Undescribed steroidal alkaloids from the bulbs of Fritillaria ussuriensis Maxim and their anti-inflammatory activities.

In total, 16 undescribed steroidal alkaloids (1-16), along with nine known ones (17-25), were isolated from the bulbs of Fritillaria ussuriensis Maxim. Among the undescribed compounds mentioned, compounds 1-6, 8 bearing an 16ß-hydroxy substituent, as well as compounds 13 and 14 exhibited an unusual seven-membered skeleton. Their structures were established based on extensive spectroscopic analyses, including HRESIMS and NMR (1D and 2D), and comparison with the data reported in the literature. Furthermore, all the compounds were evaluated for their anti-inflammatory effect on the NO production of LPS-stimulated RAW264.7 cells. Compounds 1, 4, 11, 15, 22 and 24 could significantly inhibit NO production with IC50 values below 10 µM.

Biochar-based polymeric film as sustainable and efficient sorptive phase for preconcentration of steroid hormones in environmental waters and wastewaters.

BACKGROUND: The environmental impact of sample preparation should be minimized through simplification of the procedures and the use of natural, renewable and/or reusable materials. In such scenario, thin-film microextraction fulfils the former criteria, as it enables few steps and miniaturization, thus small amount of extraction phase. At the same time, the use of sorbents such as biochars obtained from biomass waste is even more promoted due to their availability at low cost and increased life-cycle in a circular economy vision. However, it is not always easy to combine these criteria in sample preparation. RESULTS: A thin film microextraction was developed for the determination of steroids in aqueous samples, entailing a membrane made of cellulose triacetate and a wood-derived biochar (Nuchar®) as carbon precursor. Different characterization techniques showed the successful preparation, whereas the sorption kinetics experiments demonstrated that biochar is responsible for the extraction with the polymer acting as a smart support. After a study about membranes' composition in terms of biochar amounts (4 %, 10 %, 16 % wt) and type of synthesis set up, the ceramic 3D-mold was selected, achieving reproducible and ready-to-use membranes with composition fixed as 10 %. Different elution conditions, viz. type and time of agitation, type, composition and volume of eluent, were evaluated. The final microextraction followed by HPLC-MS/MS quantification was successfully validated in river and wastewater treatment plant effluent samples in terms of accuracy (R% 64-123 %, RSD<19 % in river; R% 61-118 %, RSD <18 % in effluent, n = 4), sensitivity (MQLs 0.2-8.5 ng L-1) and robustness. SIGNIFICANCE: This novel biochar-based polymeric film proved to be a valid and sustainable sorbent, in terms of extraction capability, ease of preparation and greenness. By comparison with literature and the greenness evaluation with the most recent metric tools, this method expands the potential applicability of the thin-film microextraction and opens up innovative scenarios for sustainable procedures entailing the use of biochars entrapped in bio-polymers.

Cevanine-type steroidal alkaloids from the bulbs of Fritillaria cirrhosa D. Don.

Eight previously undescribed cevanine-type steroidal alkaloids, cirrhosinones I-N and cirrhosinols A-B, along with five known analogs, were isolated from the bulbs of Fritillaria cirrhosa D. Don. Their structures were elucidated on the basis of comprehensive analysis of HRESIMS, 1D and 2D NMR spectroscopic data, and single-crystal X-ray diffraction analyses. All compounds revealed weak NO inhibitory activities in the LPS-stimulated NR8383 cells at the concentration of 20 µM, with inhibition ratios ranging from 5.1% to 14.3%.

Anti-inflammatory Steroids from the South China Sea Sponge Spongia officinalis.

One new highly degraded steroid, namely 21-nor-4-ene-chaxine A (1) furnishing a 5/6/5-tricyclic, along with one known related analogue (2), were isolated from the South China Sea sponge Spongia officinalis. Their structures including absolute configurations were established by extensive spectroscopic data analysis, TDDFT-ECD calculation, and comparison with the spectral data previously reported in the literature. Compound 1 represent the new member of incisterols family with a highly degradation in ring B. In vitro bioassays revealed compound 2 exhibited significant anti-microglial inflammatory effect on lipopolysaccharide (LPS)-induced inflammation in BV-2 microglial cells.

Fourteen undescribed steroidal saponins from Solanum capsicoides leaves and their neuroprotective effects.

