Concentrations, Sources and Health Risk Assessment of Polycyclic Aromatic Hydrocarbons in Chinese Herbal Medicines.

The determination and evaluation of 16 polycyclic aromatic hydrocarbons (PAHs) in seven Chinese herbal medicines (CHMs) were conducted through a rapid and straightforward extraction and purification method, coupled with GC-MS. A sample-based solid-phase extraction (SPE) pretreatment technique, incorporating isotopic internal standards, was employed for detecting various medicinal parts of CHMs. The assay exhibited linearity within the range of 5 to 500 ng/mL, with linear coefficients (R2) for PAHs exceeding 0.999. The recoveries of spiked standards ranged from 63.37% to 133.12%, with relative standard deviations (RSDs) ranging from 0.75% to 14.54%. The total PAH content varied from 176.906 to 1414.087 µg/kg. Among the 16 PAHs, phenanthrene (Phe) was consistently detected at the highest levels (47.045-168.640 µg/kg). Characteristic ratio analysis indicated that oil, coal, and biomass combustion were the primary sources of PAHs in CHMs. The health risk associated with CHMs was assessed using the lifetime carcinogenic risk approach, revealing potential health risks from the consumption of honeysuckle, while the health risks of consuming Lycium chinense berries were deemed negligible. For the other five CHMs (glycyrrhizae, Coix lacryma, ginseng, lotus seed, seed of Sterculia lychnophora), the health risk from consumption fell within acceptable ranges. Furthermore, sensitivity analyses utilizing Monte Carlo exposure assessment methods identified PAH levels in CHMs as health risk sensitizers. It is crucial to recognize that the consumption of herbal medicines is not a continuous process but entails potential health risks. Hence, the monitoring and risk assessment of PAH residues in CHMs demand careful attention.

Efficient Synthesis of Metastable Cyclodextrin-Based Polyrotaxanes with Tunable Threading Ratios.

Cyclodextrin-based polyrotaxanes (CD-PRs) are gaining attention for their dynamic sliding rings along the polymer axis, enabling various applications in molecular shuttles, drug delivery, and durable polymers with slidable cross-links. However, the conventional synthesis of CD-PRs with tunable threading ratios is typically laborious, time-consuming, and complicated, which limits their scalability and cost-effectiveness. Herein, we highlight the great potential of planetary centrifugal mixing, a process that significantly accelerates and simplifies the initial synthesis of polypseudorotaxanes (PPRs), followed by a thiol-ene click reaction as an efficient end-capping reaction for the synthesis of PRs. Notably, PRs synthesized with glutathione (GSH) as the end-capping reagent are in a metastable state, where GSH act as a molecular bumper that significantly prevent de-threading of α-CD rings at room temperature. Moreover, the rate of ring de-threading can be precisely controlled by heating, enabling the preparation of metastable PRs with tunable threading ratios over a wide range. The developed strategy is of great significance to the efficient synthesis of CD-PRs, thus marking a significant step towards their practical application in advanced functional materials and devices.

Robust Janus Superwetting Textile with Large Pore Sizes for Oil-in-Water Emulsion Separation.

Developing advanced oil-water separation technology is significant for environmental conservation. According to the synergetic effects of the size-sieving mechanism, superwetting materials with small pore sizes have been designed to realize high-efficiency separation for oil-water emulsions. However, the separation flux limited by the pore size and the weakness of the superwetting material impede its practical application severely. Herein, we construct a robust Janus superwetting textile with large pore sizes for oil-in-water emulsion separation. The pristine textile is coated by the as-prepared CuO nanoparticles as the bottom layer with superhydrophilicity and then grafted by 1-octadecanethiol as the top layer with superhydrophobicity to construct the Janus textile. When used as a filter, the superhydrophobic layer acts as the nucleation site to coalesce the small oil droplets facilely. Then, the coalesced oil fills the pores of the superhydrophobic layer and selectively permeates it but is blocked by the superhydrophilic layer with large pore sizes. Utilizing the unique separation mechanism, the Janus textile realizes efficient and rapid separation. Even after multicycle separation, hot liquid immersion for 24 h, tribological test for 60 min, and sandpaper abrasion for 500 cycles, the Janus textile still retains the superwettability and excellent separation performance, manifesting outstanding stability to resist severe damage. This separation strategy provides a novel guideline for high-efficiency and high-flux emulsion separation and practical application.

