A cold-water polysaccharide-protein complex from Grifola frondosa exhibited antiproliferative activity via mitochondrial apoptotic and Fas/FasL pathways in HepG2 cells.

Grifola frondosa (G. frondosa) is widely known for its anti-tumor potential, which has been demonstrated by numerous scientific researches. In this study, two water soluble polysaccharide-protein complexes were extracted from G. frondosa at 4 °C (GFG-4) and 100 °C (GFG-100) and purified. Compared with GFG-100, GFG-4 had a higher protein content and molecular weight. The main monosaccharides of GFG-4 and GFG-100 were rhamnose, glucose, and galactose, with an approximate ratio of 3.00: 1.00: 0.86 and 2.85: 1.00: 0.94, respectively. The Fourier transform infrared spectra indicated that the two polysaccharide-protein complexes displayed characteristic functional groups of polysaccharides and proteins, and mainly contain pyranose ring with α-glycosidic linkage. Atomic force microscope images showed that both GFG-4 and GFG-100 exhibited straight chains, and GFG-4 possessed a relatively abundant fraction of branched chains. Intriguingly, GFG-4 showed a stronger antiproliferative activity against HepG2 cells than GFG-100. The mechanisms were further investigated by quantitative real-time PCR and western blot, it found that GFG-4 inhibited the proliferation of HepG2 cells mainly through the intrinsic activation of mitochondrial pathway and the Fas/FasL-mediated Caspase-8/-3 pathway. Conclusively, G. frondosa cold-water extracted polysaccharide-protein complexes could be used as a functional food for preventing or treating hepatocellular carcinoma.

Concise synthesis of 2-methoxyestradiol from 17ß-estradiol through the C(sp2)-H hydroxylation.

A four-step route for the synthesis of 2-methoxyestradiol (5) starting from 17ß-estradiol (1) has been achieved with a 51% overall yield. The key step was the ruthenium-catalyzed ortho-C(sp2)-H bond hydroxylation of aryl carbamates. Using dimethyl carbamate as the directing group, [RuCl2(p-cymene)]2 as the catalyst, PhI(OAc)2 as the oxidant and trifluoroacetate/trifluoroacetic anhydride (1:1) as the co-solvent, the hydroxyl group could be singly installed at the 2-position of 3-dimethylcarbamoyloxyestradiol (2) with 65% yield. Subsequent methylation of hydroxy and removal of dimethyl carbamate afforded 2-methoxyestradiol (5).