A total of 14 previously undescribed steroidal saponins named capsicsaponins A-N were isolated from the leaves of Solanum capsicoides, encompassing various types, including cholesterol derivatives and pseudospirostanol saponins. The structures of all compounds were determined through comprehensive analysis of spectroscopic data (1D NMR and 2D NMR), along with physicochemical analysis methods (acid hydrolysis, OR, and UV). Moreover, in the H2O2-induced pheochromocytoma cell line model, compounds 1-14 were screened for their neuroprotective effects on cells. The bioassay results demonstrated compounds 8-14 were able to revive cell viability compared to the positive control edaravone. The damage neuroprotection of the most active compound was further explored.

Research progress in steroidal saponins from the genus Polygonatum: Chemical components, biosynthetic pathways and pharmacological effects.

The genus Polygonatum Mill. belongs to the Liliaceae family, which is widely distributed all over the world. Modern studies have found that Polygonatum plants are very rich in chemical compounds such as saponins, polysaccharides and flavonoids. Steroidal saponins are the most commonly studied saponins in the genus Polygonatum and a total of 156 compounds have been isolated from 10 species of the genus. These molecules possess antitumor, immunoregulatory, anti-inflammatory, antibacterial, antiviral, hypoglycemic, lipid-lowering and anti-osteoporotic activities. In this review, we summarize recent advances in studies of the chemical constituents of steroidal saponins from Polygonatum, including their structural characteristics, possible biosynthetic pathways and pharmacological effects. Then, the relationship between the structure and some physiological activities is considered. This review aims to provide reference for further exploitation and utilization of the genus Polygonatum.

Disulfated Ophiuroid Type Steroids from the Far Eastern Starfish Pteraster marsippus and Their Cytotoxic Activity on the Models of 2D and 3D Cultures.

New steroidal 3ß,21-disulfates (2-4), steroidal 3ß,22-disulfate (5), and the previously known related steroidal 3ß,21-disulfate (1) were isolated from the ethanolic extract of the Far Eastern starfish Pteraster marsippus, collected off Urup Island in the Sea of Okhotsk. The structures of these compounds were determined by intensive NMR and HRESIMS techniques as well as by chemical transformations. Steroids 2 and 3 have an oxo-group in the tetracyclic nucleus at position C-7 and differ from each other by the presence of the 5(6)-double bond. The Δ24-22-sulfoxycholestane side chain of the steroid 5 has not been found previously in the starfish or ophiuroid steroids. The cytotoxic activities of 1, 4, 5, and the mixture of 2 and 3 were determined on the models of 2D and 3D cultures of human epithelial kidney cells (HEK293), melanoma cells (SK-MEL-28), small intestine carcinoma cells (HuTu80), and breast carcinoma cells (ZR-75-1). The mixture of 2 and 3 revealed a significant inhibitory effect on the cell viability of human breast carcinoma ZR-75-1 cells, but other tested compounds were less effective.

Chemical Review of Gorgostane-Type Steroids Isolated from Marine Organisms and Their 13C-NMR Spectroscopic Data Characteristics.

Gorgostane steroids are isolated from marine organisms and consist of 30 carbon atoms with a characteristic cyclopropane moiety. From the pioneering results to the end of 2021, isolation, biosynthesis, and structural elucidation using 13C-NMR will be used. Overall, 75 compounds are categorized into five major groups: gorgost-5-ene, 5,6-epoxygorgostane, 5,6-dihydroxygorgostane, 9,11-secogorgostane, and 23-demethylgorgostane, in addition to miscellaneous gorgostane. The structural diversity, selectivity for marine organisms, and biological effects of gorgostane steroids have generated considerable interest in the field of drug discovery research.

Govanoside B, a new steroidal saponin from rhizomes of Trillium govanianum.

Trillium govanianum, commonly known as Nag Chhatri and Teen Patra, is a popular herbal supplement traditionally used for curing different inflammatory and sexual disorders, infection and wound healing. Steroidal saponins are considered as active components of this species. The present study demonstrated the isolation of nine steroidal saponins, including one new compound named as govanoside B (9) and eight known, pregna-chacotrioside (1), pennogenin-triglycoside (2), borassoside E (3), pennogenin-tetraglycoside (4), protodioscin (5), clintonioside B (6), pennogenin-diglycoside (7) and borassoside D (8). This is the first report on the isolation of 1, 2, 4, 5, 6, 7 and 8 from rhizomes of T. govanianum. The extract, fractions and isolated compounds were further evaluated for their DPPH and ABTS radical scavenging activity.

