The two important epigenetic markers in the human genome, 5-methylcytosine (mC) and 5-hydroxymethylcytosine (hmC), are involved in gene regulation processes. As a major epigenetic target, cytosines in a C-rich DNA sequence were substituted with mC and hmC to investigate the thermal stability and pH sensitivity of the corresponding i-motifs. Circular Dichroism (CD) studies indicate the formation of i-motifs at acidic pH (<6.5) for mC- and hmC-modified DNA sequences. Thermal denaturation results suggest that DNA i-motifs are stabilized when modified with one or two mCs. However, hypermethylation with mC and single modification with hmC cause destabilization of the structure. A biomimetic crowding agent does not alter the stability effect trends resulting from mC and hmC modifications, though the corresponding i-motifs show elevated melting temperatures without significant changes in pKa values.
A series of novel vanadium(III) complexes bearing iminopyrrolide chelating ligands [2-(RN=CH)C4H3N]V(THF)2Cl2 (2a: R = cyclohexyl; 2b: R = Ph; 2c: R = 2,6-iPr2C6H3; 2d: R = p-CF3C6H4; 2e: R = C6F5) have been synthesized and characterized. Single-crystal X-ray diffraction revealed that complexes 2a, 2c and 2e adopt an octahedral geometry around the vanadium center. In the presence of Et2AlCl as a co-catalyst, these complexes displayed high catalytic activities up to 48.6 kg PE mmol(V)(-1) h(-1) bar(-1) for ethylene polymerization, and produced high molecular weight polymers. 2a-e/Et2AlCl catalytic systems were tolerant to elevated temperature (70 degrees C) and yielded unimodal polyethylenes, indicating the single site behaviour of these catalysts. By pre-treating with equimolar amounts of alkylaluminums, functional alpha-olefin 10-undecen-1-ol can be efficiently incorporated into polyethylene chains. 10-Undecen-1-ol incorporation can easily reach 15.8 mol% under the mild conditions. When compared with VCl3(THF)3 or rac-Et[Ind]2ZrCl2, these vanadium(III) complexes exhibited higher activities towards the copolymerization, and can incorporate more 10-undecen-1-ol into polymer chains under the similar conditions.
A C2-protected imidazolium salt that generates an abnormal N-heterocyclic carbene (NHC) was applied for the palladium-catalyzed Suzuki-Miyaura coupling reactions. The abnormal NHC precursor promoted the reactions while suppressing homocoupling of aryl boronic acid, which was observed with the corresponding normal NHC precursor. The related well-defined abnormal NHC-based palladium complexes also showed better activity than the normal NHC-based analogues, exhibiting faster reaction rates especially at the initial stage of the reaction.
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