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In an effort to develop novel molecules with suitable insecticidal activities, 23,24-alkene-avermectin B2a derivatives have been synthesized

Molecular diodes are of considerable interest for the increasing technical demands of device miniaturization. However, the molecular diode performance remains contact-limited, which represents a major challenge for advancement of rectification ratio toward commercial availability. Here, we demonstrate that high-quality ultrathin organic semiconductor can be grown on several classes of metal substrates via solution-shearing epitaxy, with well-controlled number of layers and monolayer single crystal over 1 mm. The crystalline films are atomically smooth and free pinhole, providing a native interface for high-performance molecular diodes. As a result, the molecular diodes show record-high rectification ratio up to 5 × 108, ideality factor close to unity, aggressive unit conductance over 103 S/cm2, reverse breakdown electric field～1.1 × 108 V/cm, excellent electrical stability and well-defined contact interface. We further fabricate large-area molecular diode arrays with 100% yield and excellent uniformity in the diode metrics. Our results suggest that monolayer crystalline films have great potential to build reliable, high-performance molecular diodes and deeply understand their intrinsic electronic behavior.

Background: With the emerging resistance to mainstream insecticides, it is necessary to develop new insecticides to tackle the problem of pest threat. Diamide insecticides are widely studied because of their broad spectrum of activities, high efficiency, and low toxicity. Most thioether and oxide sulfide-containing compounds have a wide range of biological activities in agricultural chemicals. Objective: The main purpose of the study was to explore novel thioether and oxide sulfide-containing diamide compounds possessing outstanding insecticidal activity. Methods: Based on the “active substructure replacing” method by introducing methylthio groups, 29 sulfide-containing diamide compounds were designed and synthesised. The structures of all synthetic compounds were confirmed by 1H-NMR, 13C-NMR and HRMS. Moreover, the biological activities of all the compounds were tested. Results: The preliminary bioassay indicated that most of the new compounds did not exhibit better activity than the reference insecticide cyproflanilide. However, compounds 18a and 23a showed markedly potent activity against Tetranychus cinnabarinus at 100 mg/L, which was better than cyproflanilide since these compounds possessed 2-methyl-4-cyanophenyl, which might be the reason for their better internal absorption in the plant. Conclusion: The structure-activity relationship showed that some compounds were of potential value to be developed as novel insecticides, but the majority of compounds did not show superior insecticidal activity than cyproflanilide.

This article considers consensus of first-order/second-order hybrid multiagent systems (MASs) based on game modeling. In the first-order hybrid MAS (HMAS), a subset of agents select the Nash equilibrium of a multiplayer game as their states at each game time and the others update their states with first-order continuous-time (C-T) dynamics. By graph theory and matrix theory, we establish sufficient and necessary conditions for consensus of the first-order HMAS with two proposed protocols. The second-order HMAS is composed of agents whose states are determined by the Nash equilibrium of a multiplayer game and agents whose states are governed by second-order C-T dynamics. Similarly, sufficient and necessary conditions are given for consensus of the second-order HMAS with two proposed protocols. Several numerical simulations are provided to verify the effectiveness of our theoretical results.

Self-assembly processes, while promising for enabling the fabrication of complexly organized nanomaterials from nanoparticles, are often limited in creating structures with multiscale order. These limitations are due to difficulties in practically realizing the assembly processes required to achieve such complex organizations. For a long time, a hierarchical assembly attracted interest as a potentially powerful approach. However, due to the experimental limitations, intermediate-level structures are often heterogeneous in composition and structure, which significantly impacts the formation of large-scale organizations. Here, we introduce a two-stage assembly strategy: DNA origami frames scaffold a coordination of nanoparticles into designed 3D nanoclusters, and then these clusters are assembled into ordered lattices whose types are determined by the clusters' valence. Through modulating the nanocluster architectures and intercluster bindings, we demonstrate the successful formation of complexly organized nanoparticle crystals. The presented two-stage assembly method provides a powerful fabrication strategy for creating nanoparticle superlattices with prescribed unit cells.

Cryo-electron microscopy is an essential tool for high-resolution structural studies of biological systems. This method relies on the use of phase contrast imaging at high defocus to improve information transfer at low spatial frequencies at the expense of higher spatial frequencies. Here we demonstrate that electron ptychography can recover the phase of the specimen with continuous information transfer across a wide range of the spatial frequency spectrum, with improved transfer at lower spatial frequencies, and as such is more efficient for phase recovery than conventional phase contrast imaging. We further show that the method can be used to study frozen-hydrated specimens of rotavirus double-layered particles and HIV-1 virus-like particles under low-dose conditions (5.7 e/Å2) and heterogeneous objects in an Adenovirus-infected cell over large fields of view (1.14 × 1.14 μm), thus making it suitable for studies of many biologically important structures., Cryo-electron microscopy is widely employed in structural biology and uses phase contrast imaging. Here, the authors employ electron ptychography, a quantitative phase retrieval method for high-contrast, low-dose phase imaging of cryo-state rotavirus and immature HIV-1 virus-like particles, and show that electron ptychography is more efficient for phase recovery than conventional phase contrast imaging.

