Use of P450 cytochrome inhibitors in studies of enokipodin biosynthesis

Enokipodins A, B, C, and D are antimicrobial sesquiterpenes isolated from the mycelial culture medium of Flammulina velutipes, an edible mushroom. The presence of a quaternary carbon stereocenter on the cyclopentane ring makes enokipodins A-D attractive synthetic targets. In this study, nine different cytochrome P450 inhibitors were used to trap the biosynthetic intermediates of highly oxygenated cuparene-type sesquiterpenes of F. velutipes. Of these, 1-aminobenzotriazole produced three less-highly oxygenated biosynthetic intermediates of enokipodins A-D; these were identified as (S)-(-)-cuparene-1,4-quinone and epimers at C-3 of 6-hydroxy-6-methyl-3-(1,2,2-trimethylcyclopentyl)-2-cyclohexen-1-one. One of the epimers was found to be a new compound.

Role of phenolics and boron in reproductive success in seasonally transient sterile Tecoma stans L.

Quantitative and qualitative analysis of phenolics and boron in stigma of transient sterile Tecoma stans L. during seedless (May-July), partially seedbearing (August-November, April) and seedbearing periods (December-March) was made. UV absorption profile of stigmatic exudates indicated the presence of simple phenolics. Total phenolics were higher in stigma during seedless period. Thin layer chromatographic analysis of stigmatic extracts exhibited only three principal spots. Mass spectrophotometry showed the presence of derivatives of cinnamic acid, namely, caffeic acid in these spots. Quantity of boron in stigma during seedless period was lowest but the difference with other periods was not significant. It was suggested that the accumulation of higher quantity of caffeic acid in the stigma during seedless period due to high temperature (40 degrees-45 degrees C) could lead to inhibition of pollen germination in vivo, thereby rendering the plants seedless. This was confirmed by inhibition of in vitro pollen germination in the basal medium containing higher quantity of caffeic acid.