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The chemical composition of Drynaria fortunei, a traditional Chinese herbal medicine, is very complicated. In order to separate these chemicals to obtain their structural information, an orthogonal sample enrichment procedure was established. The ethyl acetate extract of D. fortunei was pre-separated by Sephadex LH-20 × polyamide columns to yield 15 fractions. These fractions were analyzed successively using a reversed-phase Agilent Zorbax SB-C18 column, coupled with diode array detection and electrospray ionization tandem mass spectrometry. The method reduced co-elution and enriched minor compounds on the basis of their chemical features. A total of 369 compounds were detected by LC/MSn, compared to less than 50 compounds without pre-separation. The pretreatment facilitated the analytical separation of flavonoids, proanthocyanidins, triterpenoids, phenolic acids, and lignans in D. fortunei, and allowed a comprehensive chemical profiling of these constituents. This method could be applied to other multicomponent herbal extracts.

A comprehensive two-dimensional liquid chromatography coupled with mass spectrometry method was established to separate and characterize triterpenoid saponins in Gleditsia sinensis, the Chinese herbal medicine Zhu-Ya-Zao used for the treatment of apoplexy. The saponins were separated on an Agilent Zorbax Eclipse plus C18 column (2.1 mm × 150 mm, 1.8 µm) for the first dimension, and a Poroshell 120 phenyl-hexyl column (3.0 mm × 50 mm, 2.7 µm) for the second dimension. Methanol and acetonitrile were used as the organic mobile phase for 1D and 2D, respectively. The theoretical peak capacity was 640, and the orthogonality was 57 %. Particularly, saponins with different numbers of monoterpene groups could be well separated on the second dimension. The structures were characterized by electrospray ionization tandem mass spectrometry in both positive and negative ion modes. In the MS/MS spectra, the relative abundances for [B α + Na]+ and [Y 0α + Na]+ were closely correlated with the number of sugar residues of the α-chain and β-chain, respectively, which facilitated the differentiation of isomers. Finally, a total of 72 saponins with molecular weights greater than 1500 Da were characterized. Among them, 49 compounds, including 2 acetylated saponins, were detected from G. sinensis for the first time.

Guan Xin II decoction (GX II) is a widely used traditional Chinese medicine (TCM) formula for the treatment of coronary heart diseases. However, the comprehensive chemical analysis of the formulated GX II is not clarified yet. An HPLC-DAD-ESI-MS n method was established to analyze GX II and its five component herbs, respectively. A total of 57 compounds, including phenolic acids, glycosides, flavonoids, and alkaloids were identified or tentatively characterized on the basis of their mass spectra or by comparison with reference standards. This is the first time that the chemical composition of GX II was elucidated by LC/MS. The established method will be used for quality control and pharmacokinetic studies of GX II. GX II:Guan Xin II, Guan Xin Er Hao (in Chinese) TCM:traditional Chinese medicine

A sophisticated LC-ESI-MS (n) method was utilized for the analysis of the phenolic compounds in five unofficial RHEUM species for the first time. These species belong to the section deserticola Maxim. of the Polygonaceae family, including Rheum racemiferum Maxim., R. nanum Siev. ex Pall., R. delavayi Franch., R. sublanceolatum C. Y. Cheng et T. C. Kao and R. pumilum Maxim. A total of 101 phenolic compounds, including sennosides, anthraquinones, stilbenes, glucose gallates, naphthalenes, procyanidins and chromones were identified or tentatively characterized based on their UV and mass spectral data from the methanol extracts. These chemical constituents were compared with those of an official species ( R. palmatum l.). The results showed that most sennosides and procyanidin derivatives were only present in R. palmatum rather than in the unofficial species; stilbenes and chromones were only found in the sect. deserticola species; while anthraquinones, glucose gallates and naphthalenes could be detected in all studied species. For anthraquinone glycosides, only emodin O-glucosides were detected in the sect. deserticola species. Moreover, remarkable difference was observed among unofficial species. These results may be useful for the quality control of rhubarb in order to guarantee its clinical effects, and may also be helpful for the further clarification of the taxonomic relationship of the plants in the sect. deserticola.

