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Phytochemical investigation of Cephalotaxus sinensis has led to the isolation of a new bisabolane sesquiterpenoid (1), a new abietane diterpenoid (2), and 13 known compounds (3–15). Their structures were elucidated by extensive spectroscopic analysis (MS, UV, IR, and NMR). [ABSTRACT FROM AUTHOR]

The nun moth, Lymantria monacha L., is one of the most important defoliators of Eurasian coniferous forests. Outbreaks during 2011-2015 in the natural/planted larch, and larch-birch mixed forests of the Greater Khingan Range in Inner Mongolia, China, caused tremendous timber losses from severe defoliation and tree mortality. A series of trapping experiments were conducted in these outbreak areas to evaluate the efficacy of a synthetic species-specific pheromone lure based on the female pheromone blend of European nun moth populations. Our results clearly show that the nun moth in Inner Mongolia is highly and specifically attracted to this synthetic pheromone, with few gypsy moths ( Lymantria dispar) captured. Flight activity monitoring of L. monacha male moths using pheromone-baited Unitraps at 2 locations during the summer of 2015 indicated that the flight period started in mid-July, peaking in early August at both locations. Based on male moth captures, there was a strong diurnal rhythm of flight activity throughout the entire scotophase, peaking between 22:00 and 24:00. Unitraps and wing traps had significantly and surprisingly higher catches than the gypsy moth traps. Unitraps fastened to tree trunks 2 m above ground caught significantly more male moths than those at the ground level or at 5 m height. Male L. monacha moths can be attracted to pheromone-baited traps in open areas 150-200 m distant from the infested forest edge. Our data should allow improvement on the performance of pheromone-baited traps for monitoring or mass-trapping to combat outbreaks of this pest in northeastern China. [ABSTRACT FROM AUTHOR]

Five new cassane diterpenoids, caesalmins I-M ( 1- 5), and 23 known analogs were isolated from the seeds of Caesalpinia minax. Their structures were elucidated by spectroscopic methods and comparison with reported data. The antioxidant properties of 1- 28 were determined by the method of oxygen radical absorbance capacity of fluorescein (ORAC-FL), and 14 compounds exhibited good antioxidant activities with ORAC-FL values of 2.24-4.89 Trolox equivalents. The structureactivity relationship of the active compounds was also discussed. [ABSTRACT FROM AUTHOR]

Under the guidance of MS/MS-based molecular networking, five new clerodane diterpenoid glucosides, tinosinesides R-V (1 – 5), along with 15 known diterpenoids (6–20), were isolated from the stems of Tinospora sinensis. Compound 1 represents the first example of diterpenoid bearing a thio sugar and compound 5 is the first 18,19-dinor-clerodane with cis -fused A/B ring. The structures of the new compounds were elucidated by spectroscopic means, and their absolute configurations were established on the basis of time-dependent density functional theory (TD-DFT) based electronic circular dichroism (ECD) calculation and chemical methods. Selected compounds were evaluated for their immunomodulatory effect and several compounds could enhance the proliferation of B lymphocytes. Preliminary mechanistic studies disclosed that 3 could promote B cell generation and inhibit B cell differentiation. [Display omitted] [ABSTRACT FROM AUTHOR]

