Good Practices in Sponge Natural Product Studies: Revising Vouchers with Isomalabaricane Triterpenes.

Species misidentification in the field of natural products is an acknowledged problem. These errors are especially widespread in sponge studies, albeit rarely assessed and documented. As a case study, we aim to revisit reports of isomalabaricane triterpenes, isolated from four demosponge genera: Jaspis, Geodia, Stelletta and Rhabdastrella. From a total of 44 articles (1981-2022), 27 unique vouchers were listed, 21 of which were accessed and re-examined here: 11 (52.4%) of these were misidentified. Overall, 65.9% of the studies published an incorrect species name: previously identified Jaspis and Stelletta species were all in fact Rhabdastrella globostellata. We conclude that isomalabaricane triterpenes were isolated from only two Rhabdastrella species and possibly one Geodia species. In addition to shedding a new light on the distribution of isomalabaricane triterpenes, this study is an opportunity to highlight the crucial importance of vouchers in natural product studies. Doing so, we discuss the impact of species misidentification and poor accessibility of vouchers in the field of sponge natural products. We advocate for stricter voucher guidelines in natural product journals and propose a common protocol of good practice, in the hope of reducing misidentifications in sponge studies, ensure reproducibility of studies, and facilitate follow-up work on the original material.

Evaluation on Antidiabetic Properties of Medicinal Plants from Myanmar.

OBJECTIVES: To explore the effective and safe medicines for treating diabetes. METHODS: Hydroalcoholic extracts of 130 medicinal plants belonging to 66 families were evaluated using porcine pancreatic lipase (PPL) inhibition and glucose uptake methods together with a literature review. RESULTS: The extracts of 22 species showed the PPL inhibition activity; 18 extracts of 15 species stimulated glucose uptake in 3T3-L1 adipocytes. Among them, Mansonia gagei J.R. Drumm., Mesua ferrea L., and Centella asiatica (L.) Urb. exhibited both activities. The extracts of Caladium lindenii (André) Madison rhizomes and Azadirachta indica A. Juss. leaves presented the utmost lipase inhibitory activity with IC50 of 6.86 ± 0.25 and 11.46 ± 0.06 µg/mL, respectively. The extracts of Coptis teeta Wall. rhizomes and Croton tiglium L. seeds stimulated the maximum glucose uptake. Ten species are reported to have antidiabetic activity for the first time. Flavonoids and triterpenoids are the dominant antidiabetic compounds in selected medicinal plants from Myanmar. CONCLUSIONS: P. zeylanica, L. cubeba, H. crenulate, M. gagei, C. teeta, and M. ferrea are worthy to advance further study according to their strong antidiabetic activities and limited research on effects in in vivo animal studies, unclear chemical constitutes, and safety.

A Review on Phytochemicals of the Genus Maytenus and Their Bioactive Studies.

The genus Maytenus is a member of the Celastraceae family, of which several species have long been used in traditional medicine. Between 1976 and 2021, nearly 270 new compounds have been isolated and elucidated from the genus Maytenus. Among these, maytansine and its homologues are extremely rare in nature. Owing to its unique skeleton and remarkable bioactivities, maytansine has attracted many synthetic endeavors in order to construct its core structure. In this paper, the current status of the past 45 years of research on Maytenus, with respect to its chemical and biological activities are discussed. The chemical research includes its structural classification into triterpenoids, sesquiterpenes and alkaloids, along with several chemical synthesis methods of maytansine or maytansine fragments. The biological activity research includes activities, such as anti-tumor, anti-bacterial and anti-inflammatory activities, as well as HIV inhibition, which can provide a theoretical basis for the better development and utilization of the Maytenus.

Comparative Studies on Polysaccharides, Triterpenoids, and Essential Oil from Fermented Mycelia and Cultivated Sclerotium of a Medicinal and Edible Mushroom, Poria Cocos.