A peroxidase catalyzes the oxidation of a substrate with a peroxide. The search for peroxidase-like and other enzyme-like nanomaterials (called nanozymes) mainly relies on trial-and-error strategies, due to the lack of predictive descriptors. To fill this gap, here we investigate the occupancy of eg orbitals as a possible descriptor for the peroxidase-like activity of transition metal oxide (including perovskite oxide) nanozymes. Both experimental measurements and density functional theory calculations reveal a volcano relationship between the eg occupancy and nanozymes’ activity, with the highest peroxidase-like activities corresponding to eg occupancies of ~1.2. LaNiO3-δ, optimized based on the eg occupancy, exhibits an activity one to two orders of magnitude higher than that of other representative peroxidase-like nanozymes. This study shows that the eg occupancy is a predictive descriptor to guide the design of peroxidase-like nanozymes; in addition, it provides detailed insight into the catalytic mechanism of peroxidase-like nanozymes.

Three dimensional scaffolded DNA origami with inorganic nanoparticles has been used to create tailored multidimensional nanostructures. However, the image contrast of DNA is poorer than those of the heavy nanoparticles in conventional transmission electron microscopy at high defocus so that the biological and non-biological components in 3D scaffolds cannot be simultaneously resolved using tomography of samples in a native state. We demonstrate the use of electron ptychography to recover high contrast phase information from all components in a DNA origami scaffold without staining. We further quantitatively evaluate the enhancement of contrast in comparison with conventional transmission electron microscopy. In addition, We show that for ptychography post-reconstruction focusing simplifies the workflow and reduces electron dose and beam damage.

Single-site catalysts feature high catalytic activity but their facile construction and durable utilization are highly challenging. Herein, we report a simple impregnation-adsorption method to construct platinum single-site catalysts by synergic micropore trapping and nitrogen anchoring on hierarchical nitrogen-doped carbon nanocages. The optimal catalyst exhibits a record-high electrocatalytic hydrogen evolution performance with low overpotential, high mass activity and long stability, much superior to the platinum-based catalysts to date. Theoretical simulations and experiments reveal that the micropores with edge-nitrogen-dopants favor the formation of isolated platinum atoms by the micropore trapping and nitrogen anchoring of [PtCl6]2-, followed by the spontaneous dechlorination. The platinum-nitrogen bonds are more stable than the platinum-carbon ones in the presence of adsorbed hydrogen atoms, leading to the superior hydrogen evolution stability of platinum single-atoms on nitrogen-doped carbon. This method has been successfully applied to construct the single-site catalysts of other precious metals such as palladium, gold and iridium., Single-atom catalysts maximize atom usage within supports, but preparations can be complex. Here, authors show a facile impregnation-adsorption method to attach single noble-metal atoms to N-doped porous carbon and demonstrate strong electrocatalytic hydrogen evolution performances for Pt catalysts.

A peroxidase catalyzes the oxidation of a substrate with a peroxide. The search for peroxidase-like and other enzyme-like nanomaterials (called nanozymes) mainly relies on trial-and-error strategies, due to the lack of predictive descriptors. To fill this gap, here we investigate the occupancy of eg orbitals as a possible descriptor for the peroxidase-like activity of transition metal oxide (including perovskite oxide) nanozymes. Both experimental measurements and density functional theory calculations reveal a volcano relationship between the eg occupancy and nanozymes’ activity, with the highest peroxidase-like activities corresponding to eg occupancies of ~1.2. LaNiO3-δ, optimized based on the eg occupancy, exhibits an activity one to two orders of magnitude higher than that of other representative peroxidase-like nanozymes. This study shows that the eg occupancy is a predictive descriptor to guide the design of peroxidase-like nanozymes; in addition, it provides detailed insight into the catalytic mechanism of peroxidase-like nanozymes., The search for peroxidase-like as well as other enzyme-like nanozymes mainly relies on trial-and-error strategies, due to the lack of predictive descriptors. Here, the authors fill this gap by investigating the occupancy of eg orbitals as a possible descriptor for the peroxidase-like activity of transition metal oxide nanozymes

Gold nanoparticles (AuNPs) with simultaneous plasmonic and biocatalytic properties provide a promising approach to developing versatile bioassays. However, the combination of AuNPs' intrinsic enzyme-mimicking properties with their surface-enhanced Raman scattering (SERS) activities has yet to be explored. Here we designed a peroxidase-mimicking nanozyme by in situ growing AuNPs into a highly porous and thermally stable metal-organic framework called MIL-101. The obtained AuNPs@MIL-101 nanozymes acted as peroxidase mimics to oxidize Raman-inactive reporter leucomalachite green into the active malachite green (MG) with hydrogen peroxide and simultaneously as the SERS substrates to enhance the Raman signals of the as-produced MG. We then assembled glucose oxidase (GOx) and lactate oxidase (LOx) onto AuNPs@MIL-101 to form AuNPs@MIL-101@GOx and AuNPs@MIL-101@LOx integrative nanozymes for in vitro detection of glucose and lactate via SERS. Moreover, the integrative nanozymes were further explored for monitoring the change of glucose and lactate in living brains, which are associated with ischemic stroke. The integrative nanozymes were then used to evaluate the therapeutic efficacy of potential drugs (such as astaxanthin for alleviating cerebral ischemic injuries) in living rats. They were also employed to determine glucose and lactate metabolism in tumors. This study not only demonstrated the great promise of combining AuNPs' multiple functionalities for versatile bioassays but also provided an interesting approach to designing nanozymes for biomedical and catalytic applications.