Ethnopharmacological relevance Salvia plebeia R. Brown, a traditional Chinese medicinal herb, has been used to treat inflammatory diseases such as cough, hepatitis, and diarrhea for a long history. Aim of the study The aim of the present study was to isolate and identify potential anti-inflammatory agents from the herb of S. plebeia , which may have contributed to its folk pharmacological use in the treatment of inflammatory diseases. Material and methods The aerial parts of S. plebeia were extracted with 95% ethanol and separated by silica gel, RP-C 18 , Sephadex LH-20, and HPLC. The structures of the isolated compounds were elucidated by extensive spectroscopic analysis (MS, NMR, and X-ray). Anti-inflammatory activities of all compounds were evaluated by the model of LPS-induced up-regulated of NO in Raw264.7 macrophages. The expression levels of cytokine (TNF-α) and proteins (iNOS and COX-2) were assessed by ELISA kit and Western blotting analysis, respectively. Furthermore, the influences of salviplenoid A ( 1 ) on NF-κB and MAPK signaling pathways were determined by Western blotting analysis and immunofluorescence assay. Results Six new ( 1 − 6 , salviplenoids A–F) and ten known ( 7 – 16 ) sesquiterpenoids were isolated from the herb of S. plebeia . The absolute configurations of compounds 1 , 2 , and 7 were determined by X-ray diffraction. The new eudesmane-type sesquiterpenoid, salviplenoid A ( 1 ), significantly decreased the release of NO and TNF-α and the expression of proteins iNOS and COX-2. In addition, the biochemical mechanistic study indicated that 1 regulated the NF-κB dependent transcriptional activity through inhibiting the nuclear translocation of p50/p65 dimer and decreasing the phosphorylation of IκB and Erk1/2. Conclusions Among all sesquiterpenoids isolated from S. plebeian , the new salviplenoid A ( 1 ) exhibited the most potent anti-inflammatory activity in LPS-induced Raw264.7 cells via inhibition of NF-κB and Erk1/2 signaling pathways. [ABSTRACT FROM AUTHOR]

Chemical fractionation of the EtOH extract of a medicinal macro fungus, Inonotus obliquus , afforded an array of lanostane-type triterpenoids (1 − 11) including two new ones (1 and 8). The structures of these compounds were determined on the basis of spectroscopic analyses, single crystal X-ray crystallography of 3 – 6 and biosynthetic considerations. With the confirmatory structural information provided by X-ray diffraction analysis in hand, several previously reported 21,24-cyclolanostanes, such as inonotsutriols A–C and (20 R ,21 S ,24 S)-21,24-cyclopenta-3 β ,21,25-trihydroxylanosta-8-ene, were structurally corrected. In addition, the NMR data of other types of 21,24-cyclo triterpenoids were also re-examined and structural revisions were thus suggested. Compounds 2 , 6 and 8 showed significant cytostatic effects against a panel of tumor cell lines with IC 50 values ranging from 7.80 to 18.5 μM. Further assays established that compound 2 exerted promising in vitro anti-breast cancer potential by inhibiting the proliferation and migration of 4T1 cells. [Display omitted] • Two new lanostane-type triterpenoids were isolated from fungus Inonotus obliquus. • The absolute configurations were characterized by single-crystal X-ray diffraction. • The structures of several previously reported 21,24-cyclolanostanes were corrected. • Selective compounds showed cytotoxicity against lung, breast & gastric tumor cells. • Compound 2 dose-dependently inhibited the proliferation and migration of 4 T1 cells. [ABSTRACT FROM AUTHOR]

Three new thiophene derivatives, ecliprostins A–C (1 – 3), have been isolated from the aerial parts of a Compositae medicinal plant Eclipta prostrata , and structures of them have been elucidated by comprehensive spectroscopic analyses. Both ecliprostins A (1) and B (2) feature an acetylenic bithiophenyl backbone and also incorporate an isovalerate moiety, while ecliprostin C (3) is a symmetrical dimer of compound 1 and represents the first example bonded via an ether bridge among the very limited natural dimers. All three compounds show antibacterial activity against Staphylococcus aureus. Three new antibacterial thiophene derivatives, including an unusual dimer with an ether bridge, were isolated and identified from the aerial parts of Eclipta prostrata. Unlabelled Image • Three new acetylenic thiophenes were isolated from the aerial parts of Eclipta prostrata. • The first example linked via an ether bond of natural acetylenic thiophene dimers was reported. • All the isolates showed antibacterial activity against Staphylococcus aureus. [ABSTRACT FROM AUTHOR]