Poria cocos, an important medicinal and edible fungus, is well known in East Asia. The main active components are water-soluble polysaccharides (WPS) and triterpenoids. Due to the growing market demand, long cultivation period, and consumption of pine trunk during cultivation, alternative methods for producing P. cocos or its active components should be investigated. In this study, WPS, triterpenoids, monosaccharide composition, and essential oil in fermented mycelia and cultivated sclerotium were analyzed using UV spectrophotometry, HPLC, pre-column derivatization, and HS-GC/MS, respectively. Our results showed that the WPS and triterpenoids in mycelia are several times higher than those in sclerotium. Among the 62 compounds identified by HS-GC/MS analysis from the essential oil obtained from the fermentation media and a fresh external layer, the two main fragrances in common were linalool and methyl phenylacetate. Our results suggested that it is applicable to produce polysaccharides and triterpenoids by the fermentation of P. cocos, and a strategy to improve triterpenoid production in the fermentation process was proposed.

Phytosterols and triterpenes from Morinda lucida Benth. exhibit binding tendency against class I HDAC and HDAC7 isoforms.

The important role of histone deacetylases (HDACs) in the development of cancer has been demonstrated by various studies. Thus targeting HDACs with inhibitors is a major focus in anticancer drug research. Although few synthetic HDAC inhibitors (HDIs) have been approved for cancer treatment, they have significant undesirable side effects. Therefore emphases have been placed on natural HDIs as substitutes for the synthetic ones. In a bid to identify more HDIs, this study evaluated the binding tendency of compounds derived from Morinda lucida Benth. towards selected HDACs for the discovery of potent HDIs as potential candidates for anticancer therapeutics, based on the report of anticancer potentials of Morinda lucida-derived extracts and compounds. Givinostat and 49 Morinda-lucida derived compounds were docked against selected HDAC isoforms using AutodockVina, while binding interactions were viewed with Discovery Studio Visualizer, BIOVIA, 2016. Druglikeness and Absorption-Distribution-Metabolism-Excretion (ADME) parameters of the top 7 compounds were evaluated using the Swiss online ADME web tool. The results revealed that out of the 49 compounds, 3 phytosterols (campesterol, cycloartenol, and stigmasterol) and 2 triterpenes (oleanolic acid and ursolic acid) exhibited high HDAC inhibitory activity compared to givinostat. These 5 compounds also fulfill oral drugability of Lipinski rule of five. Morinda lucida-derived phytosterols and triterpenes show high binding tendency towards the selected HDACs and exhibited good drugability characteristics and are therefore good candidates for further studies in the search for therapies against abnormalities linked with over-activity of HDACs.

Lanostane-Type Saponins from Vitaliana primuliflora.

The phytochemistry of the genera Androsace, Cortusa, Soldanella, and Vitaliana, belonging to the Primulaceae family is not well studied so far. Hence, in this paper, we present the results of UHPLC-MS/MS analysis of several primrose family members as well as isolation and structure determination of two new saponins from Vitaliana primuliflora subsp. praetutiana. These two nor-triterpenoid saponins were characterized as (23S)-17α,23-epoxy-29-hydroxy-3ß-[(O-ß-d-glucopyranosyl-(1→2)-O-α-l-rhamnopyranosyl-(1→2)-O-ß-d-glucopyranosyl-(1→2)-O-α-l-arabinopyranosyl-(1→6)-ß-d-glucopyranosyl)oxy]-27-nor-lanost-8-en-25-one and (23S)-17α,23-epoxy-29-hydroxy-3ß-[(O-α-l-rhamnopyranosyl-(1→2)-O-ß-d-glucopyranosyl-(1→2)-O-α-l-arabinopyranosyl-(1→6)-ß-d-glucopyranosyl)oxy]-27-nor-lanost-8-en-25-one, respectively. Their structures were determined by high resolution mass spectrometry (HRMS), tandem mass spectrometry (MS/MS), one- and two-dimensional nuclear magnetic resonance spectroscopy (1D-, and 2D-NMR) analyses. So far, the 27-nor-lanostane monodesmosides were rarely found in dicotyledon plants. Therefore their presence in Vitaliana and also in Androsace species belonging to the Aretia section is unique and reported here for the first time. Additionally, eleven other saponins were determined by HRMS and MS/MS spectra. The isolated lanostane saponins can be considered as chemotaxonomic markers of the family Primulaceae.