Unintended consequences: Disrupting microbial communities of Nilaparvata lugens with non-target pesticides.

Insects are frequently exposed to a range of insecticides that can alter the structure of the commensal microbiome. However, the effects of exposure to non-target pesticides (including non-target insecticides and fungicides) on insect pest microbiomes are still unclear. In the present study, we exposed Nilaparvata lugens to three target insecticides (nitenpyram, pymetrozine, and avermectin), a non-target insecticide (chlorantraniliprole), and two fungicides (propiconazole and tebuconazole), and observed changes in the microbiome's structure and function. Our results showed that both non-target insecticide and fungicides can disrupt the microbiome's structure. Specifically, symbiotic bacteria of N. lugens were more sensitive to non-target insecticide compared to target insecticide, while the symbiotic fungi were more sensitive to fungicides. We also found that the microbiome in the field strain was more stable under pesticides exposure than the laboratory strain (a susceptible strain), and core microbial species g_Pseudomonas, s_Acinetobacter soli, g_Lactobacillus, s_Metarhizium minus, and s_Penicillium citrinum were significantly affected by specifically pesticides. Furthermore, the functions of symbiotic bacteria in nutrient synthesis were predicted to be significantly reduced by non-target insecticide. Our findings contribute to a better understanding of the impact of non-target pesticides on insect microbial communities and highlight the need for scientific and rational use of pesticides.

Effects of CPAP treatment on electroencephalographic activity in patients with obstructive sleep apnea syndrome during deep sleep: Preliminary findings of a cross-sectional study.

Study objectives: To investigate whether electroencephalographic (EEG) activities during non-rapid eye movement sleep stage 3 (N3) in obstructive sleep apnea syndrome (OSAS) patients were changed with continuous positive airway pressure (CPAP) treatment.Methods: A cross-sectional study of EEG activity during N3 sleep was conducted in 15 patients with moderate to severe OSAS without and with CPAP treatment compared to 15 normal controls. The amplitude, and absolute and relative power of delta, theta, alpha and beta waves as well as the absolute power ratio of slow to fast EEG waves (i.e., absolute power of delta and theta waves/absolute power of alpha and beta waves) and the spectral power density of 0-30 Hz EEG activities were analyzed.Results: CPAP significantly increased N3 sleep, the absolute and relative powers, amplitudes of delta and theta waves, and absolute power ratio of slow to fast EEG waves, but decreased relative alpha and beta powers during N3 sleep. However, there were no significant differences in those parameters between the OSAS patients with CPAP treatment and normal controls.Conclusions: CPAP prolongs N3 sleep and increases the power and amplitude of slow EEG waves during N3 sleep, which indicates an improvement in sleep quality and further provides evidence for recommendation of CPAP treatment for OSAS patients.

Durable 3D Porous Superhydrophobic Composites for Versatile Emulsion Separation in Multiple Environments.

Polydopamine as a multifunctional biomimetic polymer with nonselective strong adhesion properties has become a hot research topic in recent years. However, there are a few reports on the durable and effective emulsion separation of polydopamine composites from other materials. Therefore, it is necessary to construct durable polydopamine composites to achieve selective adsorption of materials. In this work, polypyrrole (PPy)-PDA was obtained on sponges by an in situ polymerization reaction, followed by the attachment of SiO2 nanoparticles to the surface by polydimethylsiloxane to achieve superhydrophobicity. As a result, previously unreported selective superhydrophobic adsorbents for PPy-PDA coatings were obtained. The prepared sponges have an excellent adsorption capacity for oils and organic solvents. Not only can the sponges absorb 19-39 g of organic solvents per gram but they can also absorb oil from oil-in-water emulsions. The chemical oxygen demand value of the emulsion can be reduced to 219 mg/L after separation. More importantly, the performance remains good in the cycle test, and due to the construction of a durable superhydrophobic sponge, it can still maintain its relatively good performance in artificial seawater, acid-base environments, and can achieve relatively stable emulsion separation. At the same time, the potential of the polymer material composited with PDA in lasting and stable emulsion separation was also verified.

Influence of sleep bruxism on QTc interval and QT variability in patients with OSA: A pilot study.