The diterpenoid triepoxides are the major active constituents of Tripterygium wilfordii with potent antitumor and immune activities. But the strong toxicity of these compounds has restricted their application to a great extent. In order to find more effective compounds with less toxicity, structural modifications of triptonide (1) by Aspergillus niger (AS 3.739) were investigated and four biotransformed products were obtained. Based on their chemical and spectral data, their structures were elucidated as 5alpha-hydroxytriptonide (2), triptolide (3), 17-hydroxytriptonide (4), and 16-hydroxytriptonide (5), among which 2, 4 and 5 are new compounds. All the three new transformed products showed cytotoxic activities against the majority of the human tumor cell lines tested, however, they are found to possess less cytotoxic activity when compared with 1. Both compounds 4 and 5 showed similar cytotoxic activity and their IC (50) values were 5-15 fold less than 1, while 2 is about 100 times less active than 1.

Catharanthus roseus cell suspension cultures were employed for the biotransformation of 2alpha,5alpha,10beta,14beta-tetraacetoxy-4(20),11-taxadiene ( 1), and four metabolites were obtained. Based on their physical and chemical data, the structures of the four metabolites were respectively elucidated as 10beta-hydroxy-2alpha,5alpha,14beta-triacetoxy-4(20),11-taxadiene (2), 5alpha-hydroxy-2alpha,10beta, 14beta-triacetoxy-4(20),11-taxadiene (3), 6alpha,10beta-dihydroxy-2alpha,5alpha,14beta-triacetoxy-4(20),11-taxadiene (4), and 6alpha,9alpha,10beta-trihydroxy-2alpha,5alpha,14beta-triacetoxy-4(20),11-taxadiene (5), among which 3 and 5 were characterized as new taxoids. The effects of the stages of substrate addition on the biotransformation were also investigated. The results revealed that the biotransformation rate for 1 reached 85.3 % and the yield of 2 70 % when 1 was administered during the mid-linear phase (9 - 12 th day) of the cell growth cycle. On the other hand, the yield for 4 reached the highest level of 11.8 % when 1 was added in the early linear phase (6 th day).

Minor phenolic compounds in licorice (Glycyrrhiza uralensis) have recently been proved for diverse bioactivities and favorable bioavailability, indicating that they may play an important role in the therapeutic effects or herb-drug interactions of licorice. However, so far, their abundance in licorice remains unknown. In this study, a reliable solid-phase extraction coupled with a high-performance liquid chromatography and diode array detection method was established to determine the minor phenolic compounds in licorice. The analytes were enriched by a three-step solid-phase extraction method, and then separated on a YMC ODS-A column by gradient elution. Five coumarins and flavonoids were identified by electrospray ionization tandem mass spectrometry, and then quantified using high-performance liquid chromatography and diode array detection. The amounts of glycycoumarin, dehydroglyasperin C, glycyrol, licoflavonol, and glycyrin in G. uralensis were 0.81 ± 0.28, 1.25 ± 0.59, 0.20 ± 0.08, 0.12 ± 0.04, and 0.17 ± 0.08 mg/g, respectively. Abundances of these compounds in other Glycyrrhiza species (G. glabra, G. inflata, and G. yunnanesis) were remarkably lower than G. uralensis.

Cuscuta chinensis and Cuscuta australis, the two botanical sources of the Chinese herbal medicine Tu-Si-Zi, were distinguished from each other based on qualitative and quantitative chemical analysis. By HPLC‑DAD‑MS, a total of 36 compounds were characterized from these two Cuscuta species, including 14 flavonoids, 17 quinic acid derivatives, and 5 lignans. In addition, HPLC‑UV was applied to determine seven major compounds (6 flavonoids plus chlorogenic acid) in 27 batches of Tu-Si-Zi. The results revealed that the amounts of the three classes of compounds varied significantly between the species. C. australis contained more flavonoids but less quinic acid derivatives and lignans than C. chinensis. Particularly, the amounts of kaempferol and astragalin in C. australis were remarkably higher than in C. chinensis. This finding could be valuable for the quality control of Tu-Si-Zi.

