Triterpenoid saponins from Piptadeniastrum africanum (Hook. f.) Brenan

One new triterpenoid saponin, named piptadeniaoside (1), along with two known saponins (2–3) have been isolated from the stem bark of Piptadeniastrum africanum. After previous isolation of flavone derivatives from this plant, new phytochemical investigations were performed for its saponin content. Their structures were established by direct interpretation of their spectral data, mainly HRESIMS, 1D NMR (¹H, ¹³C NMR, DEPT) and 2D NMR (COSY, NOESY, HSQC and HMBC), and by comparison with the literature data.     

Quality markers based on phytochemical analysis and anti-inflammatory screening: An integrated strategy for the quality control of Dalbergia odorifera by UHPLC-Q-Orbitrap HRMS

BackgroundQuality control, key for the clinical application of traditional Chinese medicines (TCMs), should be connected to the authentication and efficacy of TCMs. The heartwood of Dalbergia odorifera has been widely used to treat inflammation-related diseases. However, in the Chinese pharmacopeia, only the total volatile oil, which does not sufficiently reflect the clinical efficacy, is used as a quality control indicator.PurposeEstablishing a “phytochemical-specificity-effectiveness-Q-marker” analytical strategy to improve the quality control of D. odorifera.MethodsCombined with biosynthetic pathway analysis, phytochemical compositions identified by UHPLC-Q-Orbitrap HRMS were used to build substantial phytochemical groups and further discover specific Q-markers. Then, lipopolysaccharide-stimulated RAW 264.7 cells were used to screen effective anti-inflammatory ingredients. Finally, a UHPLC-HRMS method was developed and validated to quantify the selected Q-markers in D. odorifera samples.ResultsAlong the constructed biosynthetic pathways, 93 phytochemical components were identified in D. odorifera, including 7 chalcones, 13 flavanones, 21 isoflavones, 21 isoflavanones, 3 flavonols, 19 neoflavones, etc. Among them, 31 compounds representing these 6 categories were further evaluated for their anti-inflammatory activities. It revealed that the extract of D. odorifera and nine flavonoids in the noncytotoxic range could alleviated lipopolysaccharide-stimulated inflammation in RAW 264.7 cells by decreasing the production of proinflammatory mediators such as nitric oxide and interleukin-6. Notably, neoflavones, as species-specific components, exhibited superior anti-inflammatory activities among the representative compounds. Finally, 12 Q-markers (butin, liquiritigenin, eriodictyol, melanettin, naringenin, butein, genistein, 4′-hydroxy-4-methoxydalbergione, isoliquiritigenin, 2,4-dihydroxy-5-methoxybenzophenone, medicarpin, and pinocembrin), which reflect specificity and effectiveness, were successfully quantified in 10 batches of samples from different origins. The origins and consistency of D. odorifera could be efficiently discriminated by hierarchical cluster analysis (HCA).ConclusionThe analysis strategy that combines phytochemical analysis with anti-inflammatory screening clarified the therapeutic material basis and discovered Q-markers, which possibly offers a more comprehensive quality assessment of D. odorifera.     

Triterpenoid saponins from Albizia boromoensis Aubrév. & Pellegr

As part of our search of new bioactive saponins from Cameroonian medicinal plants, phytochemical investigation of the roots of Albizia boromoensis led to the isolation of four new oleanane-type saponins, named boromoenosides A–D (1–4). Their structures were established by direct interpretation of their spectral data, mainly HRESIMS, 1D NMR (¹H, ¹³C NMR, and DEPT) and 2D NMR (COSY, NOESY, HSQC and HMBC), and by comparison with the literature data. All isolated saponins were assayed for their cytotoxicity against U-87 MG human glioblastoma cell lines and TG1 glioblastoma stem-like cells with no positive activity detected.     

Naturally occurring prenylated coumarins from Micromelum integerrimum twigs

A phytochemical investigation of secondary metabolites from Micromelum integerrimum was reported. Two new prenylated coumarins named as hydramicromelin D (1) and integerrimelin (2) were isolated along with 9 known coumarin derivatives. The chemical structures as well as relative stereochemistries of those coumarins were confirmed on the basis of extensive spectroscopic data interpretation and comparison with those previously published data.     