BACKGROUND: Obstructive sleep apnea (OSA) is associated with increases in QT interval corrected for heart rate (QTc interval) and QT variability index (QTVI) and sleep bruxism (SB) is prevalent in OSA patients. OBJECTIVES: To examine whether QTc interval and QT variability were changed during episodes of rhythmic masticatory muscle activities (RMMAs)/SB in SB patients with and without OSA. METHODS: The RR and QTc intervals, and QTVI during RMMAs with or without accompanied limb movements (RMMAs/LMs) in 10 normal controls and 10 SB patients without OSA and during apneic and recovery periods of OSA in 10 SB patients with OSA were analysed. RESULTS: In the SB patients without OSA and controls, QTc intervals and QTVI were significantly increased during RMMAs/LMs compared with those during the 10 s periods (from 10th to 20th s) before the onset and after the offset of RMMAs/LMs, and significantly increased during RMMAs/LMs with awakenings compared with those with microarousals and no arousals. In addition, QTc interval and QTVI were positively correlated with the duration of RMMAs/LMs. Moreover, in the SB patients with OSA, QTc interval and QTVI during the recovery period of OSA events were significantly longer and higher than those during the apneic period regardless of accompanied RMMAs/LMs, and QTc interval and QTVI during the apneic and recovery periods accompanied with RMMAs/LMs were significantly longer and higher than those without accompanied RMMAs/LMs. CONCLUSION: OSA and RMMAs/LMs events were associated with longer QTc intervals and higher QTVI, and RMMAs/LMs might contribute to these changes associated with OSA events accompanied with RMMAs/LMs.

[One new coumarin from seeds of Herpetospermum pedunculosum].

This paper aims to investigate the chemical constituents of the seeds of Herpetospermum pedunculosum. One new coumarin and two known lignans were isolated from the ethanolic extract of the seeds of H. pedunculosum with thin layer chromatography(TLC), silica gel column chromatography, Sephedax LH-20 chromatography, Semi-preparative high performance liquid chromatography and recrystallization, etc. Their structures were elucidated as herpetolide H(1), phyllanglaucin B(2), and buddlenol E(3) by analysis of their physicochemical properties and spectral data. Among them, compound 1 was a new compound, and compounds 2 and 3 were isolated from this genus for the first time. In vitro anti-inflammatory activity test showed that herpetolide H had certain NO inhibitory activity for LPS-induced RAW 264.7 cells, with its IC_(50) value of(46.57±3.28) µmol·L~(-1).

[Network pharmacological analysis and experimental verification of anti-inflammatory and analgesic effect of Zanthoxyli Pericarpium].

To explore the mechanism of anti-inflammatory and analgesic effect of Zanthoxyli Pericarpium based on network pharmacology and inflammatory or pain mouse models. The effective components of Zanthoxyli Pericarpium were screened out by TCMSP database. And their potential corresponding targets were predicted by PharmMapper software. The possible targets relating to inflammation and pain were mainly collected through DrugBank, TTD and DisGeNET databases. The "active ingredient-gene-disease" network diagram was constructed by Cytoscape 3.7.0 software. The network pharmacology results showed 5 potential effective compounds, which were related to 29 targets; 132 targets relating to inflammation and pain were screened out in the DrugBank, TTD and DisGeNET databases. The network analysis results indicated that the phosphatidylinositol 3-kinase catalytic subunit gamma isoform(PIK3 CG) gene may be the key to the anti-inflammatory and analgesic effect of Zanthoxyli Pericarpium. The anti-inflammatory and analgesic effects of essential oil extract and dichloromethane extract of Zanthoxyli Pericarpium were explored through the mouse model of inflammation induced by xylene or carrageenan and the mouse model of pain induced by acetic acid or formalin. The experimental results showed that essential oil extract and dichloromethane extract of Zanthoxyli Pericarpium could reduce xylene-induced ear swelling and carrageenan-induced paw swelling and decrease the number of writhing responses in mice induced by acetic acid and the licking foot time of mice in phase Ⅱ induced by formalin. Western blot results showed that Zanthoxyli Pericarpium extract could inhibit the expressions of PIK3 CG, phosphonated nuclear factor kappaB(p-NF-κB) and phosphonated p38(p-p38 MAPK) protein. The present study showed the anti-inflammatory and analgesic effect of Zanthoxyli Pericarpium through multiple components and targets, so as to provide a pharmacodynamic basis for the study of Zanthoxyli Pericarpium and its mechanism.

Coronavirus receptor switch explained from the stereochemistry of protein-carbohydrate interactions and a single mutation.

