RESUMO
A one-pot access to the protoberberine and tetrahydroprotoberberine scaffold has been developed from easily available primary amine-functionalized o-alkynylbenzaldehydes. The core skeleton of protoberberine was afforded via in situ generation of isochromenylium by Ag(I) catalysis, subsequent cyclization to isoquinolinium, and final hydride reduction by a continuous operation procedure. The newly developed step-economic protocol shows excellent regio- and stereoselectivity and is capable of achieving those previously unavailable derivatives/analogues with electron-deficient substituents, providing a robust tool for medicinal investigations of protoberberines and derivatives.
RESUMO
Triggering the lattice oxygen oxidation mechanism is crucial for improving oxygen evolution reaction (OER) performance, because it could bypass the scaling relation limitation associated with the conventional adsorbate evolution mechanism through the direct formation of oxygen-oxygen bond. High-valence transition metal sites are favorable for activating the lattice oxygen, but the deep oxidation of pre-catalysts suffers from a high thermodynamic barrier. Here, taking advantage of the Jahn-Teller (J-T) distortion induced structural instability, we incorporate high-spin Mn3+ ( t 2 g 3 e g 1 ${{t}_{2g}^{3}{e}_{g}^{1}}$ ) dopant into Co4N. Mn dopants enable a surface structural transformation from Co4N to CoOOH, and finally to CoO2, as observed by various in situ spectroscopic investigations. Furthermore, the reconstructed surface on Mn-doped Co4N triggers the lattice oxygen activation, as evidenced experimentally by pH-dependent OER, tetramethylammonium cation adsorption and online electrochemical mass spectrometry measurements of 18O-labelled catalysts. In general, this work not only offers the introducing J-T effect approach to regulate the structural transition, but also provides an understanding about the influence of the catalyst's electronic configuration on determining the reaction route, which may inspire the design of more efficient catalysts with activated lattice oxygen.
RESUMO
A novel annulation protocol has been successfully developed in this work for the quick generation of 1,3,4,6,11,11a-hexahydro-2H-pyrazino[1,2-b]isoquinolines from easily accessible o-alkynylbenzaldehydes. Various hexahydropyrazinoisoquinolines, including those previously unavailable with electron-deficient substituents, have been achieved via the newly developed continuously operational isochromenylium/isoquinolinium-mediated procedure. It also perfectly served as a key step to generate the basic skeleton in the new total synthesis of quinocarcinol, accompanied by the development and application of a direct late-stage stereoselective sp3 C-H hydroxymethylation.
RESUMO
Food safety incidents threaten human health and life safety. It is an effective method to prevent and control the occurrence of food safety events by enhancing the rapid and sensitive detection of food contaminants. Emerging porous materials provide for the development of efficient and stable detection methods. Covalent organic frameworks (COFs) are favored by researchers for their highly ordered pore structure, large specific surface area, and good structural and functional designability. Especially in the sensing field, COFs play the roles of carriers, conductors, quenchers, and reporters, and have broad application prospects. To better understand COFs-based sensing studies, this review briefly introduces the characteristics and different functional roles of COFs in food safety analysis, focusing on the applications of COFs in the detection of various food contaminants (including foodborne pathogens, mycotoxins, pesticides, antibiotics, heavy metals, and others). Finally, the challenges and opportunities for COFs-based sensing are discussed to facilitate further applications and development of COFs in food safety.