BackgroundGinseng (the roots of Panax ginseng Meyer) is a well-known traditional Oriental medicine and is now widely used as a health food. It contains several types of ginsenosides, which are considered the major active medicinal components of ginseng. It has recently been reported that the qualitative and quantitative properties of ginsenosides found in ginseng may differ, depending on cultivation regions, ages, species, and so on. Therefore, it is necessary to study these variations with respect to cultivation ages and regions.MethodsIn this study, 3–6-yr-old roots of P. ginseng were collected from three different cultivation regions. The contents of five ginsenosides (Rb1, Rd, Rc, Re, and Rgl) were measured by rapid resolution liquid chromatography coupled with quadruple–time-of-flight mass spectrometry. The Kruskal–Wallis Rank sum test and multiple t test were used for comparative analysis of the data to evaluate the dynamic changes in the accumulation of these ginsenosides affected by cultivation regions and ages.ResultsThe content and composition of ginsenosides varied significantly among specimens collected from different cultivation regions and having different cultivation ages. For all samples, the content of Rg1 and Re ginsenosides increases with age and this rate of increase is different for each sample. The contents of Rb1, Rc, and Rd varied with cultivation ages in samples from different cultivation regions; especially, Rb1 from a 6-yr-old root showed approximately twofold variation among the samples from three cultivation regions. Furthermore, the content of Rb1 highly correlated with that of Rd (r = 0.89 across all locations and ages).ConclusionIn our study, only the contents of ginsenosides Rg1 and Re were affected by the root age. Ginsenosides Rb1, Rc, and Rd varied widely with ages in samples from different cultivation regions.

BackgroundGinsenosides are not only the principal bioactive components but also the important indexes to the quality assessment of Panax ginseng Meyer. Their contents in cultivated ginseng vary with the growth environment and age. The present study aimed at evaluating the significant difference between 36 cultivated ginseng of different cultivation areas and ages based on the simultaneously determined contents of 14 ginsenosides.MethodsA high-performance liquid chromatography (HPLC) coupled with triple quadrupole mass spectrometer (MS) method was developed and used in the multiple reaction–monitoring (MRM) mode (HPLC-MRM/MS) for the quantitative analysis of ginsenosides. Multivariate statistical analysis, such as principal component analysis and partial least squares-discriminant analysis, was applied to discriminate ginseng samples of various cultivation areas and ages and to discover the differentially accumulated ginsenoside markers.ResultsThe developed HPLC-MRM/MS method was validated to be precise, accurate, stable, sensitive, and repeatable for the simultaneous determination of 14 ginsenosides. It was found that the 3- and 5-yr-old ginseng samples were differentiated distinctly by all means of multivariate statistical analysis, whereas the 4-yr-old samples exhibited similarity to either 3- or 5-yr-old samples in the contents of ginsenosides. Among the 14 detected ginsenosides, Rg1, Rb1, Rb2, Rc, 20(S)-Rf, 20(S)-Rh1, and Rb3 were identified as potential markers for the differentiation of cultivation ages. In addition, the 5-yr-old samples were able to be classified in cultivation area based on the contents of ginsenosides, whereas the 3- and 4-yr-old samples showed little differences in cultivation area.ConclusionThis study demonstrated that the HPLC-MRM/MS method combined with multivariate statistical analysis provides deep insight into the accumulation characteristics of ginsenosides and could be used to differentiate ginseng that are cultivated in different areas and ages.

The mechanism and pathway of heteropoly acid-derived chemical transformation of ginsenoside Re are investigated using multistage tandem mass spectrometry and high-resolution mass spectrometry.

Two quantitative methods (−ESI full scan and −ESI PRM MS) were developed to analyze ginsenosides in ginseng stem-leaf by using UPLC-Q-Exactive Orbitrap/MS. By means of −ESI PRM MS method, the contents of eighteen ginsenosides in Asian ginseng stem-leaf (ASGSL) and American ginseng stem-leaf (AMGSL) were analyzed. The principal component analysis (PCA) model was built to discriminate Asian ginseng stem-leaf (ASGSL) from American ginseng stem-leaf (AMGSL) based on −ESI PRM MS data, and six ginsenosides (F11, Rf, R2, F1, Rb1, and Rb3) were obtained as the markers. To further explore the differences between cultivated ginseng stem-leaf and forest ginseng stem-leaf, the partial least squares-discriminant analysis (PLS-DA) model was built based on −ESI full scan data. And twenty-six markers were selected to discriminate cultivated ginseng stem-leaf (CGSL) from forest ginseng stem-leaf (FGSL). This study provides reliable and effective methods to quantify and discriminate among different types of ginseng stem-leaf in the commercial market.