Hemagglutinin-esterases (HEs) are bimodular envelope proteins of orthomyxoviruses, toroviruses, and coronaviruses with a carbohydrate-binding "lectin" domain appended to a receptor-destroying sialate-O-acetylesterase ("esterase"). In concert, these domains facilitate dynamic virion attachment to cell-surface sialoglycans. Most HEs (type I) target 9-O-acetylated sialic acids (9-O-Ac-Sias), but one group of coronaviruses switched to using 4-O-Ac-Sias instead (type II). This specificity shift required quasisynchronous adaptations in the Sia-binding sites of both lectin and esterase domains. Previously, a partially disordered crystal structure of a type II HE revealed how the shift in lectin ligand specificity was achieved. How the switch in esterase substrate specificity was realized remained unresolved, however. Here, we present a complete structure of a type II HE with a receptor analog in the catalytic site and identify the mutations underlying the 9-O- to 4-O-Ac-Sia substrate switch. We show that (i) common principles pertaining to the stereochemistry of protein-carbohydrate interactions were at the core of the transition in lectin ligand and esterase substrate specificity; (ii) in consequence, the switch in O-Ac-Sia specificity could be readily accomplished via convergent intramolecular coevolution with only modest architectural changes in lectin and esterase domains; and (iii) a single, inconspicuous Ala-to-Ser substitution in the catalytic site was key to the emergence of the type II HEs. Our findings provide fundamental insights into how proteins "see" sugars and how this affects protein and virus evolution.

The temporal dynamics of detached versus positive reappraisal: An ERP study.

Detached reappraisal and positive reappraisal are regarded as two distinct types of cognitive reappraisal strategy, and the former is considered more disengaging than the latter. The conceptual framework of emotion regulation choice posits that strategies involving disengagement operate earlier and more efficiently than engagement strategies. Here, we compare for the first time the temporal dynamics of detached and positive reappraisal during the regulation and re-exposure phases thereof by measuring event-related potentials. During the regulation phase, pictures were viewed or regulated using detached or positive reappraisal. During the re-exposure phase, the same pictures were viewed again. Results showed that during regulation, central-parietal late positive potentials (LPPs) were greatly attenuated under both strategy types, with the regulation effect of detached reappraisal occurring earlier than that of positive reappraisal and resulting in a stronger attenuation of LPP amplitudes. Upon re-exposure, detached reappraisal exerted enduring effects on self-reported arousal and the central-parietal LPP, whereas positive reappraisal had an enduring effect only on pleasantness. These findings demonstrate the differential effects of detached and positive reappraisal on valence, arousal, and neural responses, and underline the striking differences in the temporal dynamics of these reappraisal strategies.

Enhanced conflict-driven cognitive control by emotional arousal, not by valence.

Emotion is widely agreed to have two dimensions, valence and arousal. Few studies have explored the effect of emotion on conflict adaptation by considering both of these, which could have dissociate influence. The present study aimed to fill the gap as to whether emotional valence and arousal would exert dissociable influence on conflict adaptation. In the experiments, we included positive, neutral, and negative conditions, with comparable arousal between positive and negative conditions. Both positive and negative conditions have higher arousal than neutral ones. In Experiment 1, by using a two-colour-word Flanker task, we found that conflict adaptation was enhanced in both positive and negative contexts compared to a neutral context. Furthermore, this effect still existed when controlling stimulus-response repetitions in Experiment 2, which used a four-colour-word Flanker task. The findings suggest emotional arousal enhances conflict adaptation, regardless of emotional valence. Thus, future studies should consider emotional arousal when studying the effect of emotion on conflict adaptation. Moreover, the unique role of the emotional context in conflict-driven cognitive control is emphasised.

The divergent effects of fear and disgust on unconscious inhibitory control.

Previous studies have shown that negative emotional distracters impair conscious inhibitory control. Recent research has shown that inhibitory control can be triggered unconsciously; therefore, in Experiment 1, we aimed to investigate whether negative emotional distracters affect unconscious inhibitory control. Furthermore, in Experiment 2, we examined whether fearful and disgusting distracters have differential effects on unconscious inhibitory control. Participants were instructed to perform a masked Go/No-Go task superimposed on a negative or neutral image cue (Experiment 1) or on a fearful, disgusting or neutral image cue (Experiment 2). Results showed that negative emotional distracters impaired unconscious inhibitory control; furthermore, disgusting distracters impeded unconscious inhibitory control when compared to fearful ones. This study is the first to provide evidence that fear and disgust may affect unconscious inhibitory control differently. These results expand the understanding of the relationship between emotions and inhibitory control.

