Latest ArticlesGlycolysis inhibition can effectively block the energy supply and interrupt tumorigenesis in many types of cancers. However, when glycolysis is inhibited, tumor cells will break down glutamine as the raw material for the replenishment pathway to maintain the tricarboxylic acid cycle ensuring energy supply, therefore inducing ineffective interruption of metabolic. Herein, we designed glutamine transporter antagonist l-γ-glutamyl-p-nitroanilide (GPNA) loaded and 4T1 cancer cell membrane coated iridium oxide nanoparticles (IrO2-GPNA@CCM) to realize a comprehensive inhibition of tumor energy supply which synergistically mediated by glycolysis and glutamine cycle. IrO2 NPs were used to catalyze the O2 generation by facilitating the decomposition of endogenous H2O2 in tumor cells, which further downregulated the expression of HIF-1α and PI3K/pAKT to interrupt the generation of lactate. Meanwhile, the loaded GPNA was released under NIR irradiation to bind to alanine-serine-cysteine transporter (ASCT2) for glutamine uptake suppression, therefore realizing the comprehensive dysfunction of cell metabolism. Moreover, both in vitro and in vivo results convinced the thorough energy inhibition effect based on IrO2-GPNA@CCM NPs, which provided an inspiring strategy for future construction of tumor therapeutic regimen.
Organics present significant prospects as environmentally friendly and sustainable electrode materials for potassium ion batteries (PIBs) because of their abundant, recyclable and highly customizable characteristics. However, small molecular organics are easily solubilized in organic electrolytes, resulting in a low capacity and poor stability. Herein, the folic acid-based supermolecules (SM-FAs) are successfully prepared by a hydrothermal assisted self-assembly strategy. Due to multi-locus hydrogen bonds (HBs) and the cyclized π-conjugated interactions, the structural stability of SM-FAs has been significantly improved, and the solubility in carbonate electrolytes has been effectively inhibited. As an anode for PIB, the SM-FA-6 sample exhibits a large capacity (206 mAh/g at 50 mA/g) and an outstanding cycle stability (capacity retention of 91% after 1000 cycles at 50 mA/g). More impressively, an integrative storage mechanism which combines both the general enolization reaction between C=O groups and K+, and the atypical π–K+ interaction within the assembled conjugation framework, is unraveled for potassium ion accumulation. It is envisioned that this facile self-assemble strategy opens up a promising avenue to modulate the stability of small molecular organic electrodes with enhanced storage capacity.
Most porous conductive frameworks are highly anisotropic in their structures thus leading to anisotropic charge transport. Here we report a supramolecular self-assembly which is constructed by intermolecular hydrogen bonding and π···π interactions. This material features a chiral, porous, cubic framework structure with π-stacked helical columns along all of the three Cartesian coordinates. As a result, isotropic charge transport with an electrical conductivity (σ) of 2.1 × 10–7 S/cm is achieved. By achieving isotropic charge transport in a π-stacked supramolecular assembly, these results provide a new type of isotropic conductive framework materials alternative to conductive metal-organic frameworks (MOFs).
We report here a generic, green synthesis of 17 valuable syn-aryl-(2S,3R)-2–chloro-3–hydroxy esters (syn-(2S,3R)-1) in 73%-99% isolated yields along with 6.1:1–83:1 dr and 31%~ > 99% ee, through dynamic reductive kinetic resolution of racemic aryl α–chloro β-keto esters (2) catalyzed by an engineered ketoreductase which was obtained via epPCR-based directed evolution. The hectogram scale synthesis of syn-(2S,3R)-1b at a substrate concentration of 120 g/L showcased the application potential of the biocatalytic method developed presently.
Selenium, an element belonging to the same group in the periodic table as sulfur, has a high electronic conductivity (1 × 10−5 S/cm) and a high volumetric energy density (3253 mAh/cm3), which is a prospective cathode material for high-energy all-solid-state rechargeable batteries. However, its wide use is hindered by large volume expansion and low utilization rate. In this work, Se-infused nitrogen-doped hierarchical meso-microporous carbon composites (Se/NHPC) are prepared by a melt-diffusion process. Amorphous Se is uniformly dispersed in meso-micropores of NHPC with a high mass loading of 81%. All-solid-state Li-Se batteries fabricated by using Se/NHPC as the cathode, a Li-In alloy as the anode, and Li6PS5Cl as the solid-state electrolyte, deliver a highly reversible capacity of 621 mAh/g (92% of theoretical capacity), a good rate capability and a high capacity retention value of 80.9% after 100 cycles. It is found that the capacity decay of Se cathode is mainly related to the interfacial degradation and the separation of Se from the carbon substrate, as suggested by the continuous increase of interfacial resistance and the structural transformation from amorphous Sen chains to Se8 rings initial discharge/charge cycle and then to the trigonally crystalline Se chains structure after the long-term cycles.