In this study, white ginseng was used as the raw material, which was fermented with Paecilomyces hepiali through solid culture medium, to produce ginsenosides with modified chemical composition. The characteristic chemical markers of the products thus produced were investigated using rapid resolution liquid chromatography coupled with quadrupole time-of-flight mass spectrometry (RRLC–QTOF–MS). Chemical profiling data were obtained, which were then subjected to multivariate statistical analysis for the systematic comparison of active ingredients in white ginseng and fermented ginseng to understand the beneficial properties of ginsenoside metabolites. In addition, the effects of these components on biological activity were investigated to understand the improvements in the phagocytic function of macrophages in zebrafish. According to the established RRLC–QTOF–MS chemical profiling, the contents in ginsenosides of high molecular weight, especially malonylated protopanaxadiol ginsenosides, were slightly reduced due to the fermentation, which were hydrolyzed into rare and minor ginsenosides. Moreover, the facilitation of macrophage phagocytic function in zebrafish following treatment with different ginseng extracts confirmed that the fermented ginseng is superior to white ginseng. Our results prove that there is a profound change in chemical constituents of ginsenosides during the fermentation process, which has a significant effect on the biological activity of these compounds.

No abstract

The quality of Radix Bupleuri is greatly affected by its growing environment. In this study, Radix Bupleuri samples that were harvested from seven different regions across northwest China were examined by high-performance liquid chromatography (HPLC) and gas chromatography (GC) coupled with mass spectrometry (MS) to reveal significant differences in quality contributed by the cultivation region. An HPLC-MS method was firstly established and used in the multiple reaction monitoring mode for the quantitative analysis of five saikosaponins in Radix Bupleuri so as to evaluate the difference in the absolute content of saikosaponins attributable to the cultivation region. The effect on the components of Radix Bupleuri was further investigated based on the profiles of the representative saponins and volatile compounds, which were extracted from the Radix Bupleuri samples and analyzed by HPLC-MS and GC-MS. Multivariate statistical analysis was employed to differentiate the Radix Bupleuri samples cultivated in different regions and to discover the differential compositions. The developed quantitative method was validated to be accurate, stable, sensitive, and repeatable for the determination of five saikosaponins. Further statistical tests revealed that the collected Radix Bupleuri samples were distinctly different from each other in terms of both saponins and volatile compounds, based on the provinces where they were grown. In addition, twenty-eight saponins and fifty-eight volatile compounds were identified as the differentially accumulated compositions that contributed to the discrimination of the Radix Bupleuri samples. The Radix Bupleuri samples grown in Shouyang county showed the highest content of saikosaponins. All of the results indicated that the cultivation region significantly affected the accumulation and diversity of the main chemical components of Radix Bupleuri. The findings of this research provide insights into the effect of the cultivation region on the quality of Radix Bupleuri and the differentiation of Radix Bupleuri cultivated in different regions based on the use of HPLC-MS and GC-MS combined with multivariate statistical analysis.

Background In the current phytochemical research on ginseng, the differentiation and structural identification of ginsenosides isomers remain challenging. In this paper, a two-dimensional mass spectrometry (2D-MS) method was developed and combined with statistical analysis for the direct differentiation, identification, and relative quantification of protopanaxadiol (PPD)-type ginsenoside isomers. Methods Collision-induced dissociation was performed at successive collision energy values to produce distinct profiles of the intensity fraction (IF) and ratio of intensity (RI) of the fragment ions. To amplify the differences in tandem mass spectra between isomers, IF and RI were plotted against collision energy. The resulting data distributions were then used to obtain the parameters of the fitted curves, which were used to evaluate the statistical significance of the differences between these distributions via the unpaired t test. Results A triplet and two pairs of PPD-type ginsenoside isomers were differentiated and identified by their distinct IF and RI distributions. In addition, the fragmentation preference of PPD-type ginsenosides was determined on the basis of the activation energy. The developed 2D-MS method was also extended to quantitatively determine the molar composition of ginsenoside isomers in mixtures of biotransformation products. Conclusion In comparison with conventional mass spectrometry methods, 2D-MS provides more direct insights into the subtle structural differences between isomers and can be used as an alternative approach for the differentiation of isomeric ginsenosides and natural products.