Hopane-type triterpenes from Cnidoscolus spinosus and their bioactivities.

Chemical investigation of the aerial parts of Cnidoscolus spinosus resulted in the isolation of relatively infrequent hopane-type triterpenes, 3ß-acetoxy-hop-22(29)-ene (1), first reported here as natural product, together with 3-oxo-hop-22(29)-ene (2), and 3ß-hydroxy-hop-22(29)-ene (3). ß-Amyrin palmitate and three phytosterols were also characterized. The structures of the compounds were established using spectroscopic methods, and those of 1 and 2 were confirmed by crystallographic analysis. Selected biological activities for the isolated hopane-type triterpenes were tested through a series of assays for determining the cytotoxic, anti-inflammatory, α-glucosidase inhibition and antiparasitic activities. Compounds 1-3 did not show cytotoxic activity, compound 1 displayed an important inhibitory effect in the mouse ear induced inflammation assay, and significantly inhibited the yeast α-glucosidase activity in vitro and in silico. Additionally, compounds 2 and 3 showed marginal activities against Trypanosoma cruzi and Leishmania mexicana. Therefore, the bioactivities of hopane-type triterpenes deserve further investigation, particularly their anti-inflammatory properties.

Flavonoids Affect the Light Reaction of Photosynthesis in Vitro and in Vivo as Well as the Growth of Plants.

Flavonoids retusin (5-hydroxy-3,7,3',4'-tetramethoxyflavone) (1) and pachypodol (5,4'-dihydroxy-3,7,3'-trimethoxyflavone) (2) were isolated from Croton ciliatoglanduliferus Ort. Pachypodol acts as a Hill reaction inhibitor with its target on the water splitting enzyme located in PSII. In the search for new herbicides from natural compounds, flavonoids 1 and 2 and flavonoid analogues quercetin (3), apigenin (4), genistein (5), and eupatorin (6) were assessed for their effect in vitro on the photosynthetic electron transport chain and in vivo on the germination and growth of the plants Physalis ixocarpa, Trifolium alexandrinum and Lolium perenne. Flavonoid 3 was the most active inhibitor of the photosynthetic uncoupled electron flow (I50 = 114 µM) with a lower log P value (1.37). Results in vivo suggest that 1, 2, 3, and 5 behave as pre- and postemergent herbicides, with 3 and 5 being more active.

Derivatives of diterpen labdane-8α,15-diol as photosynthetic inhibitors in spinach chloroplasts and growth plant inhibitors.

In a search of new efficient herbicides of natural origin, four derivatives were prepared from labdane-8α,15-diol (1) and 15-O-acetyl-8α-hydroxy labdane (2) isolated from Croton ciliatoglanduliferus. Their inhibitory activity on photosynthetic electron transport on fresh, broken spinach chloroplasts and on the growth of plants were determined. Derivative 15-O-benzoyl-8α-hydroxy labdane (5) was seven times more active than 2 as reaction Hill inhibitor. Complex of 5 with the adjuvant 2-hydroxypropyl-ß-cyclodextrin (5:HPB) (200 µM) was sprayed on Physalys ixocarpa (green tomato) plants; 48 h later the complex inhibited PS II by transforming the active reaction centers to silent reaction centers or "heat sinks". After 72 h this effect disappeared, probably 5:HPB was metabolized by the plant. Chlorophyll a fluorescence of Trifolium alexandrinum (clover) leaves was affected with 5:HPB at the level of PQ pool reduction. 5:HPB decreases the tomato and clover dry-biomass, without affecting Lolium perenne (grass) plants, suggesting that complex 5 acts as selective herbicide for dicotyledonous plants.

Natural diterpenes from Croton ciliatoglanduliferus as photosystem II and photosystem I inhibitors in spinach chloroplasts.

In our search for new natural photosynthetic inhibitors that could lead to the development of "green herbicides" less toxic to environment, the diterpene labdane-8alpha,15-diol (1) and its acetyl derivative (2) were isolated for the first time from Croton ciliatoglanduliferus Ort. They inhibited photophosphorylation, electron transport (basal, phosphorylating and uncoupled) and the partial reactions of both photosystems in spinach thylakoids. Compound 1 inhibits the photosystem II (PS II) partial reaction from water to Na(+) Silicomolibdate (SiMo) and has no effect on partial reaction from diphenylcarbazide (DPC) to 2,6-dichlorophenol indophenol (DCPIP), therefore 1 inhibits at the water splitting enzyme and also inhibits PS I partial reaction from reduced phenylmetasulfate (PMS) to methylviologen (MV). Thus, it also inhibits in the span of P(700) to Iron sulfur center X (F(X)). Compound 2 inhibits both, the PS II partial reactions from water to SiMo and from DPC to DCPIP; besides this, it inhibits the photosystem I (PS I) partial reaction from reduced PMS to MV. With these results, we concluded that the targets of the natural product 2 are located at the water splitting enzyme, and at P(680) in PS II and at the span of P(700) to F(X) in PS I. The results of compounds 1 and 2 on PS II were corroborated by chlorophyll a fluorescence.