Aims: Acquired resistance to cyclin-dependent kinase 4/6 inhibitors (CDK4/6i) frequently emerges, and CDK4/6i-containing therapies in triple-negative breast cancer (TNBC) remain to be determined., Methods: RNA-sequencing, cell viability analysis, immunoblotting, siRNA transfection et al. were used to investigate and verify the resistance mechanism. BALB/c nude mice xenograft models and spontaneous MMTV-PyMT models were used to explore in vivo efficacy., Results: The mTOR pathway was activated in acquired CDK4/6i-resistant cells and inhibition of mTORC1 restored the sensitivity. While fasting-mimicking diet (FMD) enhances the activity of anticancer agents by inhibiting the mTORC1 signaling, we assessed FMD and found that FMD restored the sensitivity of CDK4/6i-resistant cells to abemaciclib and potentiated the anti-tumor activity of CDK4/6i in TNBC. The anti-tumor effects of FMD and/or CDK4/6i were accompanied by the downregulation of S6 phosphorylation. FMD cooperated with CDK4/6i to suppress the levels of IGF1 and RAS. The combination of FMD and abemaciclib also led to a potent inhibition of tumor growth in spontaneous transgenic MMTV-PyMT mouse models., Conclusions: Our data demonstrate that FMD overcomes resistance and potentiates the anti-tumor effect of CDK4/6i by inhibiting mTORC1 signaling via lowering the levels of IGF1 and RAS, providing the rationale for clinical investigation of a potential FMD-CDK4/6i strategy in breast cancer., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Azaphilones represent a particular group of fascinating pigments from fungal source, with easier industrialization and lower cost than the traditional plant-derived pigments, and they also display a wide range of pharmacological activities. Herein, 28 azaphilone analogs, including 12 new ones, were obtained from the fermentation culture of a marine fungus Penicillium sclerotium UJNMF 0503. Their structures were elucidated by MS, NMR and ECD analyses, together with NMR and ECD calculations and biogenetic considerations. Among them, compounds 1 and 2 feature an unusual natural benzo[d][1,3]dioxepine ring embedded with an orthoformate unit, while 3 and 4 represent the first azaphilone examples incorporating a novel rearranged 5/6 bicyclic core and a tetrahydropyran ring on the side chain, respectively. Our bioassays revealed that half of the isolates exhibited neuroprotective potential against H 2 O 2 -induced injury on RSC96 cells, while compound 13 displayed the best rescuing capacity toward the cell viability by blocking cellular apoptosis, which was likely achieved by upregulating the PI3K/Akt signaling pathway., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Jie Bao, Yan-Fen Zhao, Hua Zhang, Shan-Shan Huang, Long Wang, Chun-Ying Wang, Yu Zhang has patent #Penicillium fungus and application thereof in preparing antibacterial medicine (CN115806881) issued to Jie Bao. Lei Zhou, Wen-Min Hou, Mei-Hui Hou, Jie Bao, Peng-Wei Jing, Hao Li, Yong-Mei Wu has patent #Extraction of nitrogenophilic ketone compound and its application(CN115850231) issued to Jie Bao. Jie Bao, Yan-Fen Zhao, Kongkai Zhu, Hua Zhang, Xin-Xin Wang, Ze-Long Chen, Ruo-Ping Ma has patent #Azone compounds and their preparation methods and their application in preparation of neuroprotective drugs (CN115851454) issued to Jie Bao. Jie Bao, Yan-Fen Zhao, Hua Zhang, Xin-Xin Wang, Shan-Shan Huang, Xin-Ping Liu has patent #Azurophilic ketone compounds with effect of promoting peripheral nerve injury repair and preparation method thereof (CN115960729) issued to Jie Bao. Xin-Ping Liu, Jie Bao, Ruo-Ping Ma, Long Wang, Yan-Fen Zhao, Xin-Xin Wang, Xin-Hui Cheng, Jia-Hui Xu has patent #Preparation of benzopyran compound and its application in preparation of medicine for neurodegenerative diseases (CN116410185) issued to Jie Bao. If there are other authors, they declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

