Phytotoxic polyacetylenes from roots of Russian knapweed (Acroptilon repens (L.) DC.)

There are several factors thought to assist invasive weeds in colonization of ecosystems. One of these factors is allelopathy, the negative effect of chemicals produced by one plant on neighboring plants, frequently mediated through root exudates and other plant leachates. Acroptilon repens (Asteraceae) is one of the most invasive and ecologically threatening weed species in western North America. A bioassay-guided fractionation of the root extracts of this plant led to the isolation of five polyacetylenic compounds, of which one [5′-methoxy-1′-(5-prop-1-yn-1-yl-2-thienyl)-hexa-2′,4′-diyin-6′-yl acetate] was hitherto unknown. The structures of these compounds were elucidated on the basis of spectroscopic analysis (IR, ESIMS, ¹H, ¹³C NMR and 2D NMR). All of the compounds obtained, except 1-chloro-4-(5-penta-1,3-diyn-1-yl-2-thienyl)but-3-yn-2-ol, showed phytotoxic activity against Arabidopsis thaliana seedlings. The presence of 4′-chloro-1′-(5-penta-1,3-diyn-1-yl-2-thienyl)-but-2′-yn-3′-ol was detected in the root exudates of aeroponically grown A. repens plants. None of the polyacetylenes isolated in this study were found in Colorado soils collected between September 2006 and July 2007 in an A. repens colonized site. However, polyacetylene 5 in A. repens infested soil from Washington was found in June, 2007. Contrary to our previous report, the compound 7,8-benzoflavone (6) was not detected in root exudates, nor was it encountered in extracts of roots, aerial parts or infested soil. Since we could not repeat this work, the original report has been retracted [Stermitz, F.R., Bais, H.P., Foderaro, T.A., Vivanco, J.M., 2003. 7,8-Benzoflavone: a phytotoxin from root exudates of invasive Russian knapweed [A retraction]. Phytochemistry 64, 493-497.].     

白花鬼针草中多烯炔类成分的分离及其生物活性研究

为了解白花鬼针草(Bidens pilosa var.radiata)的化学成分,采用多种色谱技术从其提取物中分离多烯炔类成分,并对其生物活性进行研究。结果表明,从白花鬼针草乙酸乙酯提取部位中分离鉴定出4个多烯炔类化合物,分别为5-acetoxy-2-phenylethinyl-thiophene (1)、1-phenylhepta-1,3,5-triyne (2)、5-phenyl-2-(1-propynyl)-thiophene (3)和icthyothereol acetate (4)。体外活性评价结果表明,化合物1～4均具有中等抗MRSA活性,且均对人肝LO_2细胞无毒性。首次为化合物1提供核磁数据并进行结构解析,化合物3、4为首次从该属植物中分离得到。     

Quantitative Comparison of Ginsenosides and Polyacetylenes in Wild and Cultivated American Ginseng

Quantitative comparison of seven ginsenosides in wild and cultivated American ginseng revealed that the Rg₁/Rd ratio presented a significantly large difference between cultivated and type‐I (one of the defined chemotypes) wild American ginseng, facilitating this ratio as a characteristic marker for differentiating these two groups. Similarly, the ratio (Rg₁+Re)/Rd, and the ratio of protopanaxatriol (PPT)‐type ginsenosides to protopanaxadiol (PPD)‐type ginsenosides showed a large difference between these two groups. On the other hand, type‐II wild samples were found to have high Rg₁/Rb₁ and Rg₁/Re ratios and low panaxydol/panaxynol ratio, which is entirely different from Type‐I American ginseng, but is very similar to that of Asian ginseng. This not only suggests that the chemotype should be taken into consideration properly when using these parameters for differentiating American and Asian ginseng, but also indicates that type‐II wild American ginseng may have distinct pharmacological activities and therapeutic effects.     

Chemical and Pharmacological Progress on Polyacetylenes Isolated from the Family Apiaceae

This review presents an up‐to‐date survey of natural polyacetylenes isolated from the family Apiaceae, and their biosynthesis and biological activities up to May 2013, with 107 references. A total of 103 polyacetylenes from 72 species of 41 genera of Apiaceae have been isolated so far, among which falcarinol‐type polyacetylenes are most widely distributed.     