New Chemical Constituents from the Bark of Dendropanax morbifera Leveille and their Evaluation of Antioxidant Activities.

Four new constituents, as cis-6-oxogeran-4-enyl-10-oxy-O-ß-arabinopyranosyl-4'-O-ß-arabinopyranosyl-2''-octadec-9''',12''',15'''-trienoate (1), geran-3(10)-enyl-1-oxy-O-ß-arabinopyranosyl-4'-O-ß-arabinopyranosyl-2''-octadec-9''',12''',15'''-trienoate (2), geranilan-8-oxy-O-α-d-xylopyranosyl-2'-n-octadec-9'',12'',15''-trienoate (3), 1-cyclohex-2', 5'-dienyl 1-cyclohexylethanol-O-ß-d-xylopyranoside (4), along with six known constituents, guaiacol-O-ß-d-arabinopyaranoside (5), n-tetradecanyl oleate (6), oleyl-O-ß-d-xyloside (7), n-octadec-9,12-dienoyl-O-ß-d-arabinopyranoside (8), linolenyl-O-ß-d-arabinofuranoside (9) andglyceryl-1,3-dipalmito-2-olein (10), were isolated and identified from the Dendropanax morbifera bark. The new structures were established by one-and two-dimensional NMR (and in combination with IR, FAB-MSand HR-ESI-FTMS. The comparative evaluation of antioxidant potential by phosphomolybdenum, DPPH, FRAP and the NO assay of four different compounds (1-4), we have found that the compounds 1 and 2 have power as a natural antioxidant, whereas the compound 3 and 4 exhibited mild activity in comparison to compounds 1 and 2.

Phytochemical Composition and Antioxidant Capacity of Seven Saskatoon Berry (Amelanchier alnifolia Nutt.) Genotypes Grown in Poland.

The basic chemical composition, bioactive compounds, and antioxidant capacity of fruits of three new Polish breeding clones (No. 5/6, type S, and type N) and four Canadian cultivars (cvs.) ("Martin", "Smoky", "Pembina", and "Honeywood") grown in Poland in 2016 were investigated. Fruits were analyzed for their contents of triterpenoids, carotenoids, chlorophylls, and polyphenolics with the ultra-performance liquid chromatography photodiode detector-quadrupole/time-of-flight mass spectrometry (UPLC-PDA-Q/TOF-MS) method, sugar with the high-performance liquid chromatography-evaporative light scattering detector (HPLC-ELSD) method, and antioxidant capacity with the ability to reduce free radical (ABTS) and ferric reducing ability of plasma (FRAP) method. Thirty-eight bioactive compounds, including twenty-eight polyphenolic compounds (four anthocyanins, nine phenolic acids, nine flavonols, and seven flavan-3-ols), four carotenoids, two chlorophylls, and three triterpenoids were identified in the fruits. The fruits of the tested Saskatoon berry genotypes were found to be rich in phenolic compounds (3773.94-6390.36 mg/100 g·dm), triterpenoids (66.55-91.31 mg/kg·dm), and carotenoids (478.62-561.57 mg/kg·dm), with high ABTS and FRAP capacity (10.38-34.49 and 9.66-25.34 mmol·Trolox/100 g·dm, respectively). Additionally, the berries of these genotypes seemed to be a good source of sugar (9.02-19.69 g/100 g), pectins (0.67%-1.33%), and ash (0.59%-0.67%). Some genotypes of Saskatoon berry, especially the clones type S, type N, and cvs. "Honeywood" and "Smoky", may be selected for their potential applications in commercial cultivation to produce fruits with valuable health-promoting nutritional effects on human health. Additionally, three new genotypes that may offer new functional materials can be recommended for fruit growers.

