Hierarchical supramolecules composed of starch-based nanocluster aggregates with light-responsive mechanical strain for remotely rapid and precise actuation.

Hierarchical supramolecular systems, characterized by nanoscale sensitivity and macroscopic tangible changes, offer promising perspectives for the design of remotely controllable, rapid, and precise actuation materials, serving as a potential substitution for non-intelligent and complex actuation switches. Herein, we reported on the disassembly of orderly and rigid starch helical covalent structures, and their subsequent reassembly into a hierarchical supramolecular gel composed of nanocluster aggregates, integrating supramolecular interactions of three different scales. The incorporation of photo-sensitive FeIIITA, a complex of trivalent iron ions and tannic acid, significantly enhances the photo-responsive strain capacity of the hierarchical supramolecular gel. The supramolecular gel exhibits its features in a rapid light-responsive rate of hardness and viscosity, enabling the actuation of objects within 22 s under light exposure when employed as a remote actuation switch. Meanwhile, this actuation mechanism of the hierarchical supramolecular gel also has a promising perspective in precise control, identifying and actuating one of the two objects in distances of 0.8 mm even smaller scales. Our work provides a reliable reference for replacing complex actuation switches with intelligent materials for remote, rapid, and accurate actuation, and offers valuable insights for actuation in harsh and vacuum outdoor environments.

In situ growth of Mn3O4 nanoparticles on accordion-like Ti3C2Tx MXene for advanced aqueous Zn-Ion batteries.

Manganese-based cathodes are competitive candidates for state-of-the-art aqueous zinc-ion batteries (AZIBs) because of their easy preparation method, sufficient nature reserve, and environmental friendliness. However, their poor cycle stability and low rate performance have prevented them from practical applications. In this study, Mn3O4 nanoparticles were formed in situ on the surface and between the interlayers of Ti3C2Tx MXene, which was pretreated by the intercalation of K+ ions. Ti3C2Tx MXene not only provides abundant active sites and high conductivity but also hinders the structural damage of Mn3O4 during charging and discharging. Benefiting from the well-designed K-Ti3C2@Mn3O4 structure, the battery equipped with the K-Ti3C2@Mn3O4 cathode achieved a maximum specific capacity of 312 mAh/g at a current density of 0.3 A/g and carried a specific capacity of approximately 120 mAh/g at a current density of 1 A/g, which remained stable for approximately 500 cycles. The performance surpasses that of most reported Mn3O4-based cathodes. This study pioneers a new approach for building better cathode materials for AZIBs.

One-pot co-crystallized hexanal-loaded ZIF-8/quaternized chitosan film for temperature-responsive ethylene inhibition and climacteric fruit preservation.

Controlling ethylene production and microbial infection are key factors to prolong the shelf life of climacteric fruit. Herein, a nanocomposite film, hexanal-loaded ZIF-8/CS (HZCF) with "nano-barrier" structure, was developed by a one-pot co-crystallized of ZIF-8 in situ growth on quaternized chitosan (CS) and encapsulation of hexanal into ZIF-8 via microporous adsorption. The resultant film realized the temperature responsive release of hexanal via the steric hindrance and hierarchical pore structure as "nano-barrier", which can inhibit ethylene production in climacteric fruit on demand. Based on this, the maximum ethylene inhibition rate of HZCF was up to 52.6 %. Meanwhile, the film exhibits excellent antibacterial, mechanical, UV resistance and water retention properties, by virtue of the functional synergy between ZIF-8 and CS. Contributed to the multifunctional features, HZCF prolonged the shelf life of banana and mango for at least 16 days, which is 8 days longer than that of control fruit. More strikingly, HZCF is washable and biodegradable, which is expected to replace non-degradable plastic film. Thus, this study provides a convenient novel approach to simplify the encapsulation of active molecule on metal-organic frameworks (MOFs), develops a packaging material for high-efficient freshness preservation, and helps to alleviate the survival crisis caused by food waste.

Self-triggered carboxymethyl chitosan hydrogel for the convenient sustained release of ClO2 gas with environmental stability and long-term antimicrobial effect.