Parisvaniosides A-E, five new steroidal saponins from Paris vaniotii.

The species of Paris genus is a prolific source of structurally diverse steroidal saponins responsible for multivarious biological properties. The first phytochemical investigation on the steroidal saponin constituents from the rhizomes of Paris vaniotii Lévl. led to the discovery and structural characterization of four new spirostanol saponins, named parisvaniosides A-D (1-4), and one new furostanol glycoside, named parisvanioside E (5), along with eleven known analogues (6-16). Their structures were unambiguously established on the basis of extensive spectroscopic analysis and comparison with the reported spectroscopic data. Compound 1 is a rare spirostanol saponin sharing with a C-9/C-11 double bond and a peroxy group located between C-5 and C-8 of the aglycone, whereas 3 and 4 are unusual C-27 steroidal sapoins with hydroxyl/methoxyl at both C-5 and C-6. Furthermore, 5 is the first furostanol saponin with a unique aglycone featuring two trisubstituted double bonds in ring B. All isolated saponins were evaluated for their anti-inflammatory effects on a lipopolysaccharide (LPS)-stimulated nitric oxide (NO) production model in RAW 264.7 macrophages.

Identification of C21 Steroidal Glycosides from Gymnema sylvestre (Retz.) and Evaluation of Their Glucose Uptake Activities.

Gymnema sylvestre (Retz.) Schult is a multi-purpose traditional medicine that has long been used for the treatment of various diseases. To discover the potential bioactive composition of G. sylvestre, a chemical investigation was thus performed. In this research, four new C21 steroidal glycosides sylvepregosides A-D (1-4) were isolated along with four known compounds, gymnepregoside H (5), deacetylkidjoladinin (6), gymnepregoside G (7) and gymnepregoside I (8), from the ethyl acetate fraction of G. sylvestre. The structures of the new compounds were established by extensive 1D and 2D nuclear magnetic resonance (NMR) spectra with mass spectroscopy data. Compounds 1-6 promoted glucose uptake by the range of 1.10- to 2.37-fold, respectively. Compound 1 showed the most potent glucose uptake, with 1.37-fold enhancement. Further study showed that compounds 1 and 5 could promote GLUT-4 fusion with the plasma membrane in L6 cells. The result attained in this study indicated that the separation and characterization of these compounds play an important role in the research and development of new anti-diabetic drugs and pharmaceutical industry.

Polyhydroxylated steroids from the Vietnamese soft coral Sarcophyton ehrenbergi.

Fourteen polyhydroxylated steroids including six new compounds, ehrensteroids A - F (1-6), were isolated from the Vietnamese soft coral Sarcophyton ehrenbergi after applying various chromatographic separations. The structure elucidation was done by detailed analysis of 1D, 2D NMR and HR QTOF mass spectra. In addition, significant cytotoxicity (IC50 values ranging from 8.45 ± 0.56 to 38.27 ± 2.39 µM) against all five tested cancer cell lines as LU-1 (lung cancer), HepG2 (hepatoma cancer), MCF-7 (breast cancer), HL-60 (acute leukemia), and SW480 (colon adenocarcinoma) was observed for compounds 1, 2, 6-10, and 12-14, whereas this activity on LU-1 (IC50 = 21.91 ± 2.72 µM) and HepG2 (IC50 = 20.32 ± 0.03 µM) cell lines was also observed for 4.

New NF-κB Inhibitory Steroids from the Marine Sponge Dysidea avara Collected from the South China Sea.

Chemical investigation of the marine sponge Dysidea avara, collected from the South China Sea, yielded 13 steroids, including nine new (1-9) and four known (10-13) ones. The new structures were elucidated as (3S,14R)-3,14-dihydroxycholesta-5,8-dien-7-one (1), (22E,24R)-7α-ethoxy-5α,6α-epoxyergosta-8(14),22-dien-3ß-ol (2), 3ß-hydroxy-7α-ethoxy-5α,6α-epoxy-8(14)-cholestene (3), 3ß,5α-dihydroxy-6α-ethoxychofesta-7,9(11)-diene (4), 3ß,5α-dihydroxy-6ß-ethoxycholest-7-ene (5), (22E,24R)-24-ethoxy-3ß,5α-dihydroxy-6ß-ethoxyergosta-7,22-diene (6), (22E)-3ß,5α-dihydroxy-6ß-ethoxycholesta-7,22-diene (7), 24-ethoxy-3ß,5α-dihydroxy-6ß-ethoxycholest-7-ene (8 and 9), by extensive spectroscopic analyses, such as HR-ESI-MS, 1D and 2D NMR data. The absolute configuration of 1 was assigned by comparison the experimental ECD spectra with the calculated ones. Among the 13 metabolites, compounds 1, 4, 11, 12, and 13 showed NF-κB inhibitory activities in human HER-293 cells with IC50 values of 6.4, 18.7, 8.1, 9.6, and 7.5 µM, respectively. Preliminary structure-activity relationship analysis unveiled that the conjugated ketones or unsaturated double bonds might be the functional groups for the five active steroids.