Comprehensive Characterization for Ginsenosides Biosynthesis in Ginseng Root by Integration Analysis of Chemical and Transcriptome.

Herbgenomics provides a global platform to explore the genetics and biology of herbs on the genome level. Panax ginseng C.A. Meyer is an important medicinal plant with numerous pharmaceutical effects. Previous reports mainly discussed the transcriptome of ginseng at the organ level. However, based on mass spectrometry imaging analyses, the ginsenosides varied among different tissues. In this work, ginseng root was separated into three tissues-periderm, cortex and stele-each for five duplicates. The chemical analysis and transcriptome analysis were conducted simultaneously. Gene-encoding enzymes involved in ginsenosides biosynthesis and modification were studied based on gene and molecule data. Eight widely-used ginsenosides were distributed unevenly in ginseng roots. A total of 182,881 unigenes were assembled with an N50 contig size of 1374 bp. About 21,000 of these unigenes were positively correlated with the content of ginsenosides. Additionally, we identified 192 transcripts encoding enzymes involved in two triterpenoid biosynthesis pathways and 290 transcripts encoding UDP-glycosyltransferases (UGTs). Of these UGTs, 195 UGTs (67.2%) were more highly expressed in the periderm, and that seven UGTs and one UGT were specifically expressed in the periderm and stele, respectively. This genetic resource will help to improve the interpretation on complex mechanisms of ginsenosides biosynthesis, accumulation, and transportation.

Cytotoxic Tirucallane and Apotirucallane Triterpenoids from the Stems of Picrasma quassioides.

Phytochemical investigation on the stems of Picrasma quassioides led to the isolation of a novel compound, picraquassin A (1), with an unprecedented 21,24-cycloapotirucallane skeleton, and four new apotirucallane-type triterpenoids (2-5), together with 15 new tirucallane-type triterpenoids (6-20) and 10 known tirucallane-type triterpenoids (21-30). To our knowledge, this is the first report demonstrating the presence of apotirucallane-type triterpenoids in the genus Picrasma. The structures of the new compounds were determined based on spectroscopic data interpretation. Cytotoxicities of the isolated compounds were evaluated using three human cancer cell lines, MKN-28, A-549, and MCF-7. Compound 2 exhibited the most potent activity against MKN-28 cells with an IC50 value of 2.5 µM. Flow cytometry and Western blot analysis revealed that 2 induces the apoptosis of MKN-28 cells via activating caspase-3/-9, while increasing Bax and Bad and decreasing Bcl-2 expression levels.

Triterpenes as potentially cytotoxic compounds.

Triterpenes are compounds of natural origin, which have numerously biological activities: anti-cancer properties, anti-inflammatory, anti-oxidative, anti-viral, anti-bacterial and anti-fungal. These substances can be isolated from plants, animals or fungi. Nowadays, when neoplasms are main cause of death, triterpenes can become an alternative method for treating cancer because of their cytotoxic properties and chemopreventive activities.

Unusual fernane and gammacerane glycosides from the aerial parts of Spergula fallax.

The aerial parts of Spergula fallax afforded four glycosides (1-4) based on two new triterpene aglycones (1a and 2a), along with the known hopane glycoside succulentoside A. Compound 1 was identified as belonging to the fernane class, unusual migrated hopane triterpenoids, mainly isolated from ferns and only rarely from higher plants. Compounds 2-4 were assigned as gammacerane glycosides, having as aglycone a hydroxylated derivative of tetrahymanol. The structures of the isolated compounds 1-4 and their aglycones 1a and 2a obtained by acid hydrolysis were elucidated by spectroscopic data interpretation. The growth inhibitory activity of the isolated compounds and their aglycones was evaluated against the HeLa and DLD-1 cancer cell lines.

Triterpenoids.

