冬凌草中三个新的对映-贝壳杉烷二萜及其细胞毒活性

目的：研究产自湖北省建始县的冬凌草（1sodon rubescens）地上部分的化学成分;方法：利用正反相硅胶柱色谱、高效液相色谱等现代分离技术进行分离;通过IR,UVMS,NMR等波谱方法鉴定了化合物结构式;对化合物1进行了单晶X-射线衍射分析,确定了其绝对构型;化合物1_9进行了对HL-60,SMMC-7721,A-549,MCF-7和SW-480细胞株的体外细胞毒活性测定：结果：分离鉴定了8个对映-贝壳杉烷二萜和1个对映-赤霉烷二萜;结论：建始冬凌草庚素-壬素（1-3）为新化合物,其中2是一个少见的、3位为半缩酮结构的3,20-环氧-对映-贝壳杉烷二萜;所有受试化合物中,4和5对某些细胞株表现出一定的体外抗增殖活性。     

Structure and cytotoxicity of diterpenoids from Isodon adenolomus

Twelve new diterpenoids, isoadenolins A-L (1-12), and 24 known ones were isolated from the aerial parts of Isodon adenolomus. Their structures were identified using spectroscopic data, and the absolute configurations of 1 and 14 were determined by single-crystal X-ray diffraction. Selected compounds were evaluated for their in vitro cytotoxicity against human tumor HL-60, SMMC-7721, A-549, MCF-7, and SW-480 cell lines. Compounds 9, 13-16, and 21 showed significant inhibitory effects on all five cells, with IC50 values in the range 0.7-9.7 μM.     

Cytotoxic diterpenoids from Sapium insigne

Chemical investigation into the twigs and leaves of Sapium insigne afforded seven new diterpenoids, sapinsignoids A-G (1-7), together with 10 known diterpenoids. The structures of 1-7 were assigned on the basis of detailed spectroscopic analysis and chemical degradation. Compounds 1-4 exhibited significant cytotoxicity against the A-549 tumor cell line (IC(50) 0.2-1.8 μM), while compounds 1-3 showed moderate cytotoxicity against the HL-60 cell line (IC(50) 2.7-6.5 μM).     

Steroidal alkaloids from the bulbs of Fritillaria puqiensis

Four new steroidal alkaloids, puqienine A (1), puqienine B (2), N-demethylpuqietinone (3), and puqietinonoside (4), along with a known steroidal alkaloid, puqietinone, were isolated from the bulbs of Fritillaria puqiensis. The structures of these compounds were elucidated on the basis of spectroscopic analysis. The compounds exhibited significant antitussive activity on ammonia liquor-induced cough in mice. Furthermore, the compounds were evaluated for activities against A549 human lung carcinoma cell line, BGC-823 human stomach adenocarcinoma cell line, SMMC-7721 human hepatocarcinoma cell line, and HL-60 human promyelocytic leukemia cell line.     

Cytotoxic diacetylenic spiroketal enol ethers from Plagius flosculosus

Three new diacetylenic spiroketal enol ethers named flosculins A (1), B (2), and C (3), along with five known compounds (4-8) of the same structural class, were isolated from the leaves of Plagius flosculosus. The structures were deduced by extensive 1D and 2D NMR spectroscopy and mass spectrometry. All isolated compounds exhibited significant cytotoxic activity against leukemia cells (Jurkat T and HL-60). Compounds 5-8 induced apoptosis in HL-60 cells with corresponding IC(50) values ranging from 4 to 6 microM.     

金丝李茎皮化学成分研究

目的对金丝李Garcinia paucinervis的茎皮化学成分进行分离鉴定,并进行抗肿瘤活性筛选。方法采用硅胶、反相RP-18,制备薄层色谱,Sephadex LH-20等柱色谱方法对乙醇提取物石油醚萃取部位化学成分进行分离和纯化,并根据其理化性质及波谱数据鉴定结构;采用MTT法进行抗肿瘤活性筛选。结果从金丝李乙醇提取物中分离得到10个化合物,分别鉴定为cambogin(1)、焦袂康酸(2)、β-谷甾醇(3)、胡萝卜苷(4)、7-prenyljacareubin(5)、parvifolixanthone A(6)、formoxanthone A(7)、termicalcicolanone A(8)、1,3,5,6-tetrahydroxy-4-prenylxanthone(9)、isogarcinol(10)。抗肿瘤活性筛选结果表明,化合物5和7对HL-60、SMMC-7721、A549、MCF-7和SW480细胞株有一定的抑制作用。结论化合物2～5和7～10均为首次从该植物中分离得到,同时首次报道了化合物5的13C-NMR数据。     

