Latest ArticlesHerein, we report the migratory hydroarylation of unactivated alkenes with aryl iodides using native and weakly coordinating amide directors under mild conditions. Synergistic coordination of the monodentate directing group and the ligand enable the highly regioselective migratory hydroarylation via a chain walking process to form the thermodynamically stable five-membered nickelacyle intermediate. The protocol provides a variety of valuable α-aryl-substituted alkylamine products, and exhibited good functional group tolerance. The modification of bioactive compounds such as fenofibrate and indomethacin further highlights the synthetic value of this protocol.
Herein, we report the NHC-Ru catalyst system that realizes the chemo-selective transformation of ketones with methanol. By simply changing the base, a broad range of structurally diverse ketones, could be selectively and efficiently converted to the corresponding β-methylated secondary alcohols or secondary alcohols. Remarkably, this catalytic system was very effective for the synthesis of bio-related molecules and deuterated alcohols, as well as the three-component coupling between methyl ketones, primary alcohols, and methanol. The reaction mechanism was further revealed by experiment and DFT mechanistic investigations.
Sulfidation of zero-valent iron (ZVI) has attracted broad attention in recent years for improving the sequestration of contaminants from water. However, sulfidated ZVI (S-ZVI) is mostly synthesized in the aqueous phase, which usually causes the formation of a thick iron oxide layer on the ZVI surface and hinders the efficient electron transfer to the contaminants. In this study, an alcohothermal strategy was employed for S-ZVI synthesis by the one-step reaction of iron powder with elemental sulfur. It is found that ferrous sulfide (FeS) with high purity and fine crystallization was formed on the ZVI surface, which is extremely favorable for electron transfer. Cr(Ⅵ) removal experiments confirm that the rate constant of S-ZVI synthesized by the alcohothermal method was 267.1- and 5.4-fold higher than those of un-sulfidated ZVI and aqueous-phase synthesized S-ZVI, respectively. Systematic characterizations proved that Cr(Ⅵ) was reduced and co-precipitated on S-ZVI in the form of a Fe(Ⅲ)/Cr(Ⅲ)/Cr(Ⅵ) composite, suggesting its environmental benignancy.
TiO2-based films are one of the most attractive photocatalysts owing to their highly cost-effective properties. Nevertheless, most TiO2-based photocatalytic films for dye degradation are in the form of robust films (without flexibility), TiO2 coatings on carbon matrix (with leakage risk), or surface-covered TiO2 hybrids (not favorite to contact with external molecules). Therefore, the development of durable and highly efficient TiO2 photocatalytic films for dye degradation is still needed. Here, we fabricated soft photocatalytic hybrid membranes (TANFs) from TiO2 nanotubes (TiNT) and aramid nanofiber (ANF) by a facile vacuum filtration process. The similar morphology and dimension of TiNT and ANF enable them intricately intertwine with each other in the membrane network. Under an appropriate mixing ratio, the TANF exhibited significantly improved optical and mechanical properties. When used for dye degradation, the membrane showed excellent photocatalytic performance and could keep stable activity and integrated state for repeated usage.
Pyrite-type sulfides (PTS) exhibit promising intrinsic activities for oxygen reduction and evolution reactions (ORR/OER). However, their poor electrical conductivities may limit the charge transfer rate to inevitably lower activity. Here, yolk-shell structured cobalt-pyrite nanospheres (CoS2 YSS) are prepared and modified with amino groups as nucleation sites for coupling highly-conductive needle-like nitrogen-doped carbon via a facile solvothermal method (CoS2 YSS@NC). The as-marked CoS2 YSS@NC-0.5 shows a gap between yolk and shell, and an obvious exterior layer of grafted NC, which can provide an integrated structure, an interior place, and three exposed surfaces on CoS2. CoS2 YSS@NC-0.5 reveals higher ORR activity (half-wave potential of 0.88 V) and methanol resistance than commercial Pt/C. Due to in-situ formation of highly-active CoOOH, CoS2 YSS@NC-0.5 shows a better overpotential (244 mV at 10 mA/cm2) and Tafel slope (135 mV/dec) than RuO2. Zinc-air battery with CoS2 YSS@NC-0.5 air-cathode exhibits good open circuit potential (1.44 V), specific capacity (772.5 mAh/g) and cycling stability. Needle-like NC layer coated on the yolk-shell structure of CoS2 effectively lowers the charge transfer resistance to obtain extraordinary ORR/OER activities. It indicates that the integration of highly-conductive carbon onto pyrite-type sulfides is an effective strategy to acquire durable bifunctional ORR/OER catalysts.