Iridoid aglycones from the underground parts of Lathraea squamaria

Two epimeric pairs of iridoid aglycones (1a, 1b, 2a, and 2b) were isolated from the underground parts of Lathraea squamaria L. (Orobanchaceae) in a phytochemical study. Their structures were elucidated by UV, 1D and 2D NMR, and comparison with data in the literature. This is the first report of the isolation of these compounds from the species L. squamaria and the family Orobanchaceae. The chemophenetic significance and possible reasons for the occurrence of such iridoid aglycones in holoparasitic plants are discussed.     

A phylogenetic groundplan of the specific complex Dactylis glomerata

A phytochemical examination of the specific complex of Dactylis glomerata L. based on flavonoid patterns, has led to a proposed evolutionary scheme. Two phyla are pointed out, originating from diploid ancestors related respectively to D.g. subsp, aschersoniana and D.g. subsp. smithii. The temperate component of the specific complex is monophyletic, derivating from a D.g. subsp, aschersoniana-like diploid ancestor. On the other hand, chemical data support a polyphyletic origin for the geographically mediterranean part of the complex with several subphyla originating from D.g. subsp. aschersoniana-like, smithii-like and secondarily juncinella-like diploids.     

Phenotypic and phytochemical diversity among different populations of Stachys lavandulifolia

Stachys lavandulifolia is an herb growing wild in Iran with interesting medicinal properties. In this research, the variability of morphological characters and phytochemical compositions among and within eight populations of this species was studied. Characteristics including inflorescence length, internode length, leaf shape, corolla color, state of calyx trichomes, state of leaf trichomes and corolla length were the most variable morphological characteristics among the examined populations. The phytochemical characterization revealed 45 components in the essential oils. Germacrene D and δ-cadinene were the main component with the highest contents. α-Copaene was positively correlated with δ-cadinene and limonene, while germacrene D was negatively correlated with δ-cadinene. UPGMA dendrogram constructed based on combined data of morphological variables and phytochemical compositions distinguished studied populations with high inter- and intra-population diversity. The high level of phytochemical and morphological variability among and within the studied populations suggests a breeding approach during the domestication, to gain new, promising, and homogenous cultivars, attractive for the industry and agriculture.     

Chemical constituents from Eucalyptus citriodora Hook leaves and their glucose transporter 4 translocation activities

Bioassay-guided phytochemical investigation of the EtOAc fraction from the leaves of a Chinese medicinal herb, Eucalyptus citriodora Hook, resulted in the isolation of a new compound rhodomyrtosone E (1), along with 12 known compounds (2–13). The structure of the new compound was established by 1D and 2D NMR, MS data and X-ray crystallographic analysis. Betulinic acid (2) and corosolic acid (5) increased glucose transporter 4 (GLUT-4) translocation by 2.38 and 1.78-fold, respectively.     

New flavonoids from the underground parts of Eriosema laurentii

Pharmacological, toxicological and phytochemical investigations of aerial parts of Eriosema laurentii De Wild. (Leguminosae), a plant used in traditional African medicine, showed a complex pattern of very rare and several new exceptional phenolic compounds. In continuation of the phytochemical work and based on the activity of an extract from the underground parts, the presented study showed the occurrence of a new pyranoisoflavone, named methyleriosemaone D, and a new highly prenylated (2S,3S)-6,8,3′-triprenyl-3,5,7,2′,4′-pentahydroxyflavanone in these parts of E. laurentii. In addition, the very rare pyranoisoflavone eriosemaone D was proven in this plant for the first time. All structures were elucidated unambiguously by extensive MS- and one and two-dimensional NMR-experiments. Detailed NMR spectra of eriosemaone D were included to rationalize the correction of some of the previously reported carbon signals in the ¹³C NMR spectrum. The estrogenic activity of the extract and isolated compounds was tested in an estrogen receptor α yeast transactivation assay.     

