Discovery of new N-Phenylamide Isoxazoline derivatives with high insecticidal activity and reduced honeybee toxicity.

Isoxazoline is a novel structure with strong potential for controlling agricultural insect pests, but its high toxicity to honeybees limits its development in agriculture. Herein, a series of N-phenylamide isoxazoline derivatives with low honeybee toxicity were designed and synthesized using the intermediate derivatization method. Bioassay results showed that these compounds exhibited good insecticidal activity. Compounds 3b and 3f showed significant insecticidal effects against Plutella xylostella (P. xylostella) with median lethal concentrations (LC50) of 0.06 and 0.07 mg/L, respectively, comparable to that of fluralaner (LC50 = 0.02 mg/L) and exceeding that of commercial insecticide fluxametamide (LC50 = 0.52 mg/L). It is noteworthy that the acute honeybee toxicities of compounds 3b and 3f (LD50 = 1.43 and 1.63 µg/adult, respectively) were significantly reduced to 1/10 of that of fluralaner (LD50 = 0.14 µg/adult), and were adequate or lower than that of fluxametamide (LD50 = 1.14 µg/adult). Theoretical simulation using molecular docking indicates that compound 3b has similar binding modes with fluralaner and a similar optimal docking pose with fluxametamide when binding to the GABA receptor, which may contribute to its potent insecticidal activity and relatively low toxicity to honey bees. This study provides compounds 3b and 3f as potential new insecticide candidates and provides insights into the development of new isoxazoline insecticides exhibiting both high efficacy and environmental safety.

Parallel two-photon lithography achieving uniform sub-200†nm features with thousands of individually controlled foci.

The limited throughput of nano-scale laser lithography has been the bottleneck for its industrial applications. Although using multiple laser foci to parallelize the lithography process is an effective and straightforward strategy to improve rate, most conventional multi-focus methods are plagued by non-uniform laser intensity distribution due to the lack of individual control for each focus, which greatly hinders the nano-scale precision. In this paper, we present a highly uniform parallel two-photon lithography method based on a digital mirror device (DMD) and microlens array (MLA), which allows the generation of thousands of femtosecond (fs) laser foci with individual on-off switching and intensity-tuning capability. In the experiments, we generated a 1,600-laser focus array for parallel fabrication. Notably, the intensity uniformity of the focus array reached 97.7%, where the intensity-tuning precision for each focus reached 0.83%. A uniform dot array structure was fabricated to demonstrate parallel fabrication of sub-diffraction limit features, i.e., below 1/4 λ or 200 nm. The multi-focus lithography method has the potential of realizing rapid fabrication of sub-diffraction, arbitrarily complex, and large-scale 3D structures with three orders of magnitude higher fabrication rate.

Exploiting Dual-Attention Networks for Explainable Recommendation in Heterogeneous Information Networks.

The aim of explainable recommendation is not only to provide recommended items to users, but also to make users aware of why these items are recommended. Traditional recommendation methods infer user preferences for items using user-item rating information. However, the expressive power of latent representations of users and items is relatively limited due to the sparseness of the user-item rating matrix. Heterogeneous information networks (HIN) provide contextual information for improving recommendation performance and interpreting the interactions between users and items. However, due to the heterogeneity and complexity of context information in HIN, it is still a challenge to integrate this contextual information into explainable recommendation systems effectively. In this paper, we propose a novel framework-the dual-attention networks for explainable recommendation (DANER) in HINs. We first used multiple meta-paths to capture high-order semantic relations between users and items in HIN for generating similarity matrices, and then utilized matrix decomposition on similarity matrices to obtain low-dimensional sparse representations of users and items. Secondly, we introduced two-level attention networks, namely a local attention network and a global attention network, to integrate the representations of users and items from different meta-paths for obtaining high-quality representations. Finally, we use a standard multi-layer perceptron to model the interactions between users and items, which predict users' ratings of items. Furthermore, the dual-attention mechanism also contributes to identifying critical meta-paths to generate relevant explanations for users. Comprehensive experiments on two real-world datasets demonstrate the effectiveness of DANER on recommendation performance as compared with the state-of-the-art methods. A case study illustrates the interpretability of DANER.

