Khellactone Derivatives and Other Phenolics of Phlojodicarpus sibiricus (Apiaceae): HPLC-DAD-ESI-QQQ-MS/MS and HPLC-UV Profile, and Antiobesity Potential of Dihydrosamidin

With obesity, the consumption of phenolic-enriched food additives as a part of traditional nutrition avoids the negative implications of eating high-calorie products. This study investigated the new herbal food additive, Phlojodicarpus sibiricus roots and herb, ubiquitously used in Siberia as a spice. Chromatographic techniques such as HPLC-DAD-ESI-QQQ-MS/MS and microcolumn HPLC-UV were the basic instruments for component profiling and quantification, and antiobesity potential was investigated using a differentiated 3T3-L1 adipocytes assay. We found that the roots and herb of P. sibiricus were high-coumarin-containing additives inhibiting triacylglycerol accumulation in 3T3-L1 preadipocytes. Forty-one phenolics were detected in P. sibiricus extracts, and 35 were coumarins, including 27 khellactone derivatives present as esters and glucosides. Total coumarin content varied from 36.16 mg/g of herb to 98.24 mg/g of roots, and from 0.32 mg/mL to 52.91 mg/mL in P. sibiricus preparations. Moreover, Siberian populations of P. sibiricus were characterised by a different HPLC-based coumarin profile. The most pronounced inhibiting effect on triacylglycerol accumulation in 3T3-L1 preadipocytes was shown for dihydrosamidin (khellactone 3′-O-isovaleroyl-4′-O-acetyl ester), which was more active than other khellactone esters and glucosides. The results demonstrated that if used as a food additive Phlojodicarpus sibiricus could be a source of bioactive coumarins of the khellactone group with high antiobesity potential.

SYNTHESIS AND REACTIONS OF 1-(4’-BROMOPHENACYL)-3-(4’-BROMO-PHENYL)-4,6-DIMETHOXYINDOLE

1-Phenacyl-3-aryl-4,6-dimethoxyindoles 2b and 2c were obtained in good yields respectively through cyclization of N,N-diphenacylaniline 1b and 1c in trifluoroacetic acid. However, instead of giving pyrroloindole 3c, treatment of phenacylindole 2c with polyphosphoric acid afforded indolizine 5 in 42% yield. Phenacylindole 2c reacts with the Vilsmeier aroylation reagent consisted of a mixture of phosphoryl chloride and p-chloro-N,N-dimethylbenzamide to give 2-aroylindole 6 (32%) and pyrroloindole 7 (22%). When treated with sodium borohydride, phenacylindole 2c gave alcohol 8 in 83% yield. Nonetheless, treatment of alcohol 8 with either p-toluenesulfonic acid in glacial acetic acid or boron trifluoride etherate in benzene did not give the desired dihydropyrroloindole 12. Instead, the reactions afforded respectively acetyl ester 9 and indole 10 in 56% and 63% yield. Keywords: phenacylindole, aroylindole, pyrroloindole, and indolizine.

Population Structure, Chemotype Diversity, and Potential Chemotype Shifting of Fusarium graminearum in Wheat Fields of Manitoba

This study was to investigate the variation of acetyl ester derivative of DON at 15-position oxygen (15ADON) and acetyl ester derivative of DON at 3-position oxygen (3ADON) chemotypes and potential chemotype shifting of Fusarium graminearum based on the population structure of this species in Manitoba. The study was conducted in 15 locations with wheat cvs. Superb and AC Barrie in Manitoba from 2004 to 2005. Percentages of chemotypes 3ADON and 15ADON of F. graminearum ranged from 0 to 95.7 and 4.3 to 100%, respectively. The 3ADON chemotype was distributed in the southern part of Manitoba and predominant in Morris and Horndean. The two chemotypes almost shared the same percentage in Portage la Prairie. The 15ADON chemotype was predominant in the other locations. Significant gene flow was found among the populations from Sanford, Portage la Prairie, Hamiota, Plumas, Rapid City, and Virden; the populations from Cartier, Rivers, Killarney, and Souris; and the populations from Morris, Kenville, and Dauphin. There were no differences between the populations from two wheat cultivars and two chemotypes. The great variation of chemotype likely resulted from the great genetic diversity of F. graminearum. Sexual recombination, population age, and cropping system could result in genetic and chemotypic diversities. Wheat seed shipment and long-distance spore transportation of F. graminearum potentially caused the genetic migration and chemotype shifting in Manitoba.