Chemical constituents from Nuxia congesta and their chemotaxonomic significance

A phytochemical investigation of the aerial parts of Nuxia congesta led to the isolation and identification of fifteen compounds, including a new flavonoid, nuxiacin (5-hydroxy-3,8-dimethoxy flavone-7-O-β-D-glycopyranoside) (1). The structure of the new compound was determined using various spectroscopic data including 1D and 2D NMR and mass spectroscopy. All compounds were isolated from N. congesta for the first time. The chemotaxonomic significance of the isolated compounds in the family Stilbaceae and order Lamiales are discussed herein.     

Four new cassane diterpenes from the seeds of Caesalpinia minax

In our survey on the chemical composition of traditional Chinese medicines to further elucidate their chemical substances for the treatment of diseases, we investigated the chemical constituents of the seeds of plants Caesalpinia minax. The investigation led to the isolation and identification of four new cassane diterpenes, caesalpines A–D (1–4). Their structures were elucidated on the basis of extensive 1D and 2D NMR (COSY, HMQC, HMBC, and NOESY) and mass (ESIMS and HR-ESIMS) spectroscopic data analyses. The phytochemical results imply that cassane diterpenes are maybe regarded as the characteristic constituents of C. minax.     

Terpenoids and other constituents from Euphorbia bupleuroides

The phytochemical investigation of the roots of Euphorbia bupleuroides Desf. (Euphorbiaceae) yielded three new compounds named 4,20-dideoxy(4α)phorbol-12-benzoate-13-isobutyrate (1), 25-hydroperoxycycloart-3β-ol (2), and 3β,7β-dihydroxy-4α,14α-dimethyl-8β,9β-epoxy-5α-ergosta-24(28)-ene (3), together with 17 known compounds 4–20. Their structures were established from analysis of 1D (¹H, ¹³C and DEPT) and 2D NMR (COSY, HSQC, HMBC and NOESY) data, and of mass spectrometry (HRESIMS), and by comparison with literature data.     

Four new cytotoxic oligosaccharidic derivatives of 12-oleanene from Lysimachia heterogenea Klatt

Cytotoxicity-guided phytochemical analysis on the extract of Lysimachia heterogenea Klatt led to the isolation of 3β,16β-12-oleanene-3,16,23,28-tetrol (1) and its four new oligosaccharidic derivatives heterogenosides A, B, C, and D (2–5). Their structural elucidation was mainly based on NMR and mass spectral data. The time course experimental results indicated that unlike the likely lysis activity of heterogenosides B–D, heterogenoside A showed a significantly time-dependent cytotoxicity.     

Chemical constituents of the roots of Ormocarpum sennoides subsp. zanzibaricum

Phytochemical investigation of the roots of O. sennoides subsp. zanzibaricum Brenan & J.B. Gillett resulted in the isolation of three biflavonoids (trime-chamaejasmin, (+)- chamaejasmin, (+)-liquiritigeninyl-(I-3,II-3)-naringenin), one bi-4-phenyldihydrocoumarin (diphysin), one isoflavan (glabridin), one triterpenoid (3-O-acetyloleanoic acid) and a phytosterol (β-sitosterol). Compounds were identified by detailed MS, 1D and 2D NMR spectroscopic analyses. Their absolute configurations were elucidated based on ECD spectra. The previously undescribed trime-chamaejasmin represents a bis-epi-chamaejasmenin C diastereomer. The chemophenetic significance is discussed in detail. The results contribute to the phytochemical characterization of the genus Ormocarpum and suggest a close chemophenetic relationship with other genera within the subfamily Papilionoideae. Furthermore, this report provides baseline data for comparing the two infraspecific taxa of O. sennoides (Willd.) DC.     

Phytochemical investigation of the rhizomes of Dryopteris crassirhizoma

A comprehensive phytochemical investigation of the rhizomes of Dryopteris crassirhizoma Nakai resulted in the isolation and identification of one new trimeric phloroglucinol, trisflavaspidic acid ABB (1) together with 12 known compounds including phloroglucinol, flavan, terpene, phenolic and acyclic analogs. Their structures were established by spectroscopic methods including IR, UV, MS and 1D and 2D NMR.     