Taccachatrones A-G, Highly Oxidized Steroids from the Rhizomes of Tacca chantrierii and Their Cytotoxicity Assessment.

Seven highly oxidized steroids, taccachatrones A-G (1-7), together with four known taccalonolides (8-11), were characterized from the rhizomes of Tacca chantrieri. The structures of 1-7 were established on the basis of spectroscopic data analysis, while the absolute configurations were determined by single-crystal X-ray diffraction. Compounds 1-4 may be derived from taccalonolide derivatives by the degradation of three carbon atoms. Compounds 7, 8, 10, and 11 exhibited cytotoxicity to human cancer cell lines, indicating that the presence of a lactone moiety, as well as a double bond between C-22 and C-23, might play key roles in mediating their cytotoxicity.

Steroidal saponins with cytotoxic effects from the rhizomes of Asparagus cochinchinensis.

In the ongoing research on potent antitumor agents from the rhizomes of Asparagus cochinchinensis, seven undescribed steroidal saponins asparagusoside A-G (1-7), along with twenty known ones (8-27), were isolated and elucidated via analyzing their 1D, 2D NMR, mass spectroscopic data and chemical methods. All isolated compounds were evaluated for their cytotoxic effects against human large cell lung carcinoma cells (NCI-H460) in vitro. Among them, compounds 7, 9 and 27 showed more significant antitumor activities than the positive control cisplatin (11.56 µM) with IC50 values of 1.39, 3.04, and 2.25 µM, respectively. Further research about asparagusoside G (7) showed G0/G1 arrest in NCI-H460 cell line cycle and induced cell death by apoptosis in a dose­dependent way.

Chemical Diversity and Biological Activity of Secondary Metabolites from Soft Coral Genus Sinularia since 2013.

Sinularia is one of the conspicuous soft coral species widely distributed in the world's oceans at a depth of about 12 m. Secondary metabolites from the genus Sinularia show great chemical diversity. More than 700 secondary metabolites have been reported to date, including terpenoids, norterpenoids, steroids/steroidal glycosides, and other types. They showed a broad range of potent biological activities. There were detailed reviews on the terpenoids from Sinularia in 2013, and now, it still plays a vital role in the innovation of lead compounds for drug development. The structures, names, and pharmacological activities of compounds isolated from the genus Sinularia from 2013 to March 2021 are summarized in this review.

Sesquiterpenes and Steroids from an Endophytic Eutypella scoparia.

A chemical investigation on the EtOAc extract of the endophytic fungus Eutypella scoparia SCBG-8 led to the isolation of eight new sesquiterpenes eutyscoparins A-H (1-8), one C-28 steroid eutyscoparene A (9), one triterpenoid eutyscoparene B (10), six known terpenoids, and two known steroids. Their structures including absolute configurations were established on the basis of spectroscopic data analysis, single-crystal X-ray diffraction experiments, and electronic circular dichroism (ECD) calculations. Compound 7 displayed antibacterial activity against S. aureus and MRSA (methicillin-resistant Staphylococcus aureus) with MIC values of 6.3 µg/mL.

Chemical constituents with inhibition against TNF-α from Merrillanthus hainanensis.

Two new steroidal glycosides oxystauntoside A (1) and oxystauntoside B (2), together with sixteen known compounds (3-18) were isolated from the 95% ethanol extract of Merrillanthus hainanensis. Their structures were characterized by extensive spectroscopic analysis including NMR and mass spectra and single crystal X-ray crystallography. The absolute configuration of 1 and 2 were further determined by ECD calculations. All of these compounds were isolated from M. hainanensis for the first time. All the fractions and compounds were tested for the anti-inflammatory activity against the TNF-α factor. The ethyl acetate fraction showed the most potent inhibition (71.3%) at 10 µg/mL and compounds 5 (78.9%) and 9 (73.4%) in this fraction with both carboxyl and phenolic hydroxyl groups showed significant inhibition at 10 µM. Our study provided the first scientific report for the medicinal value of M. hainanensis.

