Efficient and Selective Oxygenation of Cycloalkanes and Alkyl Aromatics with Oxygen through Synergistic Catalysis of Bimetallic Active Centers in Two-Dimensional Metal-Organic Frameworks Based on Metalloporphyrins.

Confined catalytic realms and synergistic catalysis sites were constructed using bimetallic active centers in two-dimensional metal-organic frameworks (MOFs) to achieve highly selective oxygenation of cycloalkanes and alkyl aromatics with oxygen towards partly oxygenated products. Every necessary characterization was carried out for all the two-dimensional MOFs. The selective oxygenation of cycloalkanes and alkyl aromatics with oxygen was accomplished with exceptional catalytic performance using two-dimensional MOF Co-TCPPNi as a catalyst. Employing Co-TCPPNi as a catalyst, both the conversion and selectivity were improved for all the hydrocarbons investigated. Less disordered autoxidation at mild conditions, inhibited free-radical diffusion by confined catalytic realms, and synergistic C-H bond oxygenation catalyzed by second metal center Ni employing oxygenation intermediate R-OOH as oxidant were the factors for the satisfying result of Co-TCPPNi as a catalyst. When homogeneous metalloporphyrin T(4-COOCH3)PPCo was replaced by Co-TCPPNi, the conversion in cyclohexane oxygenation was enhanced from 4.4% to 5.6%, and the selectivity of partly oxygenated products increased from 85.4% to 92.9%. The synergistic catalytic mechanisms were studied using EPR research, and a catalysis model was obtained for the oxygenation of C-H bonds with O2. This research offered a novel and essential reference for both the efficient and selective oxygenation of C-H bonds and other key chemical reactions involving free radicals.

MiR-125a-5p functions as a tumour suppressor in breast cancer by downregulating BAP1.

MicroRNAs (miRNAs) play an important role in the regulation of human cancers, including breast cancer (BC). In the current study, we examined the expression pattern of the miRNA miR-125a-5p in human BC tissues, tumorigenesis of BC progression. We found that miR-125a-5p was significantly downregulated in human BC tissues. Overexpression of miR-125a-5p in a xenograft mouse model indicated that miR-125a-5p may function as a tumour suppressor during carcinogenesis. To explore the molecular mechanism by which miR-125a-5p contributes to BC progression, we predicted the target genes of miR-125a-5p and identified BC susceptibility gene 1-associated protein 1 (BAP1) as a direct target. Finally, we demonstrated that BAP1 had opposing effects to those of miR-125a-5p on BC cells, suggesting that miR-125a-5p may inhibit cell proliferation and promote cell apoptosis by negatively regulating BAP1. Taken together, our findings provide the first clues regarding the role of miR-125a-5p as a tumour suppressor in BC via the inhibition of BAP1 translation.