retention times with those of reference compounds and/or tentatively assigned by matching empirical molecular formulae with those of the known compounds published in the literatures. Using the proposed approach, global chemical difference was found between traditional and dispensing granule decoctions, and berberine, palmatine, epiberberine, baicalin, wonogoside, 2-O-golloyl-1-O-cinnamoylglucose and emodin were identified as the most changed components during decocting SHXXT. It is suggested that this newly established approach could be used practically for the evaluation of chemical consistency between traditional and dispensing granule decoctions of traditional medicine combinatorial formulae.

Li SL ，Song JZ ，Qiao CF ，Zhou Y ，Xu HX ... -  《-》

UHPLC-TOFMS coupled with chemometric method as a powerful technique for rapid exploring of differentiating components between two Ziziphus species.

To rapidly explore the differentiating components and the potential chemical markers for discrimination between those Chinese medicinal herbs with similar chemical characteristics, an ultra-high-performance liquid chromatography (UHPLC)-TOFMS coupled with multivariate statistical analysis method was proposed and validated by using two Ziziphus species (Z. jujuba and Z. jujuba var. spinosa) as the model herbs. After the samples were analyzed using UHPLC-TOFMS, the data sets of retention time (RT)-m/z pairs, ion intensities and sample codes were further processed with orthogonal partial least squared discriminant analysis (OPLS-DA) to holistically compare the difference between the fruits of these two Ziziphus species, and to generate an S-plot. Those compounds correlating to the points at the two ends of "S" were regarded as the most differentiating components between these two kinds of samples. By comparing the mass/UV spectra and retention times with those of reference compounds, these components were finally characterized as zizyberenalic acid, palmitoleic acid, oleic acid, pomonic acid and rutin, and these compounds would be the potential chemical markers for discrimination of these jujube products. The results suggested that this newly established approach could be used to rapidly determine the subtle differences and explore the potential chemical markers for differentiation within the herbs with similar chemical ingredients.

Guo S ，Duan JA ，Tang Y ，Qian D ，Zhu Z ，Qian Y ，Shang E ，Su S ... -  《-》

UPLC-Q-TOF/MS coupled with multivariate statistical analysis as a powerful technique for rapidly exploring potential chemical markers to differentiate between radix paeoniae alba and radix paeoniae rubra.

Luo NC ，Ding W ，Wu J ，Qian DW ，Li ZH ，Qian YF ，Guo JM ，Duan JA ... -  《-》

Discrimination of raw and vinegar-processed Genkwa Flos using metabolomics coupled with multivariate data analysis: a discrimination study with metabolomics coupled with PCA.

In this paper, a novel approach using UPLC-MS (Ultra performance liquid chromatography tandem mass spectrometry) coupled with multivariate statistic analysis was established for the profiling and discrimination of raw and processed herb using Genkwa Flos as a model herb. A batch of raw and processed samples was analyzed, and the datasets of t(R)-m/z pairs, ion intensities and sample codes were subjected to the principal component analysis (PCA). Raw and processed herb showed a clear classification of the two groups on the score plot. Loading plot was performed, and the chemical markers having great contributions to the differentiation were screened out. The identities of the chemical markers were identified by comparing the mass spectra and retention times with those of reference compounds and/or tentatively assigned by matching empirical molecular formulae and mass fragments with those of the known compounds published in the literatures. Based on the proposed strategy, yuanhuacine, genkwadaphnin, genkwanin-5-O-β-d-primeveroside, genkwanine N, genkwanin, 3'-hydroxy-genkwanin and apigenin were explored as representative markers in distinguishing the raw from the processed herbs. The method has been successfully applied in the distinguishing raw from processed herbs. Furthermore, the underlying detoxification mechanism of traditional processing procedure on the herb was predicted, and was related to the changes in the metabolic profiling. This research could be valuable to explore the chemical markers, investigate the mechanism underlying the processing procedure, and promote the quality control and safety application of traditional Chinese herbs.

Geng L ，Sun H ，Yuan Y ，Liu Z ，Cui Y ，Bi K ，Chen X ... -  《-》