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Six new prenylated flavonoid glycosides, including four new furan-flavonoid glycosides wushepimedoside A-D (1-4) and two new prenyl flavonoid derivatives wushepimedoside E-F (5-6), and one know analog epimedkoreside B (7) were isolated from biotransformation products of the aerial parts of Epimedium wushanense. Their structures were elucidated according to comprehensive analysis of HR-MS and NMR spectroscopic data, and the absolute configurations were assigned using experimental and calculated electronic circular dichroism (ECD) data. The regulatory activity of compounds 1-7 on the production of testosterone in primary rat Leydig cells were investigated, and 4 and 5 exhibited testosterone production-promoting activities. Molecular docking analysis suggested that bioactive compounds 4 and 5 showed the stable binding with 3β-HSD and 4 also had good affinity with Cyp17A1, which suggested that these compounds may regulate testosterone production through stimulating the expression of the above two key proteins.

A strategy for rapid identification of the chemical constituents from crude extracts of Tribulus terrestris was proposed using an informatics platform for the UHPLC/Q-TOF MSE data analyses. This strategy mainly utilizes neutral losses, characteristic fragments, and in-house library to rapidly identify the structure of the compounds. With this strategy, rapid characterization of the chemical components of T. terrestris from Beijing, China was successfully achieved. A total of 82 steroidal saponins and nine flavonoids were identified or tentatively identified from T. terrestris. Among them, 15 new components were deduced based on retention times and characteristic MS fragmentation patterns. Furthermore, the chemical components of T. terrestris, including the other two samples from Xinjiang Uygur Autonomous region, China, and Rome, Italy, were also identified with this strategy. Altogether, 141 chemical components were identified from these three samples, of which 39 components were identified or tentatively identified as new compounds, including 35 groups of isomers. It demonstrated that this strategy provided an efficient protocol for the rapid identification of chemical constituents in complex samples such as traditional Chinese medicines (TCMs) by UHPLC/Q-TOF MSE with informatics platform. Graphical Abstract ᅟ.

The change of icariin( ICA) content in thirty-three samples of five Epimedium species listed in the Chinese Pharmacopoeia( 2015 edition),including E. brevicornu,E. sagittatum,E. pubescens,E. koreanum,and E. wushanense has been investigated in this study. The results indicated that the optimized process procedure was baking at 150 ℃ for 30 min,and 3'''-carbonyl-2″-β-L-quinovosyl icariin( CQICA) could not be translated into ICA and ICA could be converted under this heating process condition. ICA increased remarkably after the heating process by 1-3 times in E. brevicornu,E. wushanense and E. koreanum,and increased lightly in E. brevicornum and E. pubescens,while ICA slightly increased or decreased in E. sagittatum and E. wushanense.

A new method was developed for the chromatographic fingerprint analysis of Toosendan Fructus by HPLC coupled with the charged aerosol detector (CAD) in the present study. Samples were well separated on an Agilent ZOBAX SB C18 column (4.6 mm × 250 mm, 5 μm) by gradient elution using acetonitrile and water containing 0.1 % formic acid (v/v) at the flow rate of 1.0 mL·min−1. The column temperature was 30 ℃ and the injection volume was 5 μL. The nitrogen inlet pressure of the charged aerosol detector (CAD) was 35 psi, and the nebulizer chamber temperature was 35 ℃. In addition, the method of the chromatographic fingerprints combined with multivariate statistical analysis was effective and reasonable lead to an accurate classification of 20 batches of samples from different locations. The results showed that 28 common peaks were observed in the fingerprint and the samples were classified into three clusters. The established method was well validated, and showed high precision, good repeatability, and satisfactory stability. It may serve in the quality control and evaluation of Toosendan Fructus.