Challenges associated with the storage and uncontrolled release of ClO2 gas present significant hurdles to its practical application. Herein, a clever strategy for self-triggering the sustained release of chlorine dioxide (ClO2) gas is proposed by crosslinking carboxymethyl chitosan (CMCS) with Zn2+ to construct a novel CMCS-Zn@NaClO2 gel with eco-friendly, environmental stability, and convenient, long term, and efficient antibacterial activity. The precursor (NaClO2) in the CMCS solution was alkaline and triggered by the acidic Zn(NO3)2·6H2O solution to achieve sustained self-triggering ClO2 release. The ClO2 gas self-release could be sustained on demand at different temperatures for at least 20 days due to the environmental structure stability of the gel. The hydrogels showed an increase in pore size after sustained release. Molecular dynamics simulations showed the spontaneous release of ClO2 gas at room temperature and the contraction of the CMCS agglomeration, which were consistent with the macroscopic behaviour. The gel displayed a long-acting and high antibacterial efficacy, resulting in a bacteria-killing rate of over 99.9% (inhibitory concentrations of 2.5 mg mL-1 against E. coli and 0.16 mg mL-1 against S. aureus). The hydrogels could effectively extend the shelf life of fruits and demonstrated an excellent wide range of antibacterial properties. This work provides a new approach to solving the storage difficulty of ClO2 gas and offers a fresh perspective on the design of materials with convenient self-triggering release by a precursor, as well as the relationship between the material microstructure and sustained-release behaviour.

Interlayer Engineering of VS2 Nanosheets via In Situ Aniline Intercalative Polymerization toward Long-Cycling Magnesium-Ion Batteries.

Rechargeable magnesium batteries (RMBs) show great potential in large-scale energy storage systems, due to Mg2+ with high polarity leading to strong interactions within the cathode lattice, and the limited discovery of functional cathode materials with rapid kinetics of Mg2+ diffusion and desirable cyclability retards their development. Herein, we innovatively report the confined synthesis of VS2/polyaniline (VS2/PANI) hybrid nanosheets. The VS2/PANI hybrids with expanded interlayer spacing are successfully prepared through the exfoliation of VS2 and in situ polymerization between VS2 nanosheets and aniline. The intercalated PANI increases the interlayer spacing of VS2 from 0.57 to 0.95 nm and improves its electronic conductivity, leading to rapid Mg-ion diffusivity of 10-10-10-12 cm2 s-1. Besides, the PANI sandwiched between layers of VS2 is conducive to maintaining the structural integrity of electrode materials. Benefiting from the above advantages, the VS2/PANI-1 hybrids present remarkable performance for Mg2+ storage, showing high reversible discharge capacity (245 mA h g-1 at 100 mA g-1) and impressive long lifespan (91 mA h g-1 after 2000 cycles at 500 mA g-1). This work provides new perspectives for designing high-performance cathode materials based on layered materials for RMBs.

Controlled Synthesis of Flower-like Hierarchical NiCo-Layered Double Hydroxide Integrated with Metal-Organic Framework-Derived Co@C for Supercapacitors.

Layered double hydroxides (LDHs) have come to the foreground recently, considering their unique layered structure and short ion channels when they act as electrode materials for supercapacitors (SCs). However, due to their poor rate and cycle performance, they are not highly sought after in the market. Therefore, a flower-like hierarchical NiCo-LDH@C nanostructure with flake NiCo-LDH anchored on the carbon skeleton has emerged here, which is constructed by calcination and hydrothermal reaction and applying flake ZIF-67 as a precursor. In this structure, NiCo-LDH grows outward with abundant and homogeneously distributed Co nanoparticles on Co@C as nucleation sites, forming a hierarchical structure that is combined tightly with the carbon skeleton. The flower-like hierarchical nanostructures formed by the composite of metal-organic frameworks (MOFs) and LDHs have successfully enhanced the cycle and rate performance of LDH materials on the strength of strong structural stability, large specific surface area, and unique cooperative effect. The NiCo-LDH@C electrode displays superb electrochemical performance, with a specific capacitance of 2210.6 F g-1 at 1 A g-1 and 88.8% capacitance retention at 10 A g-1. Furthermore, the asymmetric supercapacitor (ASC) constructed with NiCo-LDH@C//RGO reveals a remarkable energy density of 45.02 W h kg-1 with a power density of 799.96 W kg-1. This project aims to propose a novel avenue to exploit NiCo-LDH electrode materials and provide theory and methodological guidance for deriving complex structures from MOF derivatives.

Electronic structure engineering on NiSe2 micro-octahedra via nitrogen doping enabling long cycle life magnesium ion batteries.

Multivalent ion batteries have attracted great attention because of their abundant reserves, low cost and high safety. Among them, magnesium ion batteries (MIBs) have been regarded as a promising alternative for large-scale energy storage device owing to its high volumetric capacities and unfavorable dendrite formation. However, the strong interaction between Mg2+ and electrolyte as well as cathode material results in very slow insertion and diffusion kinetics. Therefore, it is highly necessary to develop high-performance cathode materials compatible with electrolyte for MIBs. Herein, the electronic structure of NiSe2 micro-octahedra was modulated by nitrogen doping (N-NiSe2) through hydrothermal method followed by a pyrolysis process and this N-NiSe2 micro-octahedra was used as cathode materials for MIBs. It is worth noting that N-NiSe2 micro-octahedra shows more redox active sites and faster Mg2+ diffusion kinetics compared with NiSe2 micro-octahedra without nitrogen doping. Moreover, the density functional theory (DFT) calculations indicated that the doping of nitrogen could improve the conductivity of active materials on the one hand, facilitating Mg2+ ion diffusion kinetics, and on the other hand, nitrogen dopant sites could provide more Mg2+ adsorption sites. As a result, the N-NiSe2 micro-octahedra cathode exhibits a high reversible discharge capacity of 169 mAh g-1 at the current density of 50 mA g-1, and a good cycling stability over 500 cycles with a maintained discharge capacity of 158.5 mAh g-1. This work provides a new idea to improve the electrochemical performance of cathode materials for MIBs by the introduction of heteroatom dopant.