Anode free lithium metal batteries (AF-LMBs) have conspicuous advantages both in energy density and the compatibility of battery manufacturing process. However, the limited cycle life of AF-LMBs is a crucial factor hindering its practical application. Fluorinated or nitride artificial inorganic solid electrolyte interphase (SEI) has been found as an effective method to prolong the lifespan of AF-LMBs. Herein, by investigating the impact of nano-sized inorganic gradient layers (LiF or Li3N) on initial Li deposition behavior, we notice that the Li+ diffusion barrier and the deposition morphology are highly depended on the thickness of inorganic layers. Thicker protective layers cause larger overpotential as well as more aggregated Li+ distribution. This study reveals that the ideal SEI should be synthesized thin and uniformly enough and uncontrollable artificial SEI can cause damage to the lifespan of AF-LMBs.
Chemodynamic therapy (CDT) combined with dual phototherapy (photothermal therapy (PTT) and photodynamic therapy (PDT)) is an efficient way to synergistically improve anti-tumor efficacy. However, the combination of multiple modes often makes the composition of the system more complex, which is not conducive to clinical application. In this study, a dual phototherapy ligand carboxyl-modified Aza-BODIPY (BOD-COOH) and metal active center Cu2+ were used to construct multiple-modes metal-photosensitizer nanoparticles (BOD-Cu NPs) via one-step coordination self-assembly for combination therapy of CDT/PDT/PTT. In order to improve delivery efficiency, the targeted hydrophilic molecule pyridine-modified glucose derivative (G-Py) was synthesized and coated onto the BOD-Cu NPs to form a glycosylated nano metal-photosensitizer BOD-Cu@G by electrostatic interaction. The Cu2+ in BOD-Cu@G could not only be used as a coordination node for metal-driven self-assembly but also consume intracellular glutathione (GSH), and then catalyze Fenton-like reaction to generate hydroxyl radical (·OH) for CDT. In vitro and in vivo studies revealed that BOD-Cu@G could achieve excellent anti-tumor efficiency by CDT-enhanced dual phototherapy.
A copper(Ⅰ)-catalyzed diastereodivergent addition of phosphinothioates (HP(S)ROR') to α, β-unsaturated thioamides is disclosed, which constructs vicinal P-chiral and C-chiral centers in generally high diastereo- and enantioselectivities. In this reaction, the kinetic resolution of HP(S)ROR' occurs, which affords (R)-HP(S)PhOMe in high enantioselectivity in the addition with (R, R)-Ph-BPE as the ligand. It is found through control experiment that dual "soft-soft" interaction, indicated by both 1H and 31P NMR experiments, is indispensable in the present reaction. The first "soft-soft" interaction between copper(Ⅰ) catalyst and HP(S)ROR' enables facile deprotonation to generate nucleophilic [Cu]-SPROR' species. The second one between the [Cu]-SPROR' species and α, β-unsaturated thioamides facilitated the nucleophilic addition. Finally, both Michael adducts and (R)-HP(S)PhOMe are easily converted to synthetically useful compounds.
Lithium-sulfur batteries (LSBs) boasting remarkable energy density have garnered significant attention within academic and industrial spheres. Nevertheless, the progression of LSBs remains constrained by the languid redox kinetics intrinsic to sulfur and the pronounced shuttle effect induced by lithium polysulfides (LiPSs), which seriously affecting the energy density, cycling life and rate capacity. The conceptualization and implementation of catalytic materials stand acknowledged as a propitious stratagem for orchestrating kinetic modulation, particularly in excavating the conversion of LiPSs and has evolved into a focal point for disposing. Among them, chalcogenide catalytic materials (CCMs) have shown satisfactory catalytic effects ascribe to the unique physicochemical properties, and have been extensively developed in recent years. Considering the lack of systematic summary regarding the development of CCMs and corresponding performance optimization strategies, herein, we initiate a comprehensive review regarding the recent progress of CCMs for effective collaborative immobilization and accelerated transformation kinetics of LiPSs. Following that, the modulation strategies to improve the catalytic activity of CCMs are summarized, including structural engineering (morphology engineering, surface/interface engineering, crystal engineering) and electronic engineering (doping and vacancy, etc.). Finally, the application prospect of CCMs in LSBs is clarified, and some enlightenment is provided for the reasonable design of CCMs serving practical LSBs.
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