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Abstract: 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. [Copyright &y& Elsevier]

Abstract: 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-(α-d-glucopyranosyl-(1-6)-α-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. [Copyright &y& Elsevier]

Abstract: Eleven major isoflavonoids and three major astragalosides in the xylem and bark of cultivated Radix Astragali (RA) from different cultivated regions of China were determined by high performance liquid chromatography. The results showed that the contents of astragalosides in the bark are up to 74-fold higher than in the xylem, and that thin roots contained more astragalosides than thick roots. Although the contents of isoflavonoids varied between samples, no significant difference was observed between the isoflavonoids content of xylem and bark, or between that of thin and thick roots. It was also found that the chemical profile of isoflavonoids in the xylem and bark are related to their cultivated regions. Constituents in either xylem or bark were divided into five groups according to their chemical structures: (1) Group 1 (G1), contained calycosin and related constituents; (2) Group 2 (G2), contained ononin and related constituents; (3) Group 3 (G3), contained (6aR,11aR)-3-hydroxy-9,10-dimethoxypterocarpan and related constituents; (4) Group 4 (G4), contained (3R)-7,2′-dihydroxy-3′,4′-dimethoxyisoflavan and related constituents; and (5) Group 5 (G5), contained astragalosides, compounds AG I, AG II, and AG IV. Based on the integrated contents of constituents in each group, the cultivated region of RA was successfully distinguished by principal components analysis (PCA). Chemical constituents in RA cultivated from different regions of China were compared and it was concluded that the quality of thin RA roots is better than thick RA roots. [Copyright &y& Elsevier]

Abstract: An UPLC–Q-TOF-MS/MS based chemical profiling method was developed to evaluate decocting-induced chemical transformations in Du–Shen–Tang, the decoction of the root of Panax ginseng. Under the optimized UPLC and Q-TOF-MS/MS conditions, over 50 peaks were separated and detected in Du–Shen–Tang within 18min. The components were identified by comparing the mass spectra and retention time with that of reference compounds, and/or tentatively assigned by elucidating low energy CID fragment ions as well as matching empirical molecular formula with that of the published known compounds. Totally 45 major ginsenosides were identified in Du–Shen–Tang, 21 of which were determined to be newly generated during the decoction of ginseng. The mechanisms involved were further deduced to be hydrolysis, dehydration, decarboxylation and addition reactions of the original ginsenosides in white ginseng through analyzing mimic decoctions of 13 pure reference ginsenosides. Significant difference in chemical profiles between decoctions of two batches of white ginseng suggested that storage duration or other factors significantly influenced the quality consistency of not only the crude drug but also the decoction (Du–Shen–Tang) of white ginseng. [ABSTRACT FROM AUTHOR]

Abstract: In a well-controlled experiment, outliers discriminated by robust principal component analysis (RPCA) represent contents in samples which are of particular quality distinguishable from the rest of the others, therefore chemical constituents in a natural product causing discrimination between outliers and the majority of samples could be considered as analytical markers for quality control. Based on this strategy, a novel approach for rapidly exploring characteristic analytical markers was proposed for the quality control of extract granules of Radix Salviae Miltiorrhizae (EGRSM). In this study, large sizes of samples were analyzed via high-throughput ultra-high performance liquid chromatography–ultraviolet–quadrupole time-of-flight mass spectrometry (UHPLC–UV–Q-Tof MS). RPCA was first performed on the three groups of samples: RSM (the raw material), the in-house prepared aqueous extract of Radix Salviae Miltiorrhizae (AERSM) and commercial product of EGRSM, to determine the variation of specific constituents between raw material and the final products as well as the effect of manufacturing process on the overall quality. Then RPCA was performed on the commercial products of EGRSM to explore the applicability of identified characteristic markers for the quality control of EGRSM. Candidate markers were extracted by RPCA, and their molecular formulae were determined by high resolution electrospray ionization-mass spectrometric (ESI-MS) analysis. The suitability of identified markers was then evaluated by determining the relationship between quantities of the identified markers with their antioxidant activities biologically, and further confirmed in a variety of samples. In conclusion, the combination of RPCA with UHPLC–UV–Q-Tof MS is a reliable means to identify chemical markers for evaluating quality of herbal medicines. [Copyright &y& Elsevier]

Abstract: In this study, an ultra-performance liquid chromatography/photo-diode-array/quadrupole time-of-flight mass spectrometry (UPLC-PDA-QTOFMS) based chemical profiling method was established for rapid global quality evaluation of Radix Paeoniae. By virtue of the high resolution, high speed of UPLC and the accurate mass measurement of TOFMS, a total of 40 components including 29 monoterpene glycosides, 8 galloyl glucoses and 3 phenolic compounds were simultaneously separated within 12min, and identified through the matching of empirical molecular formulae with those of published components in the in-house library, and were further elucidated by adjusted lower energy collision-induced dissociation (CID) mass spectra. Among forty components, five monoterpene glycoside sulfonates were identified as novel components. The established method was successfully applied to rapidly and globally compare the quality of Radix Paeoniae Alba and Radix Paeoniae Rubra, two post-harvesting handled products of Radix Paeoniae. Together with paeoniflorin sulfonate, five newly assigned monoterpene glycoside sulfonates were characteristic markers to detect non-official sulfur dioxide gas fumigated Radix Paeoniae Alba samples. It could be concluded that UPLC-PDA-QTOFMS based chemical profiling is a powerful approach for the global quality evaluation of Radix Paeoniae as well as other herbal medicines. [Copyright &y& Elsevier]