RESUMEN
Substrate selectivity is one of the most attractive features of natural enzymes from their "bind-to-catalyze" working flow and is thus a goal for the development of synthetic enzyme mimics that mediate abiotic transformations. However, despite the recent success in the preparation of substrate-selective enzyme mimics based on single-chain nanoparticles, examples extending such selectivity into living systems have been absent. In this article, we report the in cellulo substrate selectivity of an enzyme-mimicking macromolecular catalyst based on a cationic dense-shell nanoparticle (DSNP) scaffold. With a systematic study on DSNP's structure-activity relationship, we demonstrate that the DSNP has excellent membrane affinity that is governed by several contributing factors, namely, charge density, type of charge, and particle size, and the best-performing phosphonium-rich DSNP can be used as a membrane-embedded catalyst (MEC) for efficient on-membrane synthesis. Importantly, the DSNP catalyst retains its selectivity toward lipophilic and anionic substrates when working as an MEC for on-membrane ligation. The usefulness of such substrate selectivity and on-membrane catalysis strategy was exemplified with several molecules of interest with low cell permeability and anionic nature, which were successfully transported into eukaryotic cells by after their formation directly on the cell membrane.
Asunto(s)
Nanopartículas , Relación Estructura-Actividad , CatálisisRESUMEN
Magnesium-ion batteries (MIBs) are emerging as potential next-generation energy storage systems due to high security and high theoretical energy density. Nevertheless, the development of MIBs is limited by the lack of cathode materials with high specific capacity and cyclic stability. Currently, transition metal sulfides are considered as a promising class of cathode materials for advanced MIBs. Herein, a template-based strategy is proposed to successfully fabricate metal-organic framework-derived in-situ porous carbon nanorod-encapsulated CuS quantum dots (CuS-QD@C nanorods) via a two-step method of sulfurization and cation exchange. CuS quantum dots have abundant electrochemically active sites, which facilitate the contact between the electrode and the electrolyte. In addition, the tight combination of CuS quantum dots and porous carbon nanorods increases the electronic conductivity while accelerating the transport speed of ions and electrons. With these architectural and compositional advantages, when used as a cathode material for MIBs, the CuS-QD@C nanorods exhibit remarkable performance in magnesium storage, including a high reversible capacity of 323.7 mAh g-1 at 100 mA g-1 after 100 cycles, excellent long-term cycling stability (98.5 mAh g-1 after 1000 cycles at 1.0 A g-1 ), and satisfying rate performance (111.8 mA g-1 at 1.0 A g-1 ).
RESUMEN
Magnesium-ion batteries (MIBs) are considered strong candidates for next-generation energy-storage systems owing to their high theoretical capacity, divalent nature and the natural abundancy of magnesium (Mg) resources on Earth. However, the development of MIBs has been mainly limited by the incompatibility of Mg anodes with several Mg salts and conventional organic-liquid electrolytes. Therefore, one major challenge faced by MIBs technology lies on developing safe electrolytes, which demonstrate appropriate electrochemical voltage window and compatibility with Mg anode. This review discusses the development of MIBs from the point-of-view of the electrolyte syntheses. A systematic assessment of promising electrolyte design strategies is proposed including liquid and solid-state electrolytes. Liquid-based electrolytes have been largely explored and can be categorized by solvent-type: organic solvent, aqueous solvent, and ionic-liquids. Organic-liquid electrolytes usually present high electrochemical and chemical stability but are rather dangerous, while aqueous electrolytes present high ionic conductivity and eco-friendliness but narrow electrochemical stability window. Some ionic-liquid electrolytes have proved outstanding performance but are fairly expensive. As alternative to liquid electrolytes, solid-state electrolytes are increasingly attractive to increase energy density and safety. However, improving the ionic conductivity of Mg ions in these types of electrolytes is extremely challenging. We believe that this comprehensive review will enable researchers to rapidly grasp the problems faced by electrolytes for MIBs and the electrolyte design strategies proposed to this date.
RESUMEN
NaTi2(PO4)3 (NTP) is a promising anode material for sodium-ion batteries (SIBs). It has drawn wide attention because of its stable three-dimensional NASICON-type structure, proper redox potential, and large accommodation space for Na+. However, the inherent low electronic conductivity of the phosphate framework reduces its charge transfer kinetics, thus limiting its exploitation. Therefore, this paper proposes a material with carbon-coated porous NTP olive-like nanospheres (p-NTP@C) to tackle the issues above. Based on experimental data and theoretical calculations, the porous structure of the material is found to be able to provide more active sites and shorten the Na+ diffusion distance. In addition, the carbon coating can effectively improve the electron and Na+ diffusion kinetics. As the anode material for SIBs, the p-NTP@C olive-like nanospheres exhibit a high reversible capacity (127.3 mAh g-1 at 0.1 C) and ultrastable cycling performance (84.8% capacity retention after 10,000 cycles at 5 C). Furthermore, the sodium-ion full cells, composed of p-NTP@C anode and Na3V2(PO4)2F3@carbon cathode, also deliver excellent performance (75.7% capacity retention after 1000 cycles at 1 C). In brief, this nanostructure design provides a viable approach for the future development of long-life and highly stable NASICON-type anode materials.