Natural NO inhibitors from the leaves of Callicarpa kwangtungensis: Structures,activities, and interactions with iNOS

A phytochemical investigation to obtain new NO inhibitors resulted in the isolation of a new diterpenoid with a rare 9,10-seco-abietane skeleton (1) and twelve known terpenoids (2–13) from Callicarpa kwangtungensis. Their structures were elucidated on the basis of extensive 1D and 2D NMR spectroscopic data analyses, and the absolute configuration of compound 1 was established by comparison of the calculated and experimental electronic circular dichroism (ECD) spectra. The inhibitory activities on lipopolysaccharide-induced NO production in murine microglial BV-2 cells of these terpenoids were evaluated, and all of the compounds showed inhibitory effects. The following molecular docking studies showed interactions of the bioactive compounds with the iNOS protein.     

Isoquinoline alkaloids from the leaves of Annona leptopetala (Annonaceae)

The phytochemical investigation of the leaves of Annona leptopetala (R. E. Fr.) H. Rainer led to the characterization of tetrahydroprotoberberine corypalmine, and four aporphine (laurotetanine, anonaine, norannuradhapurine and nornuciferine) alkaloids. The structures were established after analysis of their NMR spectral data including 2D NMR experiments. This is the first report of laurotetanine and nornuciferine in A. leptopetala as well as norannuradhapurine in the genus Annona. The ¹³C NMR data of the natural alkaloid norannuradhapurine are reported here for the first time, and the NMR data for the compound corypalmine are reviewed.     

Chemical constituents of Stenotaenia macrocarpa Freyn & Sint. (Apiaceae)

Phytochemical investigation of Stenotaenia macrocarpa Freyn & Sint. (Apiaceae) led to the isolation of ten known compounds: eight flavonoids (1–8) and two furanocoumarins (9–10). The chemical structures of the compounds were elucidated based on 1D and 2D NMR and MS spectra, as well as comparison with the relevant literature data. To the best of our knowledge, this is the first detailed phytochemical study about Stenotaenia macrocarpa and the first report on the isolation of all the compounds from the genus Stenotaenia, and manghaslin (2) and its methoxylated derivative typhaneoside (3) from Apiaceae. The chemotaxonomic significance of isolates was also discussed.     

Isoquinoline-derived alkaloids and one terpene lactone from the leaves of Duguetia pycnastera (Annonaceae)

The phytochemical investigation from the leaves of Duguetia pycnastera Sandwith (Annonaceae) led to the isolation and identification of ten compounds: nine isoquinoline-derived alkaloids, including five aporphines, anonaine, isopiline, O-methylisopiline, nornuciferine, and norstephalagine; three oxoaporphines, O-methylmoschatoline, liriodenine, and lysicamine; and one tetrahydroprotoberberine, isocorypalmine; in addition, one C₁₁-terpene lactone known as loliolide. The isolated compounds (except for O-methylmochatoline and lysicamine) are described for the first time in the species and their chemophenetics relationships were discussed. The occurrence of loliolide is reported for the first time in the Duguetia. The structure elucidation of these compounds was established by extensive analyzes of 1D and 2D NMR spectroscopy in combination with MS. The NMR spectroscopic data for norstephalagine and isocorypalmine were reviewed.     

Comparison of metabolomics of Dendrobium officinale in different habitats by UPLC-Q-TOF-MS

Dendrobium officinale has been considered over past centuries to be extremely valuable for use as an herbal medicine in South Asian countries. In this work, the chemical profiles of D. officinale from different habitats were systematically characterized using ultra-performance liquid chromatography time-of-flight mass spectrometry (UPLC-Q-TOF-MS) and multivariate analysis. The principal component analysis (PCA), partial least squares discriminate analysis (PLS-DA) and orthogonal partial least squares analysis (OPLS-DA) of UPLC-Q-TOF-MS data displayed an obvious separation. Several flavonoids and terpenoids derivatives contribute to the quantitative chemotypic variation within and between the samples as observed. These findings lead to a better understanding of the phytochemical variation of D. officinale which can aid in quality control of raw material.