Molten salt CO2 capture and electrochemical transformation (MSCC-ET) process is a desirable method to prepare various carbide materials. In this study, (NbTaTiZrHf)C high-entropy carbide (HEC) nano-sized particles were synthesized by MSCC-ET process, utilizing mixed metal oxides as the raw materials and LiCl-CaCl2-KCl molten salt system as electrolyte. To explore the reactions occurring on the molten salt and electrode surface in the MSCC-ET process, the phase structure, elemental valence states and microstructure of (NbTaTiZrHf)C HEC powders were thoroughly investigated through XRD, XPS, SEM, TEM. The supercapacitor performance was measured by electrochemical workstations. The results reveal that HEC powders display a clustered morphology, with particle sizes ranging from 20 to 100 nm. The specific capacitance reaches 63.5 F/g with a scan rate of 100 mV/s in 1 mol/L KOH solution. Remarkably, even after 2500 full charge-discharge cycles, the capacity retention remains at an impressive 89.84 %. The Tafel slope for (NbTaTiZrHf)C registers at a value of 61 mV/dec. This research provides a foundation for the preparation of various carbide materials in an environmentally friendly process.
Nanoscale face-centered cubic (FCC) (NbTaTiZrHf)C high-entropy carbide (HEC) powders were prepared by the molten salt CO2 capture and electrochemical transformation method. The (NbTaTiZrHf)C HEC have a cluster-like structure, with the size of the clusters is less than 500 nm and the diameter of the small particles on the clusters is about 50 nm. The phase transformation from the metal oxides to HEC under different electrolysis durations was investigated by XRD SEM TEM, and XPS. The results show that the electrochemical reduction process of Nb2O5, Ta2O5, and TiO2 is carried out step by step, while the electrochemical reduction process of ZrO2 and HfO2 is one-step electrochemical reduction processes to metals. The carbide is eventually formed by the solution reaction of the cathode carbon deposited and the electro-deoxidation metals. This approach offers a novel pathway for the environmentally sustainable synthesis of high-entropy carbides.
Easy injection, long-lasting barrier, and drug loading are the critical properties of submucosal injection materials for endoscopic surgery. However, conventional injectable polymers face challenges in simultaneously attaining these properties due to the inherent conflict between injectability and in situ stability. Here, a multi-arm star polymer hydrogel (denoted as βCP hydrogel) with long-lasting submucosal barrier (exceeding 120 min), rapid hemostasis, and sustained antibacterial properties is successfully developed by grafting poly(oligo(ethylene glycol) methyl ether methacrylate) (PEGMA) side-chains from β-CD via atom transfer radical polymerization (ATRP). During the onset of shearing, βCP hydrogel experiences the unwinding of polymer side-chains between neighboring star polymers, which facilitates the process of endoscopic injectability. After submucosal injection, βCP hydrogel undergoes the winding of polymer side-chains, thereby establishing a long-lasting barrier cushion. Meanwhile, owing to its distinctive structures with a hydrophobic inner cavity and an outer layer of hydrophilic polymer side-chains, βCP hydrogel enables simultaneous loading and on-demand release of diverse categories of drugs. This unique performance can adapt to the diverse demands during different stages of wound healing in a porcine endoscopic surgery model. These results indicate an appealing prospect for new application of star polymers as a good submucosal injection material in endoscopic treatments.
Detection of chiral molecules in a high-efficiency way is very important to meet the demands for chiral analysis in drug testing, asymmetric synthesis, etc. Herein, we have developed a novel route to realize the rapid determination of concentration and configuration of primary amine-based chiral molecules. An aldehyde functionalized acid & base-sensitive fluorane dye (R-C) was used as the active agent to be reacted with the chiral molecules through an aldimine condensation reaction. After the mixing operation, concentration and configuration of the detected chiral molecule could be facilely read from the UV-vis absorption spectra and CD spectra, respectively.
An efficient iodine-mediated oxythiolation of o-vinylanilides with disulfides was developed. By virtue of this method, a series of thio-tethered benzoxazine derivatives were synthesized in good to excellent yields. The reaction features high yields, is metal-free, and has a wide substrate scope.