Two heterodimers including a clovane-phenylpropanoid hybrid ( 1 ) and a clovane-menthane hybrid ( 2 ), five linear sesquiterpenoids incorporating a tetrahydrofuran ring ( 3 - 6 & 8 ), and four steroids ( 7 & 9 - 11 ), were separated from the ethanolic extract of a well-known aromatic and medicinal herb Eupatorium fortunei . Their structures were characterised by detailed analyses of spectroscopic data and comparison with known analogues, with seven ( 1 - 7 ) of them being described for the first time. The hybrids 1 and 2 represent the first examples of clovane type sesquiterpenoids hybridising with other class of natural products, and compounds 3 - 6 and 8 are first linear sesquiterpenyl constituents reported from the title species. All the isolates were evaluated for their inhibitory effect on the NO production induced by LPS in murine RAW264.7 macrophage cells, and 1 , 7 , 10 and 11 exhibited moderate activity with IC 50 values in the range of 24.4-43.5 µM.

Seven new polyketides including three chromone derivatives (1-3) and four linear ones incorporating a tetrahydrofuran ring (4-7), along with three known compounds (8-10), were obtained from the fermentation of an endophytic fungus (Chaetomium sp. UJN-EF006) isolated from the leaves of Vaccinium bracteatum. The structures of these fungal metabolites have been elucidated by spectroscopic means including MS, NMR and electronic circular dichroism. A preliminary anti-inflammatory screening with the lipopolysaccharide (LPS) induced RAW264.7 cell model revealed moderate NO production inhibitory activity for compounds 1 and 4. In addition, the expression of three LPS-induced inflammatory factors IL-6, iNOS and COX-2 was also blocked by 1 and 4., (© 2024 Wiley‐VHCA AG, Zurich, Switzerland.)

Twenty-two labdane-type diterpenoids, including ten pairs of 15-epimers and a pair of 13,15-epimers, were obtained from the aerial parts of a well-known medicinal plant Leonurus japonicus Houtt. While these epimers were separated by chiral HPLC, their structures were established mainly via spectroscopic methods especially NMR, X-ray crystallography and ECD techniques. Among them, seventeen compounds, encompassing three pairs of solvolysis artefacts likely due to the use of ethanol as extracting solvent, were reported for the first time in the current work. Our preliminary anti-inflammatory screening demonstrated that seven diterpenoids displayed noteworthy inhibitory effect on the NO production in LPS-induced RAW264.7 cells. In addition, the release of pro-inflammatory factors TNF-α, IL-1β and IL-6, as well as the expression of iNOS and COX-2 proteins, was also suppressed by the unreported 15,16-epoxy-6β-hydroxy-15α-methoxy-7,16-dioxolabd-8,13-diene. Further investigation into the preliminary anti-inflammatory mechanism of this compound indicated that it could block the activation of NF-κB signaling pathway., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

One new clerodane-type furanoditerpenoid tinosinoid A (1) and nine new nor-clerodane analogs tinosinoids B-J (2-10) have been isolated from the stems of Tinospora sinensis. The structures of the new compounds with absolute configurations have been elucidated by spectroscopic means, including MS, NMR and ECD techniques, as well as chemical correlation. Compound 1 is a rare sulfur-containing clerodane diterpenoid incorporating a 2-mercaptoethanol unit via a thioether bond, while compounds 4/5 and 9 represent two pairs of unusual equilibrium regioisomers through an interesting intramolecular transesterification. Our bioassays established that 1 and 8 displayed moderate antiproliferative effects against two human tumor cell lines, and 9 and 10 showed significant α-glucosidase inhibitory activities. A kinetics study revealed that compound 10 was a noncompetitive α-glucosidase inhibitor, and its possible binding mode to the enzyme was further probed by molecular docking experiments., (© 2022. The Pharmaceutical Society of Korea.)