Absolute structures of monoterpenoids with a δ-lactone-containing skeleton from Ligularia hodgsonii

Bioactivity-directed fractionation of a methanol extract of Ligularia hodgsonii afforded two new monoterpenoids, liguhodgcins A (1) and B (2), with an unusual δ-lactone-containing skeleton. Moreover, liguhodgcin A (1) contained a chlorine atom. The structures and absolute configurations of the two compounds were elucidated using NMR spectroscopy, X-ray crystallography, ECD data, and computational approaches. A probable biosynthesis pathway to 1 and 2 was also proposed and discussed. The cytotoxicity of compounds 1 and 2 was evaluated against the human leukemia (HL-60), human hepatoma (SMMC-7721), and human cervical carcinoma (HeLa) cell lines.     

Daphmacromines A-J, alkaloids from Daphniphyllum macropodum

Ten new yuzurine-type Daphniphyllum alkaloids, daphmacromines A-J (1-10), along with seven known alkaloids were isolated from the leaves and stems of Daphniphyllum macropodum. Their structures were elucidated by extensive spectroscopic techniques, including 2D NMR spectroscopy and mass spectrometry, and the structure of 1 was confirmed by single-crystal X-ray diffraction. The pesticidal and cytotoxic activities of the isolated alkaloids were evaluated in vitro against brine shrimp (Artemia salina) and five human cancer cell lines (HL-60, SMMC-7721, A-549, MCF-7, and SW480), respectively. This study also suggested structural revisions of oxodaphnigracine, oxodaphnigraciline, and epioxodaphnigraciline.     

Xanthanolides, germacranolides, and other constituents from Carpesium longifolium

Three new xanthanolides, 1-3, along with nine known compounds, were isolated from the aerial parts of Carpesium longifolium. The structures of the new compounds were elucidated as 1beta,4beta-epoxy-5beta-hydroxy-10alphaH-xantha-11(13)-en-12,8beta-olide (1), 1beta,4beta,4alpha,5beta-diepoxy-10alphaH,11alphaH-xantha-12,8beta-olide (2), and 4-acetoxy-1beta,5beta-epoxy-10alphaH-xantha-11(13)-en-12,8beta-olide (3) by spectroscopic methods including IR, EIMS, HRESIMS, and 1D and 2D NMR experiments. Parthenolide and michelenolide exhibited significant cytotoxic activity against cultured SMMC-7721 (human hepatoma) and HO-8910 (human ovarian carcinoma) cells.     

Prenylated Polyhydroxy-p-terphenyls from Aspergillus taichungensis ZHN-7-07

Six new prenylated polyhydroxy-p-terphenyl metabolites, named prenylterphenyllins A-C (1-3) and prenylcandidusins A-C (5-7), and one new polyhydroxy-p-terphenyl with a simple tricyclic C-18 skeleton, named 4'-dehydro-3-hydroxyterphenyllin (4), were obtained together with eight known analogues (8-15) from Aspergillus taichungensis ZHN-7-07, a root soil fungus isolated from the mangrove plant Acrostichum aureum. Their structures were determined by spectroscopic methods, and their cytotoxicity was evaluated using HL-60, A-549, and P-388 cell lines. Compounds 1 and 8 exhibited moderate activities against all three cell lines (IC50 1.53-10.90 μM), whereas compounds 4 and 6 displayed moderate activities only against the P-388 cell line (IC50 of 2.70 and 1.57 μM, respectively).     

南川斑鸠菊中的抗肿瘤倍半萜内酯（英文）

目的：研究南川斑鸠菊中的抗肿瘤活性成分方法：采用层析柱和制备高效液相进行化合物分离,运用1H和13CNMR及MS等波谱分析技术鉴定化合物结构;采用MTT法进行7个化合物对人骨髓白血病细胞（HL-60）的体外细胞毒实验。结果：分离得到6个倍半萜内酯[8α-（4-hydroxymethacryloyloxy）-10α-hydroxy-13-methoxyhirsutinolide（1）,8α-methacry-loyloxy-10α-hydroxy-13-O-methylhirsutinolide（2）,piptocarphin A（3）,8α-[4-hydroxymethacryloyloxy]-10α-hydroxyhisutinolide-13-O-acetate（4）,piptocarphin F（5）以及8α-acetoxy-10α-hydroxy-13-O-methylhirsutinolide（6）]和1个inone苷saussureosides B（7）;6个倍半萜内酯（1-6）具有抑制人骨髓白血病细胞（HL-60）的活性（IC503.87-12.5μmol·L-1）,但inone苷saussureosides B（7）对HL-60没有抑制活性。结论：化合物1,2,6和7首次从该植物中得到;南川斑鸠菊中的倍半萜内酯类化合物具有抗肿瘤活性。     