Sulfur-containing Anemarrhenae Rhizoma decoction pieces were prepared by using sulfur-fumigating procedure. The difference components before and after sulfur fumigation in Anemarrhenae Rhizoma were analyzed and on-line identified by UPLC-Q-TOF-MSE combined with UNIFI informatics platform, principal component analysis (PCA) and orthogonal partial least squares discriminant analysis (OPLS-DA) respectively. As a result, 16 major differences components were identified, and among them, 9 components were mainly from sulfur-fumigated samples. The main chemical markers in sulfur-fumigated Anemarrhenae Rhizoma were identified as the sulfite derivatives newly produced after sulfur-fumigating. Meanwhile, UPLC-Q-TOF-MSE was used to find the main chemical marker anemarrhena saponin BⅡ sulfite (m/z 983). By using this method, a rapid screening method for sulfur-fumigated Anemarrhenae Rhizoma was established. This was a convenient and accurate detection method for sulfur dioxide residue, and it can be used as an effective assistant method to control the quality of Anemarrhenae Rhizoma. At the same time, it was the first time to identify sulfited derivatives of steroidal saponins, and screen the sulfur-fumigated Anemarrhenae Rhizoma.

To compare the differences of main components between in rhizoma and fibrous root of Trillium tschonoskii and T. kamtschaticum, a simple, accurate and reliable high performance liquid chromatography coupled with the charged aerosol detector (HPLC-CAD) method was developed and then successfully applied for simultaneous quantitative analysis of three compounds, including polyphyllin Ⅶ (T1),pennogenin 3-O-α-L-rhamnopyranosyl-(1→2) [α-L-rhamnopyranosyl-(1→4)]-β-D-glucopyranoside (T2),polyphyllin Ⅵ (T3), in 16 batches of rhizome and 14 batches of fibrous root. The analytes were well separated from other constituents on TSK gel ODS (4.6 mm×250 mm, 5 μm) with acetonitrile-water (43∶57) at a flow rate of 1.0 mL•min⁻¹. The injection volume was 20 μL. The nitrogen inlet pressure for the CAD system was 35 psi and the nebulizer chamber temperature was 35 ℃.The method was validated for linearity (r0.999 0), intra and inter-day precision (0.29%-3.0%), repeatability (0.45%-1.4%), stability (1.9%-2.6%), recovery (100.1%-100.2%, 1.2%-1.8%), limits of detection (0.002 g•L⁻¹), and limits of quantification (0.005 g•L⁻¹).The obtained datasets were processed by principal component analysis (PCA) and it showed that there was almost no difference in rhizoma of T. tschonoskii and T. kamtschaticum from different areas of China. However, the 3 major compounds existed in rhizoma were different from those in fibrous root of T. tschonoskii and T. kamtschaticum.

A simple, accurate and reliable high performance liquid chromatography coupled with photodiode array detection (HPLC-DAD) method was developed and then successfully applied for simultaneous quantitative analysis of eight compounds, including chlorogenic acid (1), (R/S)-flavanomarein (2), butin-7-O-β-d-glucopyranoside (3), isookanin (4), taxifolin (5), 5,7,3′,5′-tetrahydroxyflavanone-7-O-β-d-glucopyranoside (6), marein (7) and okanin (8), in 23 batches of snow chrysanthemum of different seed provenance and from various habitats. The results showed total contents of the eight compounds in the samples with seed provenance from Keliyang (Xinjiang, China), are higher than in samples from the other five provenances by 52.47%, 15.53%, 19.78%, 21.17% and 5.06%, respectively, which demonstrated that provenance has a great influence on the constituents in snow chrysanthemum. Meanwhile, an ultra performance liquid chromatography coupled with electrospray ionization and quadrupole time-of-flight-mass spectrometry (UPLC-ESI-QTOF-MS) was also employed to rapidly separate and identify flavonoids and phenolic acids in snow chrysanthemum from Keliyang. As a result, a total of 30 constituents, including 26 flavonoids and four phenolic acids, were identified or tentatively identified based on the exact mass information, the fragmentation characteristics, and retention times of eight reference standards. This work may provide an efficient approach to comprehensively evaluate the quality of snow chrysanthemum.

Twelve new steroidal saponins, including eleven furostanol saponins, terrestrinin J–T (1–11), and one spirostanol saponin, terrestrinin U (12), together with seven known steroidal saponins 13–19 were isolated from T. terrestris. The structures of the new compounds were established on the basis of spectroscopic data, including 1D and 2D NMR and HRESIMS, and comparisons with published data.