Cytotoxic furanosesquiterpenoids and steroids from Ircinia mutans sponges.

CONTEXT: Ircinia mutans Wilson (Irciniidae) is a sponge with antimicrobial and cytotoxic constituents. OBJECTIVE: Our objective was to characterise the cytotoxic constituents of two seasonal collections of I. mutans. MATERIALS AND METHODS: The sponges were extracted in methanol-dichloromethane and their constituents were purified and characterised using column chromatography, GC-MS, 1 D and 2 D NMR. Anti-proliferative activities of the compounds, were evaluated using 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) colorimetric assay (0.25-100 µg/mL, 72 h) against leukaemia (MOLT-4), breast (MCF-7) and colon cancer (HT-29) human cells. RESULTS: Three furanosesquiterpoids; furodysin (1), ent-furodysinin (2) and furoircin (3) and ten sterols were characterised in I. mutans, for the first time. Cholesterol (4), cholesta-5, 7-dien-3ß-ol (5) and ergosterol (6) were determined in the sponge from the winter collections, while cholesta-5, 22-dien-3ß-ol (7), 24-methyldesmosterol (8), campesterol (9), stigmasterol (10), γ-ergostenol (11), chondrillasterol (12) and γ-sitosterol (13) were detected in the summer samples. The steroids from the winter collection exhibited cytotoxic activity with IC50 values of 13.0 ± 0.9, 11.1 ± 1.7 and 1.1 ± 0.4 µg/mL, against the mentioned cancer cell lines, respectively, while those from the summer sample, showed greater activity, IC50 = 1.1 ± 0.2 µg/mL against MOLT-4. The purified steroids showed potent MOLT-4 cytotoxic activity, IC50 values = 2.3-7.8 µg/mL. DISCUSSION AND CONCLUSION: The present study suggests that I. mutans is a rich source of cytotoxic steroids, and introduces 3 as new natural product. Considering the high cytotoxic activity of the steroids, these structures could be candidates for anticancer drug development in future research.

Phytochemical Profile and Antioxidant Activity of Nigella sativa L Growing in Morocco.

BACKGROUND: Nigella sativa L (NS) is a powerful antioxidant and medicinal plant with many therapeutic applications particularly in traditional medicine for respiratory, gastrointestinal, rheumatic, and inflammatory disorders, as well as cancer. OBJECTIVE: The aim of this study is to extract the active ingredients from the Moroccan Nigella sativa L and determine its antioxidant properties. We hypothesize that the separation of the compounds from Nigella sativa L has either a positive or negative effect on antioxidants. To study this, we explored different methods to simultaneously extract and separate compounds from Nigella sativa L and performed antioxidant tests (ß-carotene and DPPH) for all collected fractions. METHODS: Nigella sativa L was hot-extracted by Soxhlet and mother extracts and was separated using silica column chromatography with adequate eluents. Qualitative phytochemical tests to determine the chemical families in Nigella sativa L seeds were performed on the fractions. They were also identified and characterized by GC-MS and HPLC-DAD. Then, antioxidant activity was examined by ß-carotene bleaching and DPPH radical scavenger tests. Results and Conclusion. The mother extract hexane FH generated eight different fractions (SH1-8) and the acetone extract FA generated 11 fractions (SA1-11). The FH fractions had a high percentage of fatty acids, and the FA fractions had some interesting polyphenols derivative compounds. Phytochemical screening revealed secondary metabolites such as polyphenols flavonoids, alkaloids, steroids, terpenes coumarins, tannins, and saponins. We found that only two solvents (hexane, acetone) of different polarities could easily extract and simultaneously separate the components of Nigella sativa L. The antioxidant fractions that we collected had close activity to reference compounds but were more active than the corresponding mother extracts. Moreover, several IC50 values of fractions from acetone extract were better than those from hexane. Therefore, the antioxidant activity of Nigella sativa L is more attributed to flavonoids and polyphenols than fatty acids. In summary, the separation of hexane extract presents a more pronounced positive effect for antioxidant tests than acetone extract.