Complete assignments of 1H and 13C NMR data for two new sesquiterpenes from Cyperus rotundus L.

Two new sesquiterpenes, epi‐guaidiol A (1) and sugebiol (3), together with four known sesquiterpenes, guaidiol A(2), sugetriol triacetate (4), cyperenoic acid (5), and cyperotundone (6) were isolated from the rhizomes of Cyperus rotundus L. Their structures were identified by MS and NMR experiments, and the complete assignments of ¹H and ¹³C NMR data for two new sesquiterpenes were obtained by the aid of two‐dimensional (2D) NMR techniques, including HSQC, HMBC, ¹H‐¹HCOSY and nuclear overhauser enhancement spectroscopy(NOESY). Copyright © 2009 John Wiley & Sons, Ltd.     

A new cerebroside and its anti-proliferation effect on VSMCs from the radix of Cyperus rotundus L.

<正>A new cerebroside,1-O-(β-D-glucopyranosyloxy)-(2S,3R,4E,8Z)-2-[(2′R)-2'-hydroxylignoceranoylamino]-4,8-tetradecene-3- diol was isolated from the 60%EtOH extract of traditional Chinese medical plant Cyperus rotundus L.Its structure was determined on the basis of spectroscopic data.This new compound showed anti-proliferation effect on vascular smooth muscle cells(VSMCs).     

Two New Guaiane Sesquiterpenes from the Fruits of Daucus carota

Two new sesquiterpenes, 11‐(acetyloxy)torilolone ( 1 ) and 1β‐hydroxytorilolone ( 2 ) were obtained from the fruits of Daucus carota. Their structures were elucidated on the basis of various spectroscopic analyses and chemical evidence.     

An efficient high-speed counter-current chromatography method for the preparative separation of sesquiterpenoids from the rhizomes of Cyperus rotundus L. combined with evaluation of the anti-inflammation activity in vitro and molecular docking

Cyperus rotundus L. has been extensively used in ancient medication for the treatment of different disorders worldwide, in which sesquiterpenes are the most representative components. In this study, sesquiterpenes were effectively purified by two-dimensional counter-current chromatography in combination with continuous injection and inner-recycling mode with a solvent system of n-hexane/ethyl acetate/methanol/water (1:0.2:1:0.2, v/v/v/v). For one-dimension separation, continuous injection mode was used with three times injection and the inner-recycling mode was adopted for the separation of two mixtures for two-dimensional separation. Finally, four sesquiterpenoids, including scariodione ( 1 ), cyperenoic acid ( 2 ), scariodione ( 3 ), and α-cyperone ( 4 ), were obtained with purities over 98%. Mass spectrometry and nuclear magnetic resonance were applied to identify their structures. The results from the anti-inflammation effect with zebrafish demonstrated that cyperenoic acid exhibited stronger anti-inflammation activity. Molecular docking results suggested that cyperenoic acid possessed lower binding energies –9.4545 kcal/mol with 1CX2 to form formed hydrogen bond interaction with ARG120. In general, all the obtained findings proved that the strong anti-inflammation capacity of cyperenoic acid can have the potential of being adopted for treating diseases resulting from inflammation.     

Guaiane Sesquiterpenoids Isolated from the Fruits of Torilis japonica and Their Cytotoxic Activity

Two new guaiane sesquiterpenoids, 11‐(acetyloxy)‐1,8‐dihydroxyguai‐4‐en‐3‐one ( 5 ) and (1α,6β)‐1,6‐dihydroxytorilin ( 6 ), were isolated from the fruits of Torilis japonica (Umbelliferae), along with four known sesquiterpenes, torilin ( 1 ), torilolone ( 2 ), (1β)‐1‐hydroxytorilin ( 3 ), and (1α)‐1‐hydroxytorilin ( 4 ). During the phytochemical investigation, daucosterol, friedelin, and epifriedelanol were also isolated from the plant for the first time. The structures of the new sesquiterpenoids 5 and 6 were determined by comprehensive analyses of MS and NMR spectroscopic data. These isolates were evaluated against human breast cancer cells (MCF‐7) and Lewis lung carcinoma (LLC) cells. Compounds 1, 3 , and 4 exhibited cytotoxic activity against the LLC cells with IC₅₀ values of 31.3, 32.5, and 34.0 μg/ml, respectively. However, no significant cytotoxicity was found against the MCF‐7 cells for any of the compounds tested.     