This review covers the isolation and structure determination of triterpenoids including squalene derivatives, protostanes, lanostanes, holostanes, cycloartanes, dammaranes, euphanes, tirucallanes, tetranortriterpenoids, lupanes, oleananes, friedelanes, ursanes, hopanes, isomalabaricanes and saponins; 574 references are cited.

Differentiation of black and white pitch (Burseraceae) oleoresins: A mass spectrometry-based chemoethnotaxonomic study.

ETHNOPHARMACOLOGICAL RELEVANCE: In the quilombola communities of the municipality of Oriximiná (Pará State, Brazil), Protium spp. (Burseraceae) oleoresins are distinguished in black and white pitch. White pitch oleoresins may be superior to black pitch in terms of quality, but the criteria used for their differentiation are fairly subjective. AIM OF THE STUDY: This study was designed to provide a scientific rationale for the traditional differentiation of black and white pitch oleoresins based on their non-volatile fraction. MATERIALS AND METHODS: Black and white pitch oleoresin samples collected in quilombola territories in Oriximiná were analysed by GC-EI-MS and UPLC-APCI-MS. The feasibility of EI and APCI mass spectrometry-based pattern recognition methods PLS-DA and Random Forest Analysis (RFA) for black and white pitch oleoresins differentiation was demonstrated. RESULTS: The UPLC-APCI-MS method allowed the separation of 43 triterpenoids. Assessment of the triterpenoid fingerprints by GC-EI-MS led to the tentative identification of ursa-9(11),12-dien-3-ol as a potential marker for black pitch oleoresins. PLS-DA and RFA applied to the APCI-MS and EI-MS data gave good models for black and white pitch oleoresins classification. The most important ions for the classifications of black pitch oleoresins by APCI-MS/PLS-DA and APCI-MS/RFA likely represented triterpenoid acids. CONCLUSIONS: The triterpenoid pattern differs between black and white pitch oleoresins. The characteristic presence of ursa-9(11),12-dien-3-ol and triterpenoids acids in black pitch oleoresins, along with other field observations, suggest that black pitch oleoresins are actually aged white pitch oleoresins.

Structural characterization of schintrilactone, a new class of nortriterpenoids from Schisandra chinensis.

Two new nortriterpenoids, designated as schintrilactones A (1) and B (2), with modified five-membered D ring and delta-lactone E ring, were isolated from Schisandra chinensis. Their structures were determined to have a unique carbon skeleton by elucidation of spectroscopic evidence and density functional theory calculations of circular dichroism. Schintrilactones A and B occur as a pair of configurationally unstable and thus slowly interconverting diastereomers.

Ceanothane- and lupane-type triterpene esters from the roots of Hovenia dulcis and their antiproliferative activity on HSC-T6 cells.

Three ceanothane-type and three lupane-type triterpenoids, as well as three known compounds, were isolated from the roots of Hovenia dulcis (Rhamnaceae), based on LC-MS dereplication. The previously undescribed compounds were determined to be 27-O-protocatechuoyl-3-dehydroxyisoceanothanolic acid, 27-O-protocatechuoyl-3-dehydroxycolubrinic acid, 27-O-protocatechuoyl-3-dehydroxyepicolubrinic acid, 27-O-protocatechuoylbetulinic acid, 27-O-p-hydroxybenzoylbetulinic acid, and 27-O-syringoylbetulinic acid by 1D and 2D NMR spectroscopic and HR mass spectrometric data analysis. The isolates were examined for their antiproliferative activity in HSC-T6 hepatic stellate cells; compounds 1, 2, 3, and 6 showed IC50 values in the range of 15-50 µM.

Six New Lanostane Triterpenoids from the Fruiting Body of Tyromyces sambuceus and Antiproliferative Activity.

