Biomedical subjects
Publications and source records attributed to Jianyong Zhang.
In the absence of coordinating solvents and anions, silver salts and triphosphines form viscous, thixotropic coordination polymers in solution, which aggregate into unusual wormlike macroscopic structures and undergo cage-polymer interconversions depending on the stoichiometry and presence of templating anions.
NF-E2-related factor 2 (Nrf2) regulates antioxidant-responsive element-mediated induction of cytoprotective genes in response to oxidative stress. The purpose of this study was to determine the role of BRG1, a catalytic subunit of SWI2/SNF2-like chromatin-remodeling complexes, in Nrf2-mediated gene expression. Small interfering RNA knockdown of BRG1 in SW480 cells selectively decreased inducible expression of the heme oxygenase 1 (HO-1) gene after diethylmaleate treatment but did not affect other Nrf2 target genes, such as the gene encoding NADPH:quinone oxidoreductase 1 (NQO1). Chromatin immunoprecipitation analysis revealed that Nrf2 recruits BRG1 to both HO-1 and NQO1 regulatory regions. However, BRG1 knockdown selectively decreased the recruitment of RNA polymerase II to the HO-1 promoter but not to the NQO1 promoter. HO-1, but not other Nrf2-regulated genes, harbors a sequence of TG repeats capable of forming Z-DNA with BRG1 assistance. Similarly, replacement of the TG repeats with an alternative Z-DNA-forming sequence led to BRG1-mediated activation of HO-1. These results thus demonstrate that BRG1, through the facilitation of Z-DNA formation and subsequent recruitment of RNA polymerase II, is critical in Nrf2-mediated inducible expression of HO-1.
We present a highly unusual example of self-assembly, specifically a polar, mixed-ligand cage which forms in preference to symmetrical homo-ligand products, and which suggests that steric effects can be exploited to obtain novel non-uniform polyhedral cages. In particular, reaction between the bulky tripodal triphosphine 2,4,6-tris(diphenylphosphino)triazine, L1, the non-bulky tripodal trinitrile 2,4,6-tris(cyanomethyl)trimethylbenzene, L2 and silver hexafluoroantimonate, AgSbF6, in a 3:1:4 ratio gives the mixed-ligand aggregate [Ag4(L1)3(L2)(SbF6)]3+, 1-SbF6, instantly as the only product in quantitative yield. The X-ray crystal structure of complex 1-SbF6 is consistent with the suspected solution-state structure. The cage derives from trigonal-pyramidal geometry, the basal vertices of which are defined by three bulky triphosphines, L1, and the apical vertex by the non-bulky trinitrile, L2. There is apical elongation amounting to 19% in comparison to the ideal uniform tetrahedron. The cage also encapsulates an SbF6 anion. 19F NMR spectra in solution for the analogous PF6 complex [Ag4(L1)3(L2)(PF6)]3+, 1-PF6, confirm that one anion is also encapsulated in solution. The synthesis of the analogous CF3SO3(-) complex, [Ag4(L1)3(L2)(OTf)]3+, 1-OTf, in solution is also described, although 1-PF6 and 1-OTf could not be isolated due to slow decomposition in solution. The selective formation of these mixed-ligand cages is discussed in terms of ligand-ligand and ligand-included anion steric repulsions, which we propose prevent the formation of the competing hypothetical homo-ligand tetrahedral structure [Ag4(L1)4(SbF6)]3+, and thus favour the mixed ligand cage. "Cage cone angles" for L1 and L2 are estimated at 115 degrees and 101 degrees, respectively. Variable-temperature 31P NMR spectroscopy shows that complex 1-SbF6 and the related previously reported partial tetrahedral complex [Ag4(L1)3(anion)]3+ undergo dynamic twisting processes in solution between enantiomeric C3-symmetry conformations.
The combination of directionality and unsaturated metal sites in bowl-shaped coordination clusters [Ag(4)L(3)(SbF(6))](3+){L = 2,4,6-tris(diphenylphosphino)triazine} results in the formation of discrete dimers on reaction with additional bridging ligands.