Eight undescribed triterpenoids (pterohoonoids A-H) including four oleananes, one nor-oleanane and three nor-ursanes, along with seven known analogues, were isolated from the whole plants of Pterocephalus hookeri (Dipsacaceae). The structures with relative stereochemistries of these molecules were elucidated mainly by spectroscopic analyses, and the absolute configurations of the undescribed ones were assigned by a variety of methods, including time-dependent density functional theory (TD-DFT) based electronic circular dichroism (ECD) calculation, Rh 2 (OCOCF 3 ) 4 -induced ECD experiment and chemical transformation. The inhibitory effects toward the diabetes target α-glucosidase of all the isolates were assessed, and four of them exhibited pronounced activity with IC 50 values ranging from 6.8 to 55.8 μM. In addition, four compounds also showed inhibition against the nitric oxide (NO) production induced by lipopolysaccharide (LPS) in RAW264.7 macrophage cells (IC 50  = 12.4-63.7 μM). Further assays demonstrated that the most active compound pterohoonoid A inhibited the release of two key pro-inflammatory cytokines TNF-α and IL-6 in a dose-dependent manner., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Fifteen previously undescribed nor-clerodane diterpenoid glucosides tinosinesides C-Q (1-15), along with four known analogues (16-19), were isolated from the stems of Tinospora sinensis. The structures of the new compounds were elucidated by spectroscopic means, and their absolute configurations were established on the basis of time-dependent density functional theory (TD-DFT) based electronic circular dichroism (ECD) calculation and chemical methods. All the isolates were evaluated for their inhibitory effects on cystathionine γ-lyase (CSE), a natural enzyme responsible for the synthesis of H 2 S. Compounds 4 and 5 represent rare examples of natural CSE inhibitors and the possible binding mode to CSE was further probed by molecular docking experiment., (Copyright © 2021 Elsevier Inc. All rights reserved.)

Two new lignan glucosides, tinsinlignans A and B (1 and 2), two new oxyneolignans, tinsinlignans C and D (3 and 4), along with one known analogue (5), were isolated from the stems of Tinospora sinensis. The structures of the new compounds were elucidated based on analysis of spectroscopic data, and the absolute configuration of 1 was determined through electronic circular dichroism (ECD) calculation based on the time-dependent density functional theory (TD-DFT). Compounds 1-4 were evaluated for their inhibitory effects on nitric oxide (NO) production induced by lipopolysaccharide (LPS) in murine RAW264.7 macrophage cells and compounds 1 and 2 exhibited moderate inhibitory activities with IC 50 values of 18.5 ± 2.0 and 28.8 ± 1.2 μmol·L -1 , respectively., (Copyright © 2021 China Pharmaceutical University. Published by Elsevier B.V. All rights reserved.)

Eleven new compounds including five bisabolane (1-5) and three oplopane (6-8) sesquiterpenoids, a pair of benzopyran enantiomers (9 & 10) and a benzofuran derivative (11), along with six known sesquiterpenoid co-metabolites (12-17), have been obtained from the flower buds of Tussilago farfara. Their structures were elucidated by comprehensive spectroscopic analyses and comparison with structurally related known analogues. The absolute configurations of all the compounds except 11 were unequivocally assigned by various techniques, including Mosher's method and time-dependent density functional theory (TD-DFT) based calculations of 13 C NMR and electronic circular dichroism (ECD) data. The C-8 absolute configuration on the sidechain of this group of bisabolane sesquiterpenoids was assigned for the first time. Our bioassays have established that compounds 3, 4, 13 and 14 showed significant α-glucosidase inhibitory activities, while 6, 8 and 14 displayed moderate antiproliferative effects against two human tumor cell lines A549 and MDA-MB-231. Further flow cytometric analysis revealed that 14 effectively induced cell apoptosis and arrested cell cycle at the S/G2 phases in A549 cells, in a dose-dependent manner., (Copyright © 2021. Published by Elsevier Inc.)

