Revised structures of Arillatanosides A–C from Polygala arillata

Arillatanosides A–C are three triterpenoid saponins from Polygala arillata Buch–Ham that have been reported previously, but with partially incorrect structures. Further investigation of their NMR data led to the conclusion that the terminal α‐L ‐arabinopyranosyl unit originally proposed for Arillatanosides A–C ( I – III ) is actually a β‐D ‐xylopyranosyl unit. Thus, the correct structures of Arillatanosides A–C are represented by 1 – 3 . Complete NMR assignments of Arillatanosides A–C ( 1 – 3 ) and the related polygalasaponin XXXV ( 4 ) were achieved using modern 2D NMR techniques, such as DQF H–H COSY, HMQC, HMBC, TOCSY, 2D HMQC–TOCSY. Copyright © 2002 John Wiley & Sons, Ltd.     

Three new steroidal saponins from Helleborus thibetanus

Three new steroidal saponins including two spirostanol glycosides (1–2) and one furostanol glycoside 1-sulphate (3) were isolated from the dried roots and rhizomes of Helleborus thibetanus. Structures of the compounds were determined on the basis of extensive use of 1-D and 2-D NMR experiments, together with HR–ESI–MS and IR measurements, as well as the results of acid hydrolysis. Compounds 1–2 represented steroidal saponins with an unusual substitution pattern, which possessed a double bond at C-25 and were glycosylated at 1-OH.     

Three new triterpenoid saponins from the roots of Ardisia crenata and their cytotoxic activities

Three new triterpenoid saponins, ardisicrenoside O (1), ardisicrenoside P (2) and ardisicrenoside Q (3) together with three known compounds, 3β,16α-dihydroxy-30-methoxy-28, 30-epoxy-olean-12-en, cyclamiretin A 3-O-β-d-glucopyranosyl-(1→2) -α-l-arabinopyranoside and cyclamiretin A 3-O-β-d-glucopyranosyl-(1→4) -α-l-arabinopyranoside were isolated from the roots of Ardisia crenata Sims. Their structures were determined by one- and two-dimensional NMR techniques, including HSQC, HMBC and TOCSY experiments, as well as acid hydrolysis and GC analysis. All isolates were evaluated for the cytotoxic activities on two human cancer cell lines and compounds 3, 5 and 6 showed significant cytotoxicity.     

Efficient method for large-scale preparation of two components H and I of Sg-6 saponins from whole seeds of wild soybean (Glycine soja Sieb. and Zucc.)

New saponin components, Sg-6 saponins, have been recently reported from the seeds of wild soybean (Glycine soja) which may have specific health benefits. To evaluate the possible health benefits, a large amount of Sg-6 saponins are needed, but general group A acetyl saponins and new Sg-6 saponins are eluted in overlapping peaks by ordinal preparative high-performance liquid chromatography and/or open column methods. A new method is proposed in this report. This method includes (1) deacetylation of group A acetyl saponins in alkali condition with KOH, (2) precipitation of Sg-6 saponins in acid condition with HCl, (3) recovery of Sg-6 saponins with aqueous methanol from the precipitate, and (4) elution of Sg-6 saponins by preparative reverse-phase open column. With this method, from 450?g of wild soybean whole seed powder, about 1?g of Sg-6 saponins (mixture of six components) was clearly separated from other saponins with 61% recovery.     