Study on the quality difference of Cyperus rotundus before and after vinegar processing based on ultra-high-performance liquid chromatography-quadrupole-time of flight-mass spectrometry and molecular network combined with color parameters

Cyperus rotundus is the dry rhizome of the Cyperaceae plant Cyperus. Although there are two types of processed products in clinics, their quality differences are not clear, and the identification methods are more complex. In this study, the chemical composition of different processed products of Cyperus rotundus was characterized using ultra-high-performance liquid chromatography-quadrupole-time of flight-mass spectrometry and molecular network analysis, to identify the potential chemical markers and to establish a quick and simple color-based discrimination method. Among the 65 compounds analyzed, 12 showed significant differences. Observing the color, the surface brightness (L*) of Cyperus rotundus decreased after vinegar processing, while red (a*) and yellow (b*) values increased. These color values correlated significantly with chemical compositions. Finally, a color discriminant function was established and verified for raw Cyperus rotundus and vinegar-processing Cyperus rotundus. Based on this study, Cyperus rotundus' quality can be effectively controlled and provides a method for the comprehensive characterization of chemical components and chemical markers of other traditional Chinese medicine and processed products, as well as new ideas and methods in identification and quality evaluation.     

Two New Flavanols from Glycosmis pentaphylla and Their Cytotoxic Activities

Two new flavanols, (8S,9R)‐9,10‐dihydro‐5,9‐dihydroxy‐8‐(3,4,5‐trimethoxyphenyl)‐2H,8H‐benzo[1,2‐b:3,4‐b′]dipyran‐2‐one ( 1 ) and (2S,3R)‐3,4‐dihydro‐3,5‐dihydroxy‐2‐(3,4,5‐trimethoxyphenyl)‐2H,8H‐benzo[1,2‐b:3,4‐b′]dipyran‐8‐one ( 2 ), were isolated from the stems of Glycosmis pentaphylla. The structures of these compounds were determined by extensive spectroscopic (UV, IR, HR‐ESI‐MS, 1D‐ and 2D‐NMR) analyses. The cytotoxic activities of these compounds were evaluated using the MTT method. The results showed that compounds 1 and 2 exhibited considerable cytotoxic activities against HL‐60 and A549 cell lines.     

Synthesis of Novel Porphyrin Derivatives and Their Cytotoxic Activities against A431 Cells

Three novel porphyrins, including two Schiff‐bases porphyrins, 5,10,15‐triphenyl‐20‐[4‐(2‐(4‐formyl)phenoxy)ethoxy]phenyl porphyrin ( H₂Pp ( 1 )), 5,10,15‐triphenyl‐20‐[4‐(2‐(4‐hydroxyimino)phenoxy)ethoxy]phenyl porphyrin ( H₂Pp ( 2 )) and 5,10,15‐triphenyl‐20‐[4‐(2‐(4‐m‐hydroxyanilinodeneformyl)phenoxy)ethoxy]phenyl porphyrin ( H₂Pp ( 3 )), as well as three metalloporphyrins ( CuPp ( 1a ), ZnPp ( 1b ), and CoPp ( 1c )) of porphyrin H₂Pp ( 1 ) were synthesized. Their molecular structures were characterized by ¹H‐NMR, MS, UV/VIS, and FT‐IR spectra. Furthermore, they were evaluated by their cytotoxicities against human epidermal squamous cell carcinoma cell (A431) and normal human horn cells (HaCaT) in vitro with MTT assay. Interestingly, these porphyrins and metalloporphyrins, which had a negligible cytotoxicity to HaCaT cells, showed highly cytotoxicity against A431 cells with IC₅₀ values in the range of 6.6–9.8 μM , and metalloporphyrins exhibited higher cytotoxicity than that of metal‐free porphyrins.     

Three New Bisabolane Sesquiterpenes from Ligularia songarica

Three new bisabolane sesquiterpenes, songaricalarins F–H ( 1 – 3 , resp.), and five known analogs, 4 – 8 , were isolated from roots and rhizomes of Ligularia songarica. The structures were elucidated by spectroscopic methods, including 2D‐NMR techniques. The isolated compounds were also evaluated for their cytotoxic activities, against human lung carcinoma (A‐549) and human breast adenocarcinoma (MCF‐7) cell lines, and three compounds were found to show moderate cytotoxicities.     

