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em BORIS: Bern Open Repository and Information System - Berna - Suiça


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New fluorinated hybrid solids [Mo2F2O5(tr2pr)] (1), [Co3(tr2pr)2(MoO4)2F2]7H2O (2), and [Co3(H2O)2(tr2pr)3(Mo8O26F2)]3H2O (3) (tr2pr = 1,3-bis(1,2,4-triazol-4-yl)propane) were prepared from the reaction systems consisting of Co(OAc)2/CoF2 and MoO3/(NH4)6Mo7O24, as CoII and MoVI sources, in water (2) or in aqueous HF (1, 3) employing mild hydrothermal conditions. The tr2pr ligand serves as a conformationally flexible tetradentate donor. In complex 1, the octahedrally coordinated Mo atoms are linked in the discrete corner-sharing {Mo2(2-O)F2O4N4} unit in which a pair of tr-heterocycles (tr = 1,2,4-triazole) is arranged in cis-positions opposite to molybdenyl oxygen atoms. The antianti conformation type of tr2pr facilitates the tight zigzag chain packing motif. The crystal structure of the mixed-anion complex salt 2 consists of trinuclear [Co3(3-MoO4)2(2-F)2] units self-assembling in CoII-undulating chains (CoCo 3.0709(15) and 3.3596(7) ), which are cross-linked by tr2pr in layers. In 3, containing condensed oxyfluoromolybdate species, linear centrosymmetric [Co3(2-tr)6]6+ SBUs are organized at distances of 10.7212.45 in an -Po-like network using bitopic tr-linkers. The octahedral {N6} and {N3O3} environments of the central and peripheral cobalt atoms, respectively, are filled by triazole N atoms, water molecules, and coordinating [Mo8O26F2]6 anions. Acting as a tetradentate O-donor, each difluorooctamolybdate anion anchors four [Co3(2-tr)6]6+ units through their peripheral Co-sites, which consequently leads to a novel type of a two-nodal 4,10-c net with the Schlafli symbol {32.43.5}{34.420.516.65}. The 2D and 3D coordination networks of 2 and 3, respectively, are characterized by significant overall antiferromagnetic exchange interactions (J/k) between the CoII spin centers on the order of 8 and 4 K. The [Mo8O26F2]6 anion is investigated in detail by quantum chemical calculations.

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The identification of associations between interleukin-28B (IL-28B) variants and the spontaneous clearance of hepatitis C virus (HCV) raises the issues of causality and the net contribution of host genetics to the trait. To estimate more precisely the net effect of IL-28B genetic variation on HCV clearance, we optimized genotyping and compared the host contributions in multiple- and single-source cohorts to control for viral and demographic effects. The analysis included individuals with chronic or spontaneously cleared HCV infections from a multiple-source cohort (n = 389) and a single-source cohort (n = 71). We performed detailed genotyping in the coding region of IL-28B and searched for copy number variations to identify the genetic variant or haplotype carrying the strongest association with viral clearance. This analysis was used to compare the effects of IL-28B variation in the two cohorts. Haplotypes characterized by carriage of the major alleles at IL-28B single-nucleotide polymorphisms (SNPs) were highly overrepresented in individuals with spontaneous clearance versus those with chronic HCV infections (66.1% versus 38.6%, P = 6 10(-9) ). The odds ratios for clearance were 2.1 [95% confidence interval (CI) = 1.6-3.0] and 3.9 (95% CI = 1.5-10.2) in the multiple- and single-source cohorts, respectively. Protective haplotypes were in perfect linkage (r(2) = 1.0) with a nonsynonymous coding variant (rs8103142). Copy number variants were not detected. CONCLUSION: We identified IL-28B haplotypes highly predictive of spontaneous HCV clearance. The high linkage disequilibrium between IL-28B SNPs indicates that association studies need to be complemented by functional experiments to identify single causal variants. The point estimate for the genetic effect was higher in the single-source cohort, which was used to effectively control for viral diversity, sex, and coinfections and, therefore, offered a precise estimate of the net host genetic contribution.