Quantifying stiffness and forces of tumor colonies and embryos using a magnetic microrobot.

Stiffness and forces are two fundamental quantities essential to living cells and tissues. However, it has been a challenge to quantify both 3D traction forces and stiffness (or modulus) using the same probe in vivo. Here, we describe an approach that overcomes this challenge by creating a magnetic microrobot probe with controllable functionality. Biocompatible ferromagnetic cobalt-platinum microcrosses were fabricated, and each microcross (about 30 micrometers) was trapped inside an arginine-glycine-apartic acid-conjugated stiff poly(ethylene glycol) (PEG) round microgel (about 50 micrometers) using a microfluidic device. The stiff magnetic microrobot was seeded inside a cell colony and acted as a stiffness probe by rigidly rotating in response to an oscillatory magnetic field. Then, brief episodes of ultraviolet light exposure were applied to dynamically photodegrade and soften the fluorescent nanoparticle-embedded PEG microgel, whose deformation and 3D traction forces were quantified. Using the microrobot probe, we show that malignant tumor-repopulating cell colonies altered their modulus but not traction forces in response to different 3D substrate elasticities. Stiffness and 3D traction forces were measured, and both normal and shear traction force oscillations were observed in zebrafish embryos from blastula to gastrula. Mouse embryos generated larger tensile and compressive traction force oscillations than shear traction force oscillations during blastocyst. The microrobot probe with controllable functionality via magnetic fields could potentially be useful for studying the mechanoregulation of cells, tissues, and embryos.

Enhanced antibacterial effect and biodegradation of coating via dual-in-situ growth based on carboxymethyl cellulose.

The lack of antimicrobial effect of commercial paper coating for food packaging makes it difficult to prevent food spoilage and harms the environment by non-biodegradation. Herein, carboxymethyl cellulose (CMC) provides negatively charged sites for anchoring Ag+ and Zn2+ to grow AgNPs and ZIF-8 in situ on its molecular chains. The ZIF-8/AgNPs@CMC paper coating has excellent synergistic antibacterial activity to prolong the shelf-life of food. It not only has good thermal stability but binds closely to the paper and its adhesion force reaches 628.9 nN. Besides, the ZIF-8/AgNPs@CMC coated paper has better mechanical properties, water vapor barrier, and resists water solubility. Interestingly, due to the confinement effect of ZIF-8, the cumulative release of AgNPs after 168 h is only 2.66 % to avoid possible food safety risks. Especially, the coating can be almost biodegraded in the soil after 30 days, which provides the possibility to replace the non-biodegradable coatings in food packaging.

Enhanced Li-Ion Diffusion and Cycling Stability of Ni-Free High-Entropy Spinel Oxide Anodes with High-Concentration Oxygen Vacancies.

High-entropy oxide (HEO) is an emerging type of anode material for lithium-ion batteries with excellent properties, where high-concentration oxygen vacancies can effectively enhance the diffusion coefficient of lithium ions. In this study, Ni-free spinel-type HEOs ((FeCoCrMnZn)3O4 and (FeCoCrMnMg)3O4) were prepared via ball milling, and the effects of zinc and magnesium on the concentration of oxygen vacancy (OV), lithium-ion diffusion coefficient (DLi+), and electrochemical performance of HEOs were investigated. Ab initio calculations show that the addition of zinc narrows down the band gap and thus improves the electrical conductivity. X-ray photoelectron spectroscopy (XPS) results show that (FeCoCrMnZn)3O4 (42.7%) and (FeCoCrMnMg)3O4 (42.5%) have high OV concentration. During charge/discharge, the OV concentration of (FeCoCrMnZn)3O4 is higher than that of (FeCoCrMnMg)3O4. The galvanostatic intermittent titration technique (GITT) results show that the DLi+ value of (FeCoCrMnZn)3O4 is higher than that of (FeCoCrMnMg)3O4 during charge and discharge. All of that can improve its specific discharge capacity and enhance its cycle stability. (FeCoCrMnZn)3O4 achieved a discharge capacity of 828.6 mAh g-1 at 2.0 A g-1 after 2000 cycles. This work provides a deep understanding of the structure and performance of HEO.