Two unusual prenylated and C-methylated flavanones, (±)-5,4'-dihydroxy-2'-methoxy-6',6''- dimethypyrano-(2'',3'':7,8)-6-methyflavanone ( 1) and (2 S)-5,7,4'-trihydroxy-2'-methoxy-8,5'- di(3-methyl-2-butenyl)-6-methyflavanone ( 2), and 10 known compounds were isolated from the stems and roots of TRIPTERYGIUM WILFORDII. Their structures were elucidated based on spectroscopic analyses including 1- and 2-D NMR, HR-ESI-MS, CD, and x-ray crystallography. The anti-inflammatory, antiproliferative, and antibacterial activities of compounds 1 and 2 were investigated. Compound 2 had an inhibitory effect on lipopolysaccharides (LPS)-triggered RAW cell nitric oxide (NO) production, with an IC (50) value of 15.0 ± 0.7 µM. Both compounds showed moderate antiproliferative activity against the tumor cell lines HT-29 and ZR-75-1.

Salvia species have an extensive distribution and a long history of medical use in China. In this study, chemical differences between different Salvia species were thoroughly investigated, and 86 constituents were characterized through a sensitive HPLC-DAD-ESI-MS (n) method. In total, 19 Salvia species were screened. Our study suggested that Ser. Brachylomae, Ser. Digitaloidites, Ser. Castaneae, and Ser. Miltiorrhizae were the sibling series (Ser. is short for series) and that Ser. Brachylomae, Ser. Maximowicziana, and Ser. Campanulatae were unique with regard to their constituents in addition to having componential affinity. This study offered a simple chemotaxonomy approach and a reasonable bioactivity interpretation of Salvia species.

Glycyrrhetinic acid (GA; 1) is one of the major constituents of a traditional Chinese medicine, the roots of Glycyrrhiza uralensis, called Gancao in Chinese. In the present paper, the biotransformation of GA by Mucor polymorphosporus (AS 3.3443) was investigated and eight metabolites were obtained. Based on their chemical and spectral data, the structures of the derivatives were respectively elucidated as 24-hydroxyglycyrrhetinic acid ( 2), 6beta-hydroxyglycyrrhetinic acid ( 3), 7alpha-hydroxyglycyrrhetinic acid ( 4), 7beta-hydroxyglycyrrhetinic acid ( 5), 3- O-acetyl-7beta-hydroxyglycyrrhetinic acid ( 6), 3-oxo-7beta-hydroxyglycyrrhetinic acid ( 7), 15alpha-hydroxyglycyrrhetinic acid ( 8), 3 -oxo -15alpha-hydroxyglycyrrhetinic acid ( 9), among which metabolites 3, 4, 6, 7 and 9 are new compounds.

Catharanthus roseus cell suspension cultures were employed for the biotransformation of 2alpha,5alpha,10beta,14beta-tetraacetoxy-4(20),11-taxadiene ( 1), and four metabolites were obtained. Based on their physical and chemical data, the structures of the four metabolites were respectively elucidated as 10beta-hydroxy-2alpha,5alpha,14beta-triacetoxy-4(20),11-taxadiene (2), 5alpha-hydroxy-2alpha,10beta, 14beta-triacetoxy-4(20),11-taxadiene (3), 6alpha,10beta-dihydroxy-2alpha,5alpha,14beta-triacetoxy-4(20),11-taxadiene (4), and 6alpha,9alpha,10beta-trihydroxy-2alpha,5alpha,14beta-triacetoxy-4(20),11-taxadiene (5), among which 3 and 5 were characterized as new taxoids. The effects of the stages of substrate addition on the biotransformation were also investigated. The results revealed that the biotransformation rate for 1 reached 85.3 % and the yield of 2 70 % when 1 was administered during the mid-linear phase (9 - 12 th day) of the cell growth cycle. On the other hand, the yield for 4 reached the highest level of 11.8 % when 1 was added in the early linear phase (6 th day).