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 separation of triterpenoid saponins and flavonoid glycosides from the roots of Glycyrrhiza uralensis Fisch by pH‐zone‐refining counter‐current chromatography

Glycosides including triterpenoid saponins and flavonoid glycosides are the main constituents of Glycyrrhiza uralensis Fisch (licorice) and exhibit prominent pharmacological activities. However, conventional methods for the separation of glycosides always cause irreversible adsorption and unavoidable loss of sample due to their high hydrophilicities. The present paper describes a convenient method for the simultaneous separation of triterpenoid saponins and flavonoid glycosides from licorice by pH‐zone‐refining counter‐current chromatography. Ethyl acetate/n‐butanol/water (2:3:5, v/v) with 10 mM TFA in the upper organic stationary phase and 10 mM ammonia in the lower aqueous mobile phase was used as the biphasic solvent system. Three triterpenoid saponins and two flavonoid glycosides including licorice‐saponin A3 (63.3 mg), glycyrrhizic acid (342.2 mg), 3‐O‐[β‐d ‐glucuronopyranosyl‐(1 → 2)‐β‐d ‐galactopyranosyl]glycyrrhetic acid (56.0 mg), liquiritin apioside (232.6 mg), and liquiritin (386.5 mg) were successfully obtained from licorice ethanol extract (2 g) in one step. This method subtly takes advantage of the common acidic properties of triterpenoid saponins and flavonoid glycosides, and obviously is much more efficient and convenient than the previous methods. It is also the first time that the separation of acidic triterpenoid saponins by using pH‐zone‐refining counter‐current chromatography has been reported.     

Optimisation of extraction conditions for total saponins from Cynanchum wallichii using response surface methodology and its anti-tumour effects

Cynanchum wallichii Wight, is a traditional Chinese medicine herb, which is rich in saponins and has varieties of pharmacological activities. In this study, a standardized C. wallichii extract was established and the anti-tumor activity of the total saponins was evaluated by MTT assay. The extraction conditions of the standardized extract was optimized using response surface methodology. The experimental value was in good agreement (the yield 4.28%) with predicted values. The total saponins of the extract showed significant anti-tumor activity against three human tumor cell lines (A549, HepG2 and MCF-7), especially for MCF-7 (IC₅₀. 67.63 μg/mL) cells in vitro.     

Simultaneous Quantification of Seven Main Triterpenoid Saponins in Radix et Rhizoma Clematidis by LC–ELSD

Chinese clematis is a Chinese medicine with anti-inflammatory and anti-rheumatoid properties. Studies showed the triterpenoid saponins of this herb represent the major active components with therapeutic activities for the treatment of inflammatory diseases. The LC–ELSD method was developed to quantitatively analyze seven major triterpenoid saponins in 22 samples from different habitats. The linearity, sensitivity, precision, and accuracy were investigated. It showed the great variation of the contents of each saponin. We concluded clematichinenoside AR is the major saponin in all the samples. This method can be used to effectively evaluate and monitor the quality of Chinese clematis in clinical use.     

Imperata cylindrica: A Review of Phytochemistry,Pharmacology, and Industrial Applications

Imperata cylindrica is a medicinal plant native to southwestern Asia and the tropical and subtropical zones. To date, 72 chemical constituents have been isolated and identified from I. cylindrica Among these compounds, saponins, flavonoids, phenols, and glycosides are the major constituents. Investigations of pharmacological activities of I. cylindrica revealed that this edible medicinal herb exhibits a wide range of therapeutic potential including immunomodulatory, antibacterial, antitumor, anti-inflammatory, and liver protection activities both in vivo and in vitro. The purpose of this review is to provide an overview of I. cylindrica studies until 2019. This article also intends to review advances in the botanical, phytochemical, and pharmacological studies and industrial applications of I. cylindrica, which will provide a useful bibliography for further investigations and applications of I. cylindrica in medicines and foods.     