New bromotyrosine derivatives from an association of two sponges, Jaspis wondoensis and Poecillastra wondoensis

Three new bromotyrosine derivatives (4-6) were isolated from an association of two sponges, Jaspis wondoensis and Poecillastra wondoensis, along with the previously described (E,E)-psammaplin A (1), (E,Z)-psammaplin A (2), psammaplin D (3), bisaprasin (7), and (3-bromo-4-hydroxyphenyl)acetonitrile (8). The structures of the new compounds were established on the basis of NMR and MS spectroscopic analysis. The compounds 1, 3, and 5-7 displayed significant cytotoxicity against human lung (A549), ovarian (SK-OV-3), skin (SK-MEL-2), CNS (XF498), and colon (HCT15) cancer cell lines. Compounds 3-7 were further evaluated for antibacterial activity against methicillin- or ofloxacin-resistant Staphylococcus strains. Compound 4 exhibited more potent antibacterial activity than meropenem against several strains.     

Caffeic acid esters and lignans from Piper sanguineispicum

Three new caffeic acid esters (1-3), four new lignans (4-7), and the known compounds (7'S)-parabenzlactone (8), dihydrocubebin (9), and justiflorinol (10) have been isolated from leaves of Piper sanguineispicum. Their structures were determined by spectroscopic methods, including 1D and 2D NMR, HRCIMS, CD experiments, and chemical methods. Compounds 1-10 were assessed for their antileishmanial potential against axenic amastigote forms of Leishmania amazonensis. Caffeic acid esters 1 and 3 exhibited the best antileishmanial activity (IC(50) 2.0 and 1.8 μM, respectively) with moderate cytotoxicity on murine macrophages.     

Tumoral cytotoxic and antioxidative phenylpropanoid glycosides in Smilax riparia A. DC

Ethnopharmacological relevance

Smilax riparia A. DC., known as “Niu-Wei-Cai” in China, is distributed through the south and middle of China. The roots and rhizomes of Smilax riparia have been used not only as traditional Chinese medicines (TCMs) for the treatment of bronchitis, lumbago of renal asthenia, traumatic injury, asthenia edema, and cancer but also as edible wild herbs in some areas of China.

Aim of the study

To identify the phytochemicals in the roots and rhizomes of Smilax riparia and to investigate their antioxidant activities and cytotoxicities toward several tumor cell lines.

Materials and methods

Four fractions and five phenylpropanoid glycosides were obtained from roots and rhizomes of Smilax riparia under bioassay-guided screenings. The structures of five compounds were elucidated by spectroscopic methods and compared with published data. We evaluated their antioxidant activities and their cytotoxicities on five cancer cell lines: human promyelocytic leukemia (HL-60), human hepatocellular carcinoma (SMMC-7721), human lung cancer (A-549), human breast cancer (MCF-7), and human colon cancer (SW480).

Results

Of the five glycosides, one new compound (3, smilaside P) was isolated from an EtOAc fraction. Compound 1 was cytotoxic toward HL-60, SMMC-7721, A-549, MCF-7, and SW480 (IC₅₀ 2.70, 3.80, 11.91, 3.79, and 3.93 μM, respectively). Moreover, compounds 1–3 showed moderate scavenging activities against the 2, 2-diphenyl-1-picrylhydrazyl (DPPH) radical (IC₅₀ 339.58, 330.66, 314.49 μM, respectively).

Conclusions

Five phenylpropanoid glycosides were reported for the first time from this TCM. Each was studied, as observed here for the first time, in the cytotoxic experiments toward HL-60, SMMC-7721, and SW480 cell lines. Compound 1, bearing three feruloyl groups and three acetyl groups, had the greatest cytotoxicity toward the five tumor cell lines. Compounds 1–3 showed moderate antioxidant activities. All results reflect that compounds 1–3 are cytotoxic for a wide variety of cancer cell lines of differing tissue origins and that the cytotoxicities of these compounds may be related to their antioxidant activities.     