Three Escin‐Like Triterpene Saponins: Assamicins VI,VII, and VIII from the Seeds of Aesculus assamica Griff

Three new escin‐like triterpene saponins, assamicins VI ( 1 ), VII ( 2 ), and VIII ( 3 ), were isolated from the seeds of A. assamica, together with a known saponin, isoescin Ib ( 4 ). Their structures were established as 28‐O‐acetyl‐21‐O‐(3,4‐di‐O‐angeloyl‐6‐deoxy‐β‐glucopyranosyl)‐3‐O‐{O‐β‐glucopyranosyl‐(1→2)‐O‐[β‐glucopyranosyl‐(1→4)]‐β‐glucopyranuronosyl}protoaescigenin ( 1 ), 21‐O‐angeloyl‐3‐O‐{O‐α‐rhamnopyranosyl‐(1→2)‐O‐[β‐glucopyranosyl‐(1→3)]‐β‐glucopyranuronosyl}protoaescigenin ( 2 ), and 21‐O‐angeloyl‐3‐O‐{O‐[β‐glucopyranosyl‐(1→3)]‐β‐glucopyranuronosyl}protoaescigenin ( 3 ) on the basis of spectroscopic analysis (protoaescigenin=(3β,4β,16α,21β,22α)‐olean‐12‐ene‐3,16,21,22,23,28‐hexol; angelic acid=(2Z)‐2‐methylbut‐2‐enoic acid).     

Quantitative determination of 15 bioactive triterpenoid saponins in different parts of Acanthopanax henryi by HPLC with charged aerosol detection and confirmation by LC–ESI‐TOF‐MS

Triterpenoid saponins are difficult to analyze using high‐performance liquid chromatography coupled to UV/vis spectrophotometry due to their lack of chromophores. This study describes the first analytical method for the determination of 15 triterpenoid saponins from the leaves, stems, root bark, and fruits of Acanthopanax henryi, using a high‐performance liquid chromatography with charged aerosol detection coupled with electrospray ionization mass spectrometry method. The separation was carried out on a Kinetex XB‐C18 column with an acetonitrile/water gradient as the mobile phase, followed by charged aerosol detection. The operating conditions of charged aerosol detection were set at 24 kPa for nitrogen pressure and 100 pA for the detection range. Liquid chromatography with electrospray ionization mass spectrometry is described for the identification of compounds in plant samples. The electrospray ionization mass spectrometry method involved the use of the [M + Na]⁺ and [M + NH₄]⁺ ions for compounds 1 – 15 in the positive ion mode with an extracted ion chromatogram. The developed method was fully validated in terms of linearity, sensitivity, precision, repeatability, and recovery, then subsequently applied to evaluate the quality of A. henryi.     

Simultaneous quantification of triterpenoid saponins in rat plasma by UHPLC–MS/MS and its application to a pharmacokinetic study after oral total saponin of Aralia elata leaves

A rapid, sensitive, and reliable analytical ultra performance liquid chromatography with tandem mass spectrometry method was developed for the simultaneous determination of Aralia‐saponin IV, 3‐O‐β‐d ‐glucopyranosyl‐(1→3)‐β‐d ‐glucopyranosyl‐(1→3)‐β‐d ‐glucopyranosyl oleanolic acid 28‐O‐β‐d ‐glucopyranoside, Aralia‐saponin A and Aralia‐saponin B after the oral administration of total saponin of Aralia elata leaves in rat plasma. Plasma samples were pretreated by protein precipitation with methanol. The analysis was performed on an ACQUITY UPLC HSS T3 column. The detection was performed on a triple quadrupole tandem mass spectrometer in multiple reaction monitoring mode using an electrospray ionization source with negative ionization mode. Under the experimental conditions, the calibration curves of four analytes had good linearity values (r > 0.991). The intra‐ and inter‐day precision values of the four analytes were ≤ 11.6%, and the accuracy was between –6.2 and 4.2%.The extraction recoveries of four triterpenoid saponins were in the range of 84.06–91.66% (RSD < 10.5%), and all values of the matrix effect were more than 90.30%. The developed analytical method was successfully applied to pharmacokinetic study on simultaneous determination of the four triterpenoid saponins in rat plasma after oral administration of total saponin of Aralia elata leaves, which helps guiding clinical usage of Aralia elata leaves.     