Two New Indole Alkaloids from Emmenopterys henryi

Two new indole alkaloids, 5‐oxodolichantoside ( 1 ) and deglycocadambine ( 2 ), were isolated from the twigs and leaves of Emmenopterys henryi, together with four known indole alkaloids and five known iridoids. The structures of the new compounds were elucidated on the basis of extensive spectroscopic analyses, including 1D‐ and 2D‐NMR experiments, and confirmed by single‐crystal X‐ray diffraction studies. This is the first report on the isolation of indole alkaloids from this species. The indole alkaloids were evaluated for their cytotoxic activities against five human cancer lines.     

New triterpenoid saponins from the roots of Platycodon grandiflorum

Bioassay-directed fractionation of the antiviral active fraction of the roots of Platycodon grandiflorum leads to the isolation of three new triterpenoid saponins, platycosides G1-G3 (1-3), as well as two known saponins, platycodin D3 (4), and platycoside E (5). The structures of the new compounds were elucidated on the basis of their spectral data and chemical evidences. The isolated saponins were tested for their antiviral activities against respiratory syncytial virus (RSV), herpes simplex type 1 virus (HSV-1) and influenza type A virus (Flu A). Compound 4 showed weak anti-RSV activity.     

Comparative chemical diversity and antioxidant activities of three species of Akebia herbal medicines

Akebia stem has long been used extensively as a rare Chinese herbal medicine. The three most significant Akebia medicinal species are Akebia quinata (Thunb.) Decne. (A. quinata), Akebia trifoliata (Thunb.) Koidz. (A. trifoliata), and Akebia trifoliata (Thunb.) Koidz. var. Australis (Diels) Rehd. (A. trifoliata. var). They have significant therapeutic effects and are widely used in the pharmaceutical and cosmetics industries. Only a few studies compared their chemical differences and antioxidant activities. To better demonstrate each species' characteristics and antioxidant properties, the ultra-performance liquid chromatography coupled with quadrupole Orbitrap mass spectrometry (UPLC-Q-Orbitrap/MS)-based metabolomics was applied to investigate the chemome diversity of three Akebia species. Their antioxidant activities were evaluated by DPPH and ABTS assays. In total, 65 different metabolites were identified, including 5 phenolic acids, 2 phenylpropanoids, 4 lignan glycosides, and 54 triterpenoid saponins. The different aglycone types of triterpenoid saponins were found to be the component differences between the three Akebia species. The chemical composition of A. trifoliata and A. trifoliata. var is similar. The 2-(3,4-dihydroxyphenyl)-ethyl-O-β-d-glucopyranoside has been found only in A. quinata. In contrast, the triterpenoid saponins akemisaponin B, akemisaponin D, oleanolic-acid-3-O-arabinopyranosyl-28-O-glucopyranosyl-glucopyranosyl-rhamnopyranosyl-arabinopyranosyl, akemisaponin C and saponin P_j1 have been found A. trifoliata and A. trifoliata. var. As a result, these six compounds can be considered marker compounds that distinguish three Akebia species. The antioxidant activities results indicated that the antioxidants of three Akebia species were the same in different antioxidative test systems. A. trifoliata (IC₅₀: 2.28–6.97 mg·mL^?1) and A. trifoliata. var (IC₅₀: 2.09–6.87 mg·mL^?1) showed 2–3 times higher antioxidant activity than A. quinata (IC₅₀: 5.56–11.21 mg·mL^?1). This study reveals the antioxidant activity differences of three Akebia species, laying a foundation for further development and utilization. This type of study can lead to the identification of a compound that, with further work and more extensive studies, has the potential to be used as a biomarker, in this case to distinguish different medicinal species.     

Bellisosides A-F, six novel acylated triterpenoid saponins from Bellis perennis (compositae)

Six new acylated triterpenoid saponins, bellisosides A-F (1-6), were isolated from the roots of Bellis perennis (Compositae) together with a known saponin, bellissaponin BS2 (7). These saponins which bear polygalacic acid as sapogenin, are bisdesmosidic glycosides. The structures were elucidated on the basis of chemical and physicochemical evidence. The cytotoxic activities of 1-7 against HL-60 human promyelocytic leukemia cells are also reported.     