Phenanthrene derivatives from Cymbidium Great Flower Marie Laurencin and their biological activities

A new phenanthrendione, ephemeranthoquinone B (1), two phenanthrenes, marylaurencinols A (2) and B (3), and a phenanthrene glucoside, marylaurencinoside A (4), were isolated from the roots of Cymbidium Great Flower Marie Laurencin, along with six known phenanthrenes, 5-10. The structures of these compounds were established by a combination of extensive NMR spectroscopy and/or X-ray crystallographic analysis and chemical degradation. The compounds were tested for antibacterial activities against Bacillus subtilis and Klebsiella pneumoniae and for cytotoxic activity against the human promyelocytic leukemia (HL-60) cell line. Compounds 1, 3, and 6 showed antibacterial activities with minimum inhibitory concentration (MIC) values in the range of 4.88 to 65.10 μM. Notably, ephemeranthoquinone B (1) had a strong antibacterial effect on B. subtilis. Furthermore, 1 exhibited moderate cytotoxic activity (IC(50) 2.8 μM) against HL-60 cells. Compounds 4-9 also showed weak cytotoxic activity against the HL-60 cell line with IC(50) values of 19.3-52.4 μM.     

Cytotoxic sesquiterpene lactones from Eupatorium kiirunense, a coastal plant of Taiwan

Phytochemical investigation of Eupatorium kiirunense has resulted in the isolation of eight new sesquiterpene lactones, constituted by five germacranolides, eupakirunsins A-E (1-5), and three heliangolides, eupaheliangolide A (6), 15-acetoxyheliangin (7), and 3-epi-heliangin (8), in addition to the known heliangin (9) and 8,10-epoxy-9-acetoxythymol angelate (10). The structures of the new compounds were established through detailed analysis of their spectroscopic data. Compounds 6, 8, and 9 exhibited cytotoxicity against human oral epidermoid (KB), cervical epitheloid (Hela), and liver (hepa59T/VGH) carcinoma cells.     

湿地真菌Talaromyces flavus中2个新的聚酯类化合物

从一株蓝状菌属真菌Talaromyces flavus(No.BYD07-13)固体发酵物中分离得到了2个聚酯类新化合物talapolyesters G~H(1~2),采用质谱和核磁共振谱确定了它们的结构。化合物 1~2 的绝对构型是通过碱水解确定。对化合物 1~2 还评价对5株肿瘤细胞(HL-60, SMMC-7721, A-549, MCF-7, SW480)的生长抑制活性。     

Cytotoxic sesquiterpene lactones from Pseudoelephantopus spicatus

Five new sesquiterpene lactones, spicatolides D-H (1-5), along with four known compounds, pitocarphin D (6), 8 alpha-acetoxy-10 alpha-hydroxy-13-O-methylhirsutinolide (7), spicatolide A (8), and 13-O-methylvernojalcanolide 8-O-acetate (9), were isolated from an ethyl acetate extract of the aerial parts of Pseudoelephantopus spicatus. The structures of the new compounds were elucidated on the basis of spectroscopic data interpretation. All of the compounds isolated were evaluated for their cytotoxic effects against five human cancer cell lines. Compounds 1, 3, and 4 showed cytotoxicity (IC50 < 5 micro g/mL) against the Hep3B and MCF-7 cancer cell lines.     

Cytotoxic alkaloids and antibiotic nordammarane triterpenoids from the marine-derived fungus Aspergillus sydowi

Three new diketopiperazine alkaloids, 6-methoxyspirotryprostatin B (1), 18-oxotryprostatin A (2), and 14-hydroxyterezine D (3), with an oxaspiro[4.4]lactam moiety, 14-norpseurotin A (4), and the 29-nordammarane triterpenoid 6beta,16beta-diacetoxy-25-hydroxy-3,7-dioxy-29-nordammara-1,17(20)-dien-21-oic acid (5), as well as 12 known compounds (6- 17), were isolated from the ethyl acetate extract of a marine-derived fungal strain, Aspergillus sydowi PFW1-13. The structures of compounds 1- 5 were elucidated by comprehensive spectroscopic analysis. Compounds 1- 3 exhibit weak cytotoxicity against A-549 cells, with IC 50 values of 8.29, 1.28, and 7.31 microM, respectively. Compound 1 also shows slight cytotoxicity against HL-60 cells, with an IC 50 value of 9.71 microM. Compounds 4 and 5 display significant antimicrobial activities against Escherichia coli, Bacillus subtilis, and Micrococcus lysoleikticus with MICs of 3.74, 14.97, and 7.49 microM and 10.65, 5.33, and 10.65 microM, respectively.     

Trigonosins A-F, daphnane diterpenoids from Trigonostemon thyrsoideum

Phytochemical study of the roots of Trigonostemon thyrsoideum led to the isolation of four new oxygenated daphnane-type diterpenoids, trigonosins A-D (1-4), and two new modified daphnanes, trigonosins E and F (5 and 6). The structures and relative configurations were elucidated on the basis of extensive spectroscopic analysis, including 1D and 2D NMR experiments. All compounds isolated were evaluated for their cytotoxicity against HL-60, A549, and MCF-7 human cancer cell lines.