The chemistry of cationic forms of clusterfullerenes remainl ess explored than that of the corresponding neutralo ra nionic species. In the presentw ork, M 3 N@I h -C 80 (M = Sc or Lu) cationsw ere generated by both electrochemical and chemical oxidationm ethods. The as-obtained cations successfully underwentt he typical Bingel-Hirsch reactiont hat fails with neutral Sc 3 N@I h -C 80 .T wo isomeric Sc 3 N@I h -C 80 cation derivatives, [5,6]-open and [6,6]open adducts,w ere synthesized, and the former has never been prepared by meanso faB ingel-Hirsch reactionw ith neutralc lusterfullerenes.I nt he case of the Lu 3 N@I h -C 80 cation,h owever,o nly a[ 6,6]-open adduct was obtained. Densityf unctional theory (DFT) calculations indicated that the oxidized M 3 N@I h -C 80 was much more reactive than the neutralc ompound upon addition of the diethylb romomalonate anion.T he Bingel-Hirschr eaction of M 3 N@I h -C 80 cationso ccurredb ym eanso fa nu nusual outer-sphere single-electron transfer( SET) processf rom the diethyl bromomalonate anion to the stable intermediate [M 3 N@C 80 (C 2 H 5 COO) 2 CBr]C.R emarkably,t he diethyl bromomalonate anion was found to act as both an ucleophile and an electrond onor.
Host genotype may be closely related to the different outcomes of Hepatitis B virus (HBV) infection. To identify the association of variants and HBV infection, we comprehensively investigated the cytokine- and immune-related gene mutations in patients with HBV associated hepatocellular carcinoma (HBV-HCC). Fifty-three HBV-HCC patients, 53 self-healing cases (SH) with HBV infection history and 53 healthy controls (HCs) were recruited, the whole exon region of 404 genes were sequenced at >900× depth. Comprehensive variants and gene levels were compared between HCC and HC, and HCC and SH. Thirty-nine variants (adjusted P<0.0001, Fisher’s exact test) and 11 genes (adjusted P<0.0001, optimal unified approach for rare variant association test (SKAT-O) gene level test) were strongly associated with HBV-HCC. Thirty-four variants were from eight human leukocyte antigen (HLA) genes that were previously reported to be associated with HBV-HCC. The novelties of our study are: five variants (rs579876, rs579877, rs368692979, NM_145007:c.*131_*130delTG, NM_139165:exon5:c.623-2->TT) from three genes (REAT1E, NOD-like receptor (NLR) protein 11 (NLRP11), hydroxy-carboxylic acid receptor 2 (HCAR2)) were found strongly associated with HBV-HCC. We found 39 different variants in 11 genes that were significantly related to HBV-HCC. Five of them were new findings. Our data implied that chronic hepatitis B patients who carry these variants are at a high risk of developing HCC.
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