Cytotoxic Triterpenoid Saponins Acetylated with Monoterpenoid Acid from Albizia julibrissin

Three new triterpenoid saponins, named julibroside J₁₆ ( 2 ), julibroside J₁₇ ( 3 ), and julibroside J₂₁ ( 4 ), each of which possesses an oleanane triterpenoid aglycone of acacic acid, two monoterpenoid acids, and nine sugar moieties, together with one known saponin, julibroside II ( 1 ), were isolated from the stem bark of Albizia julibrissin by chromatographic methods. Their structures were established by chemical and spectroscopic means. Saponins 1, 2 , and 4 showed inhibitory activities against Bel 7402 human cancer cell line in vitro.     

Cytotoxic 13,28 Epoxy Bridged Oleanane-Type Triterpenoid Saponins from the Roots of Ardisia crispa

Ardisiacrispin D–F (1–3), three new 13,28 epoxy bridged oleanane-type triterpenoid saponins, together with four known analogues (4–7) were isolated from the roots of Ardisia crispa. The structures of 1–7 were elucidated based on 1D and 2D-NMR experiments and by comparing their spectroscopic data with values from the published literatures. Ardisiacrispin D–F (1–3) are first examples that the monosaccharide directly linked to aglycone C-3 of triterpenoid saponins in genus Ardisia are non-arabinopyranose. In the present paper, all compounds are evaluated for the cytotoxicity against three cancer cell lines (HeLa, HepG2 and U87 MG) in vitro. The results show that compounds 1, 4 and 6 exhibited significant cytotoxicity against Hela and U87 MG cells with IC₅₀ values in the range of 2.2 ± 0.6 to 9.5 ± 1.8 µM. The present investigation suggests that roots of A. crispa could be a potential source of natural anti-tumor agents and their triterpenoid saponins might be responsible for cytotoxicity.     

Cadinane and Eudesmane Sesquiterpenoids from Chloranthus henryi

Chemical investigation of the leaves and stems of Chloranthus henryi resulted in the isolation and characterization of the three new cadinane‐type sesquiterpenes 1 – 3 and of the new eudesmane‐type sesquiterpene 4 , together with three known compounds. Among the new compounds, the two cadinane‐type sesquiterpenes 1 and 2 possess an unusual aromatic ring B in their molecule. These structures were established on the basis of spectroscopic evidence. In addition, antitumor activities of the isolates were also evaluated.     

New dammarane-type saponins from the leaves of Panax notoginseng

Two new triterpenoid saponins, notoginsenoside-Ng3 (1) and notoginsenoside-Ng4 (2), along with three known saponins (3-5), were isolated from a water extract of the leaves of Panax notoginseng. The absolute configuration of notoginsenoside Fa (3) with five sugars was confirmed by the single-crystal X-ray diffraction for the first time.     

Systematic characterization of the chemical constituents in vitro and prototypes in vivo of Dingkun Dan using ultra-high-performance liquid chromatography quadrupole time-of-flight mass spectrometry combined with the UNIFI™ software

Dingkun Dan (DKD), a famous traditional Chinese medicine, has been widely used in the treatment of irregular menstruation, leucorrhea abnormality, and postpartum gynecological diseases since Qing dynasty (1739). It comprises 30 flavors of Chinese medicinal materials, which results in its complex chemical composition. In this study, an integrative method was developed to rapidly characterize the chemical components of DKD using ultra-high-performance liquid chromatography quadrupole time-of-flight mass spectrometry combined with the UNIFI™ software. A total of 234 compounds, including 47 triterpenoid saponins, 55 flavonoids, and 38 alkaloids, were identified. Of them, 170 compounds were characterized initially and 61 compounds were identified unambiguously using reference standards. Under the same analysis conditions, 43 prototypical components, which were tentatively assigned as triterpenoid saponins, flavonoids, alkaloids, terpenoids, phenylpropanoids, and others, were absorbed in rat by serum pharmacochemistry analysis. DKD exhibited diverse pharmacological activities through the combined effect of these components. This study was the first systematic study of chemical components in vitro originating from 30 medicinal materials and prototypes in vivo of DKD, which could provide scientific evidence for explaining its therapeutic effect.     