A total of 64 haplotypes were obtained from the complete Cytochrome b gene (Cyt b) of 77 Sorex isodon collected from three populations (Daxing'anling, Xiaoxing'anling, and Changbai Mountains) in Northeast China. The haplotype diversity was 0.9920 and the nucleotide diversity was 0.0105, indicating high genetic diversity. The genetic diversity of Changbai Mountains population was significantly higher than that of Daxing'anling and Xiaoxing'anling populations. The F-statistics, the number of migrants per generation and the genetic distance results showed that the genetic distances among the populations and among the sampling sites were generally consistent with geographical distance. Analysis of molecular variance showed that the differentiation among populations, among sampling sites, and within sampling site accounted for 33.4%, 10.2% and 56.4% of total variation, respectively. The analysis of population history showed that S. isodon in Northeast China experienced no population expansion. The reported complete sequence of Cyt b gene of S. isodon (GenBank) of Europe and other parts of Asia was downloaded to examine the genetic structure of S. isodon. The phylogenetic tree was divided into two large branches. One branch consisted mainly of Daxing'anling and Xiaoxing'anling samples. The other branch was departed into two sub-branches. Median-joining network analysis showed that there were three lineages: one lineage mainly consisted of haplotypes from Daxing'anling and Xiaoxing'anling, and also four haplotypes of Changbai Mountains, while the other lineage included a few haplotypes of three populations in Northeast China, and those from Baikal Lake, Russia and Finland. The last lineage was entirely composed of haplotypes from Changbai Mountains. The results of genetic diversity, phylogenetic tree and median-joining network all suggested that the Changbai Mountains was the refuge for S. isodon during last glacial.

Chemical fractionation of the ethanolic extract of Eclipta prostrata yielded a series of unreported terpenoid constituents, including a rare 6/6/6/6-fused tetracyclic triterpenoid, a pentacyclic triterpenoid, two pentacyclic triterpenoid saponins, a diterpenoid and a sesquiterpenoid. Structures were assigned to these compounds on the basis of comprehensive spectroscopic analyses, with the absolute configurations of the tetracyclic triterpenoid, the diterpenoid and the sesquiterpenoid being determined via explanation of electronic circular dichroism data. Screening of these isolates in an array of bioassays revealed antibacterial, cytotoxic and α-glucosidase inhibitory activities for selective compounds. Of particular interest, the tetracyclic triterpenoid showed very strong inhibition against α-glucosidase with an IC 50 of 0.82 ± 0.18 μM, being 10 3 -fold as active as the positive control acarbose., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Seven previously undescribed polycyclic diterpenoids, euphonoids A-G, including four ent-abietanes, two ent-atisanes, and one ent-kaurene, along with 26 known analogues were isolated from the roots of Euphorbia fischeriana. The structures of the undescribed compounds were elucidated by spectroscopic analysis, ECD calculations, and single crystal X-ray diffraction. Besides, the structure of a previously reported ent-abietane diterpenoid, fischeriabietane A, was revised. All the isolates were screened for the cytotoxicities against five cancer cell lines. Euphonoid A, fischeriabietane A, 11-oxo-ebracteolatanolide B, caudicifolin, jolkinolide B, and methyl-8,11-3-dihydroxy-12-oxo-ent-abietadi-13,15(17)-ene-16-oate showed significant inhibitory activities against human prostate cancer C4-2B and C4-2B/ENZR cell lines, with IC 50 values being less than 10 μM. The brief structure-activity relationships (SARs) of these diterpenoids were also discussed., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Four new octadecanoid derivatives (1-4) including a pair of enantiomers (1/2), along with 12 known analogues (5-16), were isolatedfrom the seeds of Ipomoea nil. Their structures were determined by detailed spectroscopic analyses and comparison with reported data of structurally related compounds, with the absolute configurations of 1 and 2 being assigned by an in situ dimolybdenum ECD method. Our bioassays revealed that these isolates did not show ABTS radical scavenging activity while 10 and 13 displayed better α-glucosidase inhibitory activity than the positive control acarbose (IC 50 167.7 ± 1.55 μmol·L -1 ), with IC 50 of 92.73 ± 3.12 and 11.39 ± 2.18μmol·L -1 , respectively., (Copyright © 2019 China Pharmaceutical University. Published by Elsevier B.V. All rights reserved.)

Two pairs of new neolignan enantiomers, (±)-torreyayunan A (1a/1b) and (±)-torreyayunan B (2a/2b), featuring a rare C-8 - C-9' linked skeleton, were isolated from leaves and twigs of Torreya yunnanensis. Their absolute configuration involving two chiral centers was determined by combined spectral and Density Functional Theory (DFT) calculation. This is the first report of the absolute configuration of this group of neolignans., (© 2014 Wiley Periodicals, Inc.)