Synthesis of Trisubstituted Furans via Copper(I)-Catalyzed Strain-Driving Cycloisomerization/Annulative Fragmentation

The in situ formed furan-fused cyclobutenes via Cu­(I)-catalyzed cycloisomerization of readily available allenyl ketones bearing a cyclopropyl moiety are a highly reactive and powerful species, which undergo annulative fragmentation with terminal ynones to afford a wide variety of functional furans in moderate to high yields. This ring-distortion protocol features an unprecedented strain-controlled cycloisomerization/Diels–Alder/retro-Diels–Alder (CDRD) sequence under mild conditions

Ag–O–Co Interface Modulation-Amplified Luminol Cathodic Electrogenerated Chemiluminescence

It remains a great challenge to develop effective strategies for improving the weak cathodic electrogenerated chemiluminescence (ECL) of the luminol-dissolved O2 system. Interface modulation between metal and supports is an attractive strategy to improve oxygen reduction reaction (ORR) activity. Therefore, the design of electrocatalysts via interface modulation would provide new opportunities for the ECL amplification involving reactive oxygen species (ROSs). Herein, we have fabricated an Ag single-atom catalyst with an oxygen-bridged interface (Ag–O–Co) through the electrodeposition of Ag on a CoAl layered double hydroxide (LDH) modified indium tin oxide (ITO) electrode (Ags/LDH/ITO). Interestingly, it was found that the cathodic ECL intensity of the luminol-dissolved O2 system at the Ags/LDH/ITO electrode was extraordinarily enhanced in comparison with those at bare ITO and other Ag nanoparticle-based electrodes. The enhanced ECL performances of the Ags/LDH/ITO electrode were attributed to the increasing amounts of ROSs by electrocatalytic ORR in the Ag–O–Co interface. The electron redistribution of Ag and Co bimetallic sites could accelerate electron transfer, promote the adsorption of O2, and sufficiently activate O2 through a four-electron reaction pathway. Finally, the luminol cathodic ECL intensity was greatly improved. Our findings can provide inspiration for revealing the interface effects between metal and supports, and open up a new avenue to improve the luminol cathodic ECL

Addressing the Origin of Single-Atom-Activated Supports Monitored by Electrochemiluminescence

Currently, much attention has been paid to the efforts to stabilize and regulate single atoms through supports to obtain decent electrocatalytic behaviors. However, little concern was given to the effect of single atoms on modulating the electronic structure of supports, despite the catalytic activities and large quantities of supports in the catalytic reactions. Herein, we have localized Ru single atoms onto two-dimensional layered double hydroxide (NiFe-LDH) and studied the role of Ru single atoms in adjusting the electronic structure of the NiFe-LDH support. Spin polarization of 3d electrons for Fe and electron redistribution in NiFe-LDH were effectively modulated through the interaction between Ru single atoms and NiFe-LDH. As a result, the luminol redox reaction and reactive oxygen revolution were simultaneously promoted by Ru single-atom-modulated NiFe-LDH, manifested as boosted electrochemiluminescence (ECL). Therefore, we have provided valid information to reveal the regulation effect of single atoms on the spin state and electronic structure of the supports. It is anticipated that our strategy may arouse wide interest in manipulating single-atom-modulated supports

Modular Synthesis of Tetrasubstituted Pyrroles via an Annulative Migration Reaction of Allenyl Ketones and <i>p</i>‑Toluenesulfonylmethyl Isocyanide

The metal-free cyclization of allenyl ketones and p-toluenesulfonylmethyl isocyanide (TosMIC), promoted by Cs2CO3, provides a convenient access to tetrasubstituted pyrroles in which an acyl group undergoes 1,2-migration. This tandem Michael addition/annulative migration synthetic strategy is general and high-yielding for various substituted allenyl ketones. Moreover, a phosphoryl or ester moiety is also a suitable functionality to enable such migration

Gold(I)-Catalyzed [8+4] Cycloaddition of 1,4-All-Carbon Dipoles with Tropone

Herein, we describe a gold­(I)-catalyzed generation of nonclassical gold-containing 1,4-all-carbon dipoles from cycloisomerization/1,2-carbene transfer/ring opening cascade reactions of readily accessible allenyl ketones bearing a cyclopropyl moiety and its cyclization with tropone. This method features an unprecedented formal [8+4] high-order cycloaddition under mild conditions for delivering structurally complex 7,7,5-tricycles in generally moderate to high yields

Image_1_Hemagglutinin expressed by yeast reshapes immune microenvironment and gut microbiota to trigger diverse anti-infection response in infected birds.tif

IntroductionThe H5N8 influenza virus is a highly pathogenic pathogen for poultry and human. Vaccination is the most effective method to control the spread of the virus right now. The traditional inactivated vaccine, though well developed and used widely, is laborious during application and more interests are stimulated in developing alternative approaches.MethodsIn this study, we developed three hemagglutinin (HA) gene-based yeast vaccine. In order to explore the protective efficacy of the vaccines, the gene expression level in the bursa of Fabricius and the structure of intestinal microflora in immunized animals were analyzed by RNA seq and 16SrRNA sequencing, and the regulatory mechanism of yeast vaccine was evaluated.ResultsAll of these vaccines elicited the humoral immunity, inhibited viral load in the chicken tissues, and provided partial protective efficacy due to the high dose of the H5N8 virus. Molecular mechanism studies suggested that, compared to the traditional inactivated vaccine, our engineered yeast vaccine reshaped the immune cell microenvironment in bursa of Fabricius to promote the defense and immune responses. Analysis of gut microbiota further suggested that oral administration of engineered ST1814G/H5HA yeast vaccine increased the diversity of gut microbiota and the increasement of Reuteri and Muciniphila might benefit the recovery from influenza virus infection. These results provide strong evidence for further clinical use of these engineered yeast vaccine in poultry. </p

Data_Sheet_1_Recombinant hemagglutinin displaying on yeast reshapes congenital lymphocyte subsets to prompt optimized systemic immune protection against avian influenza infection.docx

IntroductionProphylactic vaccination is regarded as the most effective means to control avian flu infection. Currently, there is a need for a universal vaccine that provides broad and long-lasting protection against influenza virus. Meanwhile, although yeast-based vaccines have been used in clinic, studies are still required to further understand the molecular mechanism of yeast-based vaccines under physiological conditions.MethodsWe generated a yeast-based vaccine against influenza hemagglutinin (HA) of H5, H7 and H9 using surface displaying technology and evaluated the protective efficacy of chickens after exposure to H9N2 influenza virus.ResultsOral yeast vaccine provided less clinical syndrome, reduced viral loading and alleviated airway damage significantly. Compared to the commercial inactivated vaccine, yeast vaccine stimulated the activation of splenic NK and APCs cells and boosted TLR7-IRF7-IFN signaling in spleen. Meanwhile, γδ T cells in the bursa of Fabricius were activated and the innate lymphoid cells (ILCs) in the bursa of Fabricius promoted the CILPs to differentiate to ILC3 cells in oral yeast birds. Moreover, the reshaped gut microbiota and a suppressed Th17-IL17-mediated inflammation in intestine was observed in oral yeast chickens, which might facilitate the recovery of intestinal mucosal immunity upon virus infection. Collectively, our findings suggest that oral yeast based multivalent bird flu vaccines provide an attractive strategy to update host defense function via reshapes of multi-systemic immune homeostasis.</p