The inflammasome-mediated cleavage of gasdermin D (GSDMD) causes pyroptosis and inflammatory cytokine release to control pathogen infection, but how pathogens evade this immune response remains largely unexplored. Here we identify the known protein phosphatase PtpB from Mycobacterium tuberculosis as a phospholipid phosphatase inhibiting the host inflammasome-pyroptosis pathway. Mechanistically, PtpB dephosphorylated phosphatidylinositol-4-monophosphate and phosphatidylinositol-(4,5)-bisphosphate in host cell membrane, thus disrupting the membrane localization of the cleaved GSDMD to inhibit cytokine release and pyroptosis of macrophages. Notably, this phosphatase activity requires PtpB binding to ubiquitin. Disrupting phospholipid phosphatase activity or the ubiquitin-interacting motif of PtpB enhanced host GSDMD-dependent immune responses and reduced intracellular pathogen survival. Thus, pathogens inhibit pyroptosis and counteract host immunity by altering host membrane composition.
An electrochemical amino-azidation of 2-aminostyre ne with sodium azide(NaN 3 ) was developed,which can be carried out smoothly in water under metal-free condition,affording a series of 3-azido indolines with high yields.
A metal-free electrochemical intramolecular C(sp2)-H amination using iodine as a mediator was developed. This method enables a switchable synthesis of indoline and indole derivatives, respectively, from easily available 2-vinyl anilines.
Highly enantioselective Friedel–Crafts alkylation of pyrroles with 2-enoyl-pyridine N-oxides in water/chloroform (10:1) was developed under catalysis of Lewis acid. The Friedel–Crafts alkylation products can be obtained in high yields and excellent enantioselectivities. Moreover, several control experiments were carried out to study the reaction mechanism.
A copper-catalyzed 1,1-difunctionalization of terminal alkynes was achieved via a three-component reaction, providing a variety of vinyl sulfones with good yields and excellent chemo- and stereoselectivity. Preliminary mechanistic studies indicated that the reaction probably underwent a Cu-catalyzed formal C–H insertion to produce an allene intermediate, which was then trapped by a sulfonyl anion to give the corresponding product.
An interesting and recyclable activated carbon/water catalytic system for efficient synthesis of pyrrolo[1,2-a]quinoxaline derivatives was developed.The intramolecular C-N and C-C bond can be easily constructed in water under mild condition.This reaction features a broad substrate scope,a good tolerance to water and air,metal-free,additive-free and redox reagent-free.
A copper(I)-catalyzed geminal difunctionalization of terminal alkynes was developed via a carbene migratory insertion and an addition of a sulfonyl anion to the triple bond at the same time under mild reaction conditions, providing a variety of vinyl sulfones with good yields and excellent stereoselectivities.
An environmentally friendly diamination was developed in the presence of TMDAI/H2O2 with water as the only by-product. A series of 3-amino indolines can be obtained in good to excellent yields. The reaction conditions are very mild and no any organic solvent or metal was involved in the reaction.
An efficient synthesis of benzimidazoles was developed by virtue of a recycled palladium catalyzed hydrogen transfer. The reaction can be carried out smoothly under mild conditions to give rise to a variety of benzimidazoles with good to excellent yields. The palladium catalyst could be recovered easily and reused six times with great catalytic activity.
An iodine-mediated decarboxylative cyclization was developed from α-amino acids and 2-methyl quinolines under metal-free conditions, affording a variety of imidazo[1,5-a]quinolines with moderate to good yields.
An unusual and highly effective asymmetric annulation of nitrosoarenes with hydroxymaleimides catalyzed by a chiral bifunctional amine squaramide catalyst has been disclosed. A wide range of highly fused chiral N-hydroxyindolines with two consecutive quaternary stereocenters and multifunctional groups were directly and effectively prepared in excellent yields (up to >99%) with complete regioselective cyclization and excellent stereoselectivities (up to >99:1 dr and >99% ee). The efficiency and potentials of the new reaction and the target chiral entities were well demonstrated by delicate transformations into a series of new chiral indolines.
Chiral diamine catalysts 11a-e derived from α,α-diphenyl prolinol were prepared and successfully applied to the Michael addition of aromatic oximes to α,β-unsaturated aldehydes in mediocre to good yields (up to 78%) and good to high enantioselectivities (up to 93% ee).
A copper-catalyzed S-methylation of sulfonyl hydrazides with TBHP for the synthesis of methyl sulfones in water.