Visible light-induced Mallory reaction of tertiary benzanilides via iminium intermediates.

The Mallory reaction, which involves the photocyclization of stilbenes/diarylethenes and their analogues into polycyclic aromatics, is of significant synthetic importance. However, its application to tertiary benzanilides has not been explored to date. Besides, most of the reported Mallory reactions require ultraviolet irradiation. In this study, we show the first Mallory reaction of tertiary benzanilides promoted by visible light via iminium intermediates formed in situ from tertiary benzanilide, Tf2O (triflic anhydride) and pyridine. UV/vis absorption spectroscopy combined with density functional theory (DFT) calculations revealed that the formation of the iminium intermediate decreased the HOMO-LUMO energy gap, thereby enhancing visible light absorption. This study provides a rapid and practical approach for the preparation of the phenanthridinone skeleton and provides a new idea for the design of new visible light photoswitches.

FRET-Based Host-Guest Supramolecular Probe for On-Site and Broad-Spectrum Detection of Pyrethroids in the Environment.

The massive use of pyrethroid pesticides in agriculture has brought growing concerns about food safety due to their several harmful effects on human health, especially through the accumulation of the food chain. To date, most of the available analytical methods for pyrethroids still suffer from insufficient detection universality, complicated sample pretreatment, and detection processes, which severely limit their practical applications. Herein, a novel Förster resonance energy transfer (FRET)-assisted host-guest supramolecular nanoassembly is reported, for the first time, successfully realizing ratiometric fluorescent detection of pyrethroids in real samples through the indicator displacement assay (IDA) mechanism. This method is capable of detecting a broad spectrum of pyrethroids, including bifenthrin, cyfluthrin, cypermethrin, deltamethrin, etofenprox, fenvalerate, and permethrin, with ultrahigh detection sensitivity, great selectivity, high anti-interference ability, and, in particular, distinct emission color response from red to green. Such a large chromatic response makes this method available for fast and on-site detection of pyrethroids in real samples with the aid of several simple portable analytical apparatuses.

Discovery of Arylfluorosulfates as Novel Fungicidal Agents against Plant Pathogens.

A series of arylfluorosulfates were synthesized as fungicide candidates through a highly efficient sulfur fluoride exchange (SuFEx) reaction. A total of 32 arylfluorosulfate derivatives with simple structures have been synthesized, and most of them exhibited fungal activities in vitro against five agricultural pathogens (Rhizoctonia solani, Botrytis cinerea, Fusarium oxysporum, Pyricularia oryzae, and Phytophthora infestans). Among the target compounds, compound 31 exhibited great antifungal activity against Rhizoctonia solani (EC50 = 1.51 µg/mL), which was comparable to commercial fungicides carbendazim and thiabendazole (EC50 = 0.53 and 0.70 µg/mL, respectively); compounds 17 and 30 exhibited antifungal activities against Pyricularia oryzae (EC50 = 1.64 and 1.73 µg/mL, respectively) comparable to carbendazim (EC50 = 1.02 µg/mL). The in vitro antifungal effect of compound 31 was also evaluated on rice plants against Rhizoctonia solani. Significant preventive and curative efficacies were observed (89.2% and 91.8%, respectively, at 200 µg/mL), exceeding that of thiabendazole. Primary study on the mechanism of action indicated that compound 31 could suppress the sclerotia formation of Rhizoctonia solani even at a very low concentration (1.00 µg/mL), destroy the cell membrane and mitochondria, trigger the release of cellular contents, produce excessive reactive oxygen species (ROS), and suppress the activity of several related enzymes. This work could bring new insights into the development of arylfluorosulfates as novel fungicides.

Preparation and Characterization of Insecticide/Calix[4]arene Complexes and Their Enhanced Insecticidal Activities against Plutella xylostella.