The influence of the fungal pathogen Mycocentrospora acerina on the proteome and polyacetylenes and 6-methoxymellein in organic and conventionally cultivated carrots (Daucus carota) during post harvest storage

Many carrots are discarded during post harvest cold storage due to development of fungal infections, caused by, e.g., Mycocentrospora acerina (liquorice rot). We compared the susceptibility of carrots grown under conventional and organic agricultural practices. In one year, organically cultivated carrots showed 3 × to 7 × more symptoms than conventionally cultivated, when studying naturally occurring disease at 4 and 6 months, respectively. On the other hand, we have developed a bioassay for infection studies of M. acerina on carrots and observed that organic roots were more susceptible after one month of storage than conventional ones, but no differences were apparent after four or six months storage. Levels of polyacetylenes (falcarinol, falcarindiol and falcarindiol-3-acetate) did not change, whereas the isocoumarin phytoalexin (6-methoxymellein) accumulated in infected tissue as well as in healthy tissue opposite the infection. The proteomes of carrot and M. acerina were characterized, the intensity of 33 plant protein spots was significantly changed in infected roots including up regulation of defence and stress response proteins but also a decrease of proteins involved in energy metabolism. This combined metabolic and proteomic study indicates that roots respond to fungal infection through altered metabolism: simultaneous induction of 6-methoxymellein and synthesis of defence related proteins.     

Sequestration of polyacetylenes by the parasite Orobanche hederae (Orobanchaceae) from its host Hedera helix (Araliaceae)

Orobanche hederae Duby and its host Hedera helix L. were collected in the North Italian Trentino-Südtirol region and analyzed for their content of polyacetylenes. Both, the host plant (Hedera) and the parasite (Orobanche) contained the polyacetylene falcarinol and two of its dehydroderivatives. The contents of polyacetylenes in Hedera decrease from roots via stems to leaves and contents in Orobanche are only about one-tenth of the contents in the Hedera roots it parasites on. Moreover, relative contents of the more polar polyacetylenes are higher in Orobanche than in Hedera, implying a bias toward the sequestration of more polar compounds.     

Polyacetylenes of Brazilian species of Didymopanax (Araliaceae)

Analysis of ethereal extracts of the roots of Didymopanax macrocarpus and D. vinosus gave falcarinol, dehydrofalcarinol, falcarinone, dehydrofalcarinone and octa-9(Z); 17-diene-12,14-diyne-1,16-diol. The presence of these dehydro compounds in the Araliaceae is very unusual and may constitute an index for chemotaxonomic characterization of the genus.     

A New Prenylated Flavanonol from Seseli annuum Roots Showing Protective Effect on Human Lymphocytes DNA

A new prenylated flavanonol named seselinonol ( 1 ) was isolated from the roots of Seseli annuum, together with the well‐known biologically active polyacetylenes falcarinol ( 2 ) and falcarindiol ( 3 ), and the prenylated furanocoumarin phellopterin ( 4 ). Its structure was elucidated by extensive spectroscopic analysis, including HR‐ESI‐MS, 1D‐ and 2D‐NMR. Seselinonol and phellopterin were tested for in vitro protective effect on chromosome aberrations in peripheral human lymphocytes using cytochalasin‐B blocked micronucleus (CBMN) assay. The new compound exerted a beneficial effect by decreasing DNA damage of human lymphocytes.     

The anti-staphylococcal activity of Angelica dahurica (Bai Zhi)

Bioassay-guided fractionation of a hexane extract prepared from the roots of the Chinese drug Angelica dahurica (Bai Zhi) led to the isolation of the polyacetylenic natural product falcarindiol (1). The absolute stereochemistry of this compound was confirmed by careful 1H NMR analysis of its (R)- and (S)-Mosher ester derivatives as the 3(R), 8(S) isomer. Activity was tracked using a Mycobacterium fortuitum screening assay and the purified product was evaluated against multidrug-resistant and methicillin-resistant strains of Staphylococcus aureus (MRSA). The minimum inhibitory concentrations (MIC) of this metabolite ranged from 8 to 32 microg/ml highlighting the potential of the acetylene natural product class as antibiotic-lead compounds. These MIC values compare favourably with some of the newest agents in development for the treatment of MRSA infection and indicate that further evaluation of the antibiotic activity of acetylenes is warranted.     

多炔类化合物对亚洲玉米螟产卵驱避作用及玉米螟的触角电位反应

以茵陈二炔为结构母体,人工合成了11个多炔类化合物。采用蜡纸接卵法,测定了11 个化合物对亚洲玉米螟Ostrinia furnacalis的产卵驱避活性。结果表明: 当处理浓度为20 μg/cm²时,受试的化合物对亚洲玉米螟的产卵行为具有一定程度的驱避作用,其中化合物9（1-苯基-4-甲基-丁二炔）对亚洲玉米螟产卵驱避作用明显, 调查处理后的3天、4天、 5天和6天,其产卵驱避率分别为85.71%、80.00%、61.27%和62.51%。触角电位测定表明,受试的11个化合物对亚洲玉米螟成虫触角感受器具有刺激作用,其中化合物6和化合物9能强烈地刺激产生高振幅的动作电位。10 mg/mＬ浓度处理,测得化合物6触角电位相对值, 雌、雄虫分别为68.22% 和106.60%,化合物9分别为199.19% 和220.60%。经回归分析所测11个化合物的产卵驱避活性与触角电位反应相对值,两者呈现一定程度上的相关性。还讨论了合成的多炔类化合物对亚洲玉米螟可能的作用靶标和结构与活性间的关系。