During the search for secondary metabolites with antiproliferative activity, six new lanostane triterpenoids, tyrosamic acids A-F (1-6) together with ten known compounds (7-16), were isolated from the fruiting body of Tyromyces sambuceus. Their structures were elucidated using MS analyses, extensive 2D-heteronuclear NMR data interpretation and the structure of 3 was further confirmed by single-crystal X-ray data analyses. All lanostane triterpenoids (1-16) possesses a carboxy group at C-20 position and their strength of antiproliferative activity was affected by the presence or absence of a hydroxy group at C-15 position and at the side chain. Four of the compounds (1, 6, 10, 14) showed antiproliferative activities against human cancer cell lines with IC50 values of 16.8-48.3 µM (HL-60).

Comparison of the Chemical Profiles and Antioxidant and Antidiabetic Activities of Extracts from Two Ganoderma Species (Agaricomycetes).

The objective of this study was to compare the mycochemical profiles, antioxidant activities, and antidiabetic effects of 2 species of genus Ganoderma, the red lingzhi (G. lucidum) and purple lingzhi (G. sinense) mushrooms. In Chinese medicinal practice, hot water and ethanol are used as solvents to extract samples. In this study, a total of 4 extracts (ethanol and hot water extracts from G. lucidum and G. sinense) were prepared for further assays. Hot water extracts presented much higher values for total phenolic content and ferric-reducing antioxidant power than the ethanol extracts. Ethanol (70%) extract of G. lucidum had the strongest α-glycosidase inhibitory capacity, but the lingzhi polysaccharides showed no inhibitory effect. It also had the largest amount of total ganoderic acids. The results indicated that ethanol extracts from both G. lucidum and G. sinense showed better antidiabetic effects than the hot water extracts. Ganoderic acids, rather than polysaccharides, may contribute the antidiabetic effects of both the Ganoderma species.

Compound representatives of a new type of triterpenoid from Aglaia odorata.

[structure: see text] A novel triterpenoid, 21,25-cyclodammar-20(22)-ene-3beta,24alpha-diol, has been isolated from Aglaia odorata. Its structure was elucidated on the basis of 1D- and 2D-NMR and MS spectra and then confirmed by X-ray diffraction. It represents a new type of natural five-membered-ring triterpenoid, named cyclodammarane. Its possible biopathway was that squalene-2,3;22,23-diepioxide was directly cyclized to form 24,25-epoxydammar-20(21)-en-3-ol, followed by protonation of the remaining 24,25-epoxide and the cation attacking 21(20) methylene to generate the E ring.

Biological and taxonomic perspective of triterpenoid glycosides of sea cucumbers of the family Holothuriidae (Echinodermata, Holothuroidea).

Since the discovery of saponins in sea cucumbers, more than 150 triterpene glycosides have been described for the class Holothuroidea. The family Holothuriidae has been increasingly studied in search for these compounds. With many species awaiting recognition and formal description this family currently consists of five genera and the systematics at the species-level taxonomy is, however, not yet fully understood. We provide a bibliographic review of the triterpene glycosides that has been reported within the Holothuriidae and analyzed the relationship of certain compounds with the presence of Cuvierian tubules. We found 40 species belonging to four genera and 121 compounds. Holothurin A and B are the most common saponins for Actinopyga, Holothuria, and Pearsonothuria. The genus Bohadschia presents mainly bivittoside C and D. Actinopyga has only sulfated saponins mainly oxidized, Bohadschia non-sulfated ones mainly non-oxidized, Holothuria and Pearsonothuria contain both types of compounds, mainly oxidized. Within the genus Holothuria, the subgenus Panningothuria only has non-sulfated saponins. The presence of sulfated and non-sulfated compounds seemingly relates to the expellability or the absence of Cuvierian tubules and the temporal or permanent concealing habits of the species. Our study concludes that better insights into the systematic distribution of saponins in Holothuriidae will only be possible if the identifications of the investigated species are confirmed by a taxonomist, especially in this group wherein cryptic species and variation between life-history stages are common and yet poorly understood. Understanding of saponin distribution within the Holothuriidae would also benefit from a stabilization of triterpene glycoside nomenclature.