Applications of supramolecular materials in plant protection have attracted significant interest in recent years. To develop a feasible method to improve the efficacy and reduce the usage of chemical pesticides, the effect of calix[4]arene (C4A) inclusion on enhancing the insecticidal activity of commercial insecticides was investigated. Results showed that all three tested insecticides (chlorfenapyr, indoxacarb, and abamectin) with distinct molecular sizes and modes of action were able to form stable 1:1 host-guest complexes with C4A through simple preparation steps. The insecticidal activities of the complexes against Plutella xylostella were effectively enhanced compared to the guest molecule, with the synergism ratio being up to 3.05 (for indoxacarb). An obvious correlation was found between the enhanced insecticidal activity and the high binding affinity between insecticide and C4A, while the improvement in water solubility may not be a determining factor. The work would provide hints for the further development of functional supramolecular hosts as synergists in pesticide formulations.

Naphthalene-based fluorescent probe for on-site detection of hydrazine in the environment.

The widespread occurrence of hydrazine residues in the environment, including in water, soil, and organisms, is a potential health threat to humans. Therefore, the development of an efficient method for the detection of hydrazine in environmental samples is highly desirable although it poses a significant challenge. In this study, we designed and synthesized a series of naphthalene-based fluorescent dyes through structural engineering and developed a novel probe for hydrazine detection. The probe could provide a distinct fluorescence response toward hydrazine in aqueous solution with high sensitivity and selectivity. Moreover, paper-based test strips can be easily fabricated using this probe, enabling the portable on-site detection of hydrazine with the aid of a smartphone. Furthermore, we demonstrated that this probe is capable of recognizing hydrazine in various environmental samples, including water, soil, plants, and zebrafish embryos. This research provides a promising tool for the detection of hydrazine in the environment.

A surfactant-assisted approach enables the fluorescence tracking of benfluralin in plants.

Developing an effective detection method for benfluralin (BFA) is of great significance, since BFA as most widely used herbicides can be bioaccumulated by aquatic organisms in environment, possessing potential risks to human health. Owing to aggregation-caused quenching effect, most fluorescent detection methods based on donor-acceptor organic fluorophores suffered from very low sensitivity towards BFA in water system, hampering the bioimaging application in plants. In this work, we reported a novel surfactant-assisted fluorescent probe enabling detection of BFA in water with a high sensitivity. The involvement of specific surfactant Triton X100 (TX100) could amplify the response signal of probe more than 100-fold. The detection limit for BFA was determined to be 80 nM, satisfying the environmental protection requirements. Moreover, we demonstrated applications of this strategy for the fluorescent imaging of BFA in plant. The absorbance of BFA into roots of Arabidopsis thaliana and castor seedlings was successfully observed based on this method.

Azocalixarene-Based Supramolecular System for the Detection of Paraquat via an Improved Indicator Displacement Assay.

In view of the lethal toxicity of paraquat (PQ) on human health, herein, a simple indicator displacement assay (IDA) based on an azo-modified calixarene host (azoCX[4]) and a fluorophore guest (p-DPD) were elaborately constructed for PQ detection in environmental water samples and plant surfaces. The fluorescent signal of p-DPD in the probe can be quenched by azoCX[4] through a photon-induced electron transfer process and recovered upon the addition of PQ within 10 s. The detection range of the p-DPD@azoCX[4] probe was calculated to be 0.35-8 µM in the Tris-HCl buffer solutions (pH = 7.4). Moreover, this probe exhibited excellent detection selectivity toward PQ over five herbicides (glyphosate, bispyribac, atrazine, ametryn, and bensulfuron methyl), together with anti-interference abilities in the presence of inorganic ions (K+, Na+, Zn2+, Ni2+, Li+, F-, Cl-, Br-, CO32-, HCO3-, and NO3-) and amino acids (Asp, Arg, Glu, Ala, and Cys). Particularly, the probe was successfully used to detect PQ in real water samples with acceptable accuracy and showed potential applications for on-site detection with paper-based test strips and on the leaf surface. We believe that this simplified IDA-based probe provided an effective detecting tool for PQ, and the design strategy would guide the further development of new IDA sensing systems.