The Effects of New Zealand Grown Ginseng Fractions on Cytokine Production from Human Monocytic THP-1 Cells

Pro-inflammatory cytokines and anti-inflammatory cytokines are important mediators that regulate the inflammatory response in inflammation-related diseases. The aim of this study is to evaluate different New Zealand (NZ)-grown ginseng fractions on the productions of pro-inflammatory and anti-inflammatory cytokines in human monocytic THP-1 cells. Four NZ-grown ginseng fractions, including total ginseng extract (TGE), non-ginsenoside fraction extract (NGE), high-polar ginsenoside fraction extract (HPG), and less-polar ginsenoside fraction extract (LPG), were prepared and the ginsenoside compositions of extracts were analyzed by HPLC using 19 ginsenoside reference standards. The THP-1 cells were pre-treated with different concentrations of TGE, NGE, HPG, and LPG, and were then stimulated with lipopolysaccharide (LPS). The levels of pro-inflammatory cytokines, including tumor necrosis factor-alpha (TNF-α), interleukin-1 beta (IL-1β), interleukin-6 (IL-6), interleukin-8 (IL-8), and anti-inflammatory cytokines, such as interleukin-10 (IL-10), and transforming growth factor beta-1 (TGF-β1), were determined by enzyme-linked immunosorbent assay (ELISA). TGE at 400 µg/mL significantly inhibited LPS-induced TNF-α and IL-6 productions. NGE did not show any effects on inflammatory secretion except inhibited IL-6 production at a high dose. Furthermore, LPG displayed a stronger effect than HPG on inhibiting pro-inflammatory cytokine (TNF-α, IL-1β, and IL-6) productions. Particularly, 100 µg/mL LPG not only significantly inhibited the production of pro-inflammatory cytokines TNF-α, IL-1β, and IL-6, but also remarkably enhanced the production of anti-inflammatory cytokine IL-10. NZ-grown ginseng exhibited anti-inflammatory effects in vitro, which is mainly attributed to ginsenoside fractions (particularly less-polar ginsenosides) rather than non-saponin fractions.     

Concise Synthesis and Antidiabetic Effect of Three Natural Triterpenoid Saponins Isolated from Fadogia ancylantha (Makoni tea)

The first concise synthesis of the bidesmosidic oleanolic acid saponins 1 – 3 isolated from Fadogia ancylantha (Makoni tea) have been accomplished through a ‘one‐pot sequential glycosylation’ strategy with two glycosyl 1‐(trichloroacetimidate)s as glycosyl donors. The synthesized natural products 1 – 3 were then evaluated for their inhibitory activities against α‐glucosidase, α‐amylase, and lipase. Among the assayed compounds 1 – 3 , compound 1 showed strong α‐glucosidase and α‐amylase inhibition, with IC₅₀ values of 160 and 180 μM , respectively. Moreover, compounds 2 and 3 showed strong inhibition against α‐glucosidase and lipase, with the respective IC₅₀ values of 170 and 190 μM , and 190 and 200 μM .     

Simultaneous quantification of six major triterpenoid saponins in Schefflera kwangsiensis using high-performance liquid chromatography coupled to orbitrap mass spectrometry

A simple and accurate analytical method was developed for simultaneous and quantitative analysis of six triterpenoid saponins in Schefflera kwangsiensis via high-performance liquid chromatography (HPLC) with mass spectrometry (MS) in this study. Separation was performed on a Thermo hypersil GOLD C₁₈ column (150 mm × 2.1 mm, 5 μm). A mobile phase consisting of methanol/acetonitrile/8 mM ammonium acetate in water was used with a flow rate of 0.3 mL/min. The analytes were detected by MS with the electrospray ionisation (ESI) source combined with negative monitoring and full scan mode, and were analysed by extracted ion chromatography. This established HPLC-ESI-MS analysis demonstrated good linearity, sensitivity, stability, precision, accuracy and recovery. Therefore, this analytical method has great potential to be a novel tool to qualify S. kwangsiensis.