Triterpenoids from the Roots of Camellia oleifera C.Abel and Their Cytotoxic Activities

Three new triterpenoids, 21β,22α‐diangeloyloxy‐3β,15α,16α,28‐tetrahydroxyolean‐12‐en‐23‐al ( 1 ), 21β‐angeloyloxy‐3β,15α,16α,28‐tetrahydroxy‐22α‐(2‐methylbutanoyloxy)olean‐12‐en‐23‐al ( 2 ), and 21β‐angeloyloxy‐3β,16α,28‐trihydroxy‐22α‐(2‐methylbutanoyloxy)olean‐12‐en‐23‐al ( 3 ), along with six known triterpenoids, were isolated from the roots of Camellia oleifera C.Abel . The structures of compounds 1 – 3 were elucidated on the basis of spectroscopic analyses. Moreover, all compounds isolated were evaluated for their cytotoxic activities by MTT (=3‐(4,5‐dimethylthiazol‐2‐yl)‐2,5‐diphenyl‐2H‐tetrazolium bromide) assay.     

Mammalian Arginase Inhibitory Activity of Methanolic Extracts and Isolated Compounds from Cyperus Species

Polyphenolic enriched extracts from two species of Cyperus, Cyperus glomeratus and Cyperus thunbergii, possess mammalian arginase inhibitory capacities, with the percentage inhibition ranging from 80% to 95% at 100 µg/mL and 40% to 64% at 10 µg/mL. Phytochemical investigation of these species led to the isolation and identification of two new natural stilbene oligomers named thunbergin A-B (1–2), together with three other stilbenes, trans-resveratrol (3), trans-scirpusin A (4), trans-cyperusphenol A (6), and two flavonoids, aureusidin (5) and luteolin (7), which were isolated for the first time from C. thunbergii and C. glomeratus. Structures were established on the basis of the spectroscopic data from MS and NMR experiments. The arginase inhibitory activity of compounds 1–7 was evaluated through an in vitro arginase inhibitory assay using purified liver bovine arginase. As a result, five compounds (1, 4–7) showed significant inhibition of arginase, with IC₅₀ values between 17.6 and 60.6 µM, in the range of those of the natural arginase inhibitor piceatannol (12.6 µM). In addition, methanolic extract from Cyperus thunbergii exhibited an endothelium and NO-dependent vasorelaxant effect on thoracic aortic rings from rats and improved endothelial dysfunction in an adjuvant-induced arthritis rat model.     

异维A酸糖基衍生物的合成及其细胞毒活性研究

采用两种方法合成了2类新的异维A酸糖基衍生物(5a~5d, 6a, 10a~10c, 11a), 并进行了结构表征与确认. 采用MTT法测试了它们对肺癌细胞(A549)等的细胞毒活性. 结果显示, 含有糖苷结构的异维A酸衍生物明显比含有糖酯结构的异维A酸衍生物具有更好的细胞毒活性; 将糖环上的乙酰基脱去后, 相应的化合物活性有明显提高.     

New Cytotoxic Laurene‐, Cuparene‐, and Laurokamurene‐Type Sesquiterpenes from the Red Alga Laurencia obtusa

Three new sesquiterpene alcohols, laur‐2‐ene‐3,12‐diol ( 1 ), cuparene‐3,12‐diol ( 2 ), and 8,11‐dihydro‐1‐methoxylaurokamuren‐12‐ol ( 3 ), along with one known diterpene, kahukuen‐10‐ol ( 4 ) have been isolated from the organic extract of the red alga Laurencia obtusa. The chemical structures were elucidated on the basis of spectroscopic analysis. The cytotoxicity of the isolated compounds were evaluated against three cancer cell lines, i.e., KB, HepG2, and MCF‐7. Compound 4 exhibited a wide range of cytotoxic activity against KB, HepG2, and MCF‐7 cell lines with IC₅₀ of 0.100, 0.057, and 0.054 μm, respectively. In addition, 1 showed moderate activities towards KB and MCF‐7 cell lines with IC₅₀ values of 0.171 and 0.184 μM , respectively and 2 exhibited a moderate activity against KB cell line at a concentration of 0.213 μg/ml. On the other hand, compound 3 exhibited no cytotoxic activity against any of the three cell lines.     