Hydrogen evolution from water electrolysis has become an important reaction for the green energy revolution. Traditional precious metals and their compounds are excellent catalysts for producing hydrogen; however, their high cost limits their large-scale practical application. Therefore, the development of affordable electrocatalysts to replace these precious metals is important. Transition metal phosphides (TMPs) have shown remarkable performance for hydrogen evolution and garnered considerable interest in the field of electrolysis. Based on the detailed introduction of TMPs in previous studies, we have systematically summarized the preparation methods, improvement methods, and development opportunities of TMPs and proposed “stimulatory factors” as a fundamental factor affecting the performance of TMPs herein. As the core of this research, “stimulatory factors” can provide numerous solutions to improve the performance of TMP materials and provide a good starting point for TMP research.
Two dimensional (2D) materials are promising gas sensing materials, but the most of them need to be heated to show promising sensing performance. Sensing structures with high sensing performance at room-temperature are urgent. Here, another 2D material, violet phosphorus (VP) nanoflake is investigated as gas sensing material. The VP nanoflakes have been effectively ablated to have layers of 1–5 layers by laser ablation in glycol. The VP nanoflakes are combined with graphene to form VP/G heterostructures-based NO sensor. An ultra-high gauge factor of 3 × 107 for ppb-level sensing and high resistance response of 59.21% with ultra-short recovery time of 6s for ppm-level sensing have been obtained. The sensing mechanism is also analysed by density functional theory (DFT) calculations. The adsorption energy of VP/G is calculated to be −0.788 eV, resulting in electrons migration from P to N to form a P−N bond in the gap between VP and graphene sheet. This work provides a facile approach to ablate VP for mass production. The as-produced structures have also provided potential gas sensors with ultrasensitive performance as ppb-level room-temperature sensors.
Uranium is the main fuel of nuclear power and elimination uranium from nuclear wastewater is significant both in environmental protection and fuel recycle. Here we report for the first time the synthesis of carbon dots/polyurethane (CDs/PU) composite materials for the photoinduced elimination of uranium from water. Irradiated with visible light, CDs/PU could eliminate uranium efficiently with the generation of (UO2)O2·2H2O as solid products in air. The further investigated mechanism showed that the addition of CDs/PU could produce more H2O2 under visible light, which reacted with uranyl ions to form (UO2)O2·2H2O. Importantly, the sponge-like CDs/PU could be easily removed from water with high reusability as the elimination efficiency remained above 95% after 5 cycles. CDs/PU also displayed good selectivity in the presence of other metal ions. Our work affords exciting strategies for developing photocatalysts and eliminating uranium from water.
Transition metal sulfides are demonstrated to play an increasingly important role in boosting the deployment of ecofriendly electrocatalytic energy conversion technologies. It is also widely recognized that the introduction of vacancies is now becoming an important and valid approach to promote the electrocatalytic performance. In this review, the significance of sulfur vacancies on the enhancement of catalytic performance via four main functionalities, including tuning the electronic structure, tailoring the active sites, improving the electrical conductivity, and regulating surface reconstruction, is comprehensively summarized. Many effective strategies for the sulfur vacancy engineering, such as plasma treatment, heteroatom doping, and chemical reduction are also comprehensively provided. Subsequently, recent achievements in sulfur vacancy fabrication on various hotspot electrocatalytic reactions are also systematically discussed. Finally, a summary of the recent progress and challenges of this interesting field are organized, which hopes to guide the future development of more efficient metal sulfide electrocatalysts.
Herein, copper-catalyzed 1,4-protosilylation and 1,4-protoborylation of enynic orthoesters have been developed. The enynic orthoesters as precursors of unstable enynic esters were applied to produce the functionalized 2, 3-allenoate products. Meanwhile, the asymmetric 1,4-protosilylation of enynic orthoesters with PhMe2Si-Bpin was also studied. The chiral monopyridine imidazoline ligand was efficient to provide the asymmetric 1,4-protosilylation products with high enantioselectivity.