A Novel Alkaloid from Melodinus henryi

The isolation and structure elucidation of a novel alkaloid, namely of the 14‐O‐ethyl‐substituted (3α,14α,16α)‐2,7‐secoeburnamine derivative 1 from the leaf of Melodinus henryi is reported. Ten known alkaloids were also isolated. Their structures were determined spectroscopically. The isolates were evaluated for their cytotoxicity.     

Determination of flavonoids and saponins in Gynostemma pentaphyllum (Thunb.) Makino by liquid chromatography-mass spectrometry

Gynostemma pentaphyllum (Thunb.) Makino, a traditional Chinese herb possessing antitumor and antioxidant activities, has been shown to contain several functional components like saponins and flavonoids. However, their identities remain uncertain. The objectives of this study were to develop an appropriate extraction, purification and HPLC-MS method to determine saponins and flavonoids in G. pentaphyllum. Both flavonoids and saponins were extracted with methanol, followed by purification with a C18 cartridge to elute the former with 50% methanol and the latter with 100% methanol. A total of 34 saponins were separated within 40 min by a Gemini C18 column and a gradient mobile phase of acetonitrile and 0.1% formic acid in water, in which 18 saponins were identified by LC-MS with ESI mode and Q-TOF (LC/MS/MS). Similarly, a total of eight flavonoids were separated within 45 min by the same column and a gradient solvent system of methanol and 0.1% formic acid in water, with identification being carried out by a post-column derivatization method and LC-MS with ESI mode. The amounts of flavonoids in G. pentaphyllum ranged from 170.7 to 2416.5 μg g⁻¹, whereas saponins were from 491.0 to 89,888.9 μg g⁻¹.     

Triterpene glycosides from <Emphasis Type="Italic">Lonicera</Emphasis>. II. Isolation and structural determination of glycosides from flower buds of <Emphasis Type="Italic">Lonicera macranthoides</Emphasis>

Two new triterpenoid saponins, lonimacranthoide II (8) and III (9), were isolated from the flower buds of Lonicera macranthoides Hand.-Mazz. (Caprifoliaceae), as well as one known saponin 10. The structures of the saponins were established based on chemical and spectral methods.     

New Dammarane‐Type Saponins from the Rhizomes of Panax japonicus

Phytochemical investigation of the rhizomes of Panax japonicus C. A. Meyer (Araliaceae) resulted in the isolation of two new dammarane‐type triterpenoid saponins, yesanchinoside R₁ ( 1 ) and yesanchinoside R₂ ( 2 ), together with one new natural product, 6′′′‐O‐acetylginsenoside Re ( 3 ). In addition, 25 known compounds, including 23 triterpenoid saponins, 4 – 26 , β‐sitosterol 3‐O‐β‐D ‐glucopyranoside ( 27 ), and ecdysterone ( 28 ), were also identified. The known saponins 12, 15 , and 18 – 22 were reported for the first time from the title plant. Their structures were elucidated on the basis of detailed spectroscopic analyses, including 1D‐ and 2D‐NMR techniques, as well as acidic hydrolysis.     

Triterpene saponins fromThalictrum minus. II. Structure of an artefact

The acid hydrolysis of the predominating saponins isolated fromThalictrum minu? L. has led to the formation of a triterpenoid (I), which is an artefact of the native genin. The structure of (I) has been established as 22,25-epoxylanost-9(11)-ene-3β,16β,29-triol.