Cytotoxic arylbenzofuran and stilbene derivatives from the twigs of Artocarpus heterophyllus

Four new natural products, including three arylbenzofurans named heterophyllenes A-C (1–3), and one stilbene named heterophyllene D (4), together with twenty-one known compounds were isolated from the twigs of Artocarpus heterophyllus and their structures elucidated by spectroscopic methods, mainly 1D and 2D NMR spectroscopy. The cytotoxic activity of selected compounds against KB, MCF-7 and NCI-H187 cell lines was evaluated. Heterophyllene C (3) exhibited cytotoxicity against the MCF-7 cell line with an IC₅₀ value of 12.56 μM. Additionally, the known compounds norartocarpin and artocarpin showed cytotoxic activity against MCF-7 and KB cell lines with IC₅₀ values of 10.04 and 13.57 μM, respectively. Both compounds also displayed cytotoxicity against the NCI-H187 cell line with values of 14.78 and 14.21 μM, respectively.     

New Cytotoxic Triterpenoids from the Aerial Parts of Euphorbia sieboldiana

Phytochemical investigation of the EtOH extract of Euphorbia sieboldiana led to the isolation of four new oleanane‐type triterpenoids, (1β,2α,3β,19β)‐1,2,3,19‐tetrahydroxyolean‐12‐en‐28‐oic acid, (1β,3β,19β)‐1,3,19‐trihydroxyolean‐12‐en‐28‐oic acid, (1β,2α,3β,16β,19β)‐1,2,3,16,19‐pentahydroxyolean‐12‐en‐28‐oic acid, and (1β,2α,3β,19β,23)‐1,2,3,19,23‐pentahydroxyolean‐12‐en‐28‐oic acid, along with 16 known compounds. Their structures were established by extensive 1D‐ and 2D‐NMR, as well as other spectral analyses. Biological evaluation of the four new triterpenoids revealed potent cytotoxic activities against HeLa and Hep‐G2 cells.     

Cytotoxic and Antiproliferative Effects of Diarylheptanoids Isolated from Curcuma comosa Rhizomes on Leukaemic Cells

Curcuma comosa belongs to the Zingiberaceae family. In this study, two natural compounds were isolated from C. comosa, and their structures were determined using nuclear magnetic resonance. The isolated compounds were identified as 7-(3,4-dihydroxyphenyl)-5-hydroxy-1-phenyl-(1E)-1-heptene (1) and trans-1,7-diphenyl-5-hydroxy-1-heptene (2). Compound 1 showed the strongest cytotoxicity effect against HL-60 cells, while its antioxidant and anti-inflammatory properties were stronger than those of compound 2. Compound 1 proved to be a potent antioxidant, compared to ascorbic acid. Neither compounds had any effect on red blood cell haemolysis. Furthermore, compound 1 significantly decreased Wilms’ tumour 1 protein expression and cell proliferation in KG-1a cells. Compound 1 decreased the WT1 protein levels in a time- and dose- dependent manner. Compound 1 suppressed cell cycle at the S phase. In conclusion, compound 1 has a promising chemotherapeutic potential against leukaemia.     

Synthesis and Characterization of Novel Azo-containing or Azoxy-containing Schiff Bases and Their Antiproliferative and Cytotoxic Activities

A series of novel Schiff base derivatives was designed and synthesized from 3,3'-azobenzaldehyde and 3,3'-azoxybenzaldehyde. The newly synthesized compounds were characterized by FTIR, ¹H NMR, MS and elemental analysis and tested for their in vitro antiproliferative activities against HeLa cell lines. At the same time, the impact on the antitumor activity of the sulfanilamido, benzamido, phenolic hydroxyl or thiourea groups was investigated and discussed. Compounds 4, 6 and 10 were found to exhibit strong cytotoxic activity.     

Four New Pregnane Steroids from Aglaia abbreviata and Their Cytotoxic Activities

Four new pregnane steroids, aglaiasterols A–D ( 1 – 4 ), have been isolated from the EtOH extract of stems of Aglaia abbreviata. They were identified as (3α,5α,17Z)‐3‐hydroxypregn‐17‐en‐16‐one ( 1 ), (3β,5α,17E)‐3‐hydroxypregn‐17‐en‐16‐one ( 2 ), (3β,5α,17Z)‐3‐hydroxypregn‐17‐en‐16‐one ( 3 ), and (3α,5α,20S*)‐3‐hydroxy‐16‐oxopregnan‐20‐yl acetate ( 4 ) on the basis of spectroscopic methods, including 1D‐ and 2D‐NMR techniques. Compounds 1 – 4 were evaluated for their cytotoxic activities against K562 (human leukemia), MCF‐7 (human breast cancer), and KB (human oral epithelium cancer) cells, and drug‐resistant cells of K562/A02, MCF‐7/ADM, and KB/VCR. These isolates showed weak to moderate inhibitory effects on the growth of the tested cell lines.