The murine coronavirus hemagglutinin-esterase receptor-binding site: a major shift in ligand specificity through modest changes in architecture.

The hemagglutinin-esterases (HEs), envelope glycoproteins of corona-, toro- and orthomyxoviruses, mediate reversible virion attachment to O-acetylated sialic acids (O-Ac-Sias). They do so through concerted action of distinct receptor-binding ("lectin") and receptor-destroying sialate O-acetylesterase ("esterase") domains. Most HEs target 9-O-acetylated Sias. In one lineage of murine coronaviruses, however, HE esterase substrate and lectin ligand specificity changed dramatically as these viruses evolved to use 4-O-acetylated Sias instead. Here we present the crystal structure of the lectin domain of mouse hepatitis virus (MHV) strain S HE, resolved both in its native state and in complex with a receptor analogue. The data show that the shift from 9-O- to 4-O-Ac-Sia receptor usage primarily entailed a change in ligand binding topology and, surprisingly, only modest changes in receptor-binding site architecture. Our findings illustrate the ease with which viruses can change receptor-binding specificity with potential consequences for host-, organ and/or cell tropism, and for pathogenesis.

A putative endonuclease reduces the efficiency of oral RNA interference in Nilaparvata lugens.

BACKGROUND: The RNA interference (RNAi) efficiency of double-stranded RNA (dsRNA) delivery to insects by various methods is different and the reduced efficacy of feeding dsRNA is partly due to the presence of DNA/RNA non-specific endonuclease in the insect gut. However, the mechanism leading to the low RNAi efficiency of Nilaparvata lugens by feeding remains elusive. RESULTS: In this study, we identified a putatively DNA/RNA non-specific endonuclease gene in the N. lugens genome database that was highly expressed in the first nymphal instar and the midgut. Different expression levels of NldsRNase after feeding and injection suggested that NldsRNase might interfere with oral RNAi in N. lugens. A co-delivery RNAi strategy further revealed that the presence of NldsRNase reduces RNAi efficiency. In vitro dsRNA degradation experiments also showed that the stability of dsRNA was higher in a gut mixture from nymphs injected with dsNldsRNase. These results support the idea that the low oral RNAi response observed in N. lugens is likely due to the presence of NldsRNase. CONCLUSIONS: Our study provides insight into the differences in RNAi response between the injection and feeding of dsRNA in N. lugens and sheds light on the mechanisms underlying the reduced efficacy of RNAi via feeding. These findings may help to inform the development of more-effective RNAi-based strategies controlling N. lugens and other insect pests. © 2024 Society of Chemical Industry.

Mussel-Inspired Robust Peony-like Cu3(PO4)2 Composite Switchable Superhydrophobic Surfaces for Bidirectional Efficient Oil/Water Separation.

To alleviate the economic and environmental damage caused by industrial discharges of oily wastewater, materials applied for efficient oil/water separation are receiving significant attention from researchers and engineers. Among others, switchable wettable materials for bidirectional oil/water separation show great potential for practical applications. Inspired by mussels, we utilized a simple immersion method to construct a polydopamine (PDA) coating on a peony-like copper phosphate surface. Then, TiO2 was deposited on the PDA coating surface to build a micro-nano hierarchical structure, which was modified with octadecanethiol (ODT) to obtain a switchable wettable peony-like superhydrophobic surface. The water contact angle of the obtained superhydrophobic surface reached 153.5°, and the separation efficiency was as high as 99.84% with a flux greater than 15,100 L/(m2·h) after 10 separation cycles for a variety of heavy oil/water mixtures. Notably, the modified membranes have a unique photoresponsiveness, transforming to superhydrophilic upon ultraviolet irradiation, achieving separation efficiencies of up to 99.83% and separation fluxes greater than 32,200 L/(m2·h) after 10 separation cycles for a variety of light oil/water mixtures. More importantly, this switch behavior is reversible, and the high hydrophobicity can be restored after heating to achieve efficient separation of heavy oil/water mixtures. In addition, the prepared membranes can maintain high hydrophobicity under acid-base conditions and after 30 sandpaper abrasion cycles, and damaged membranes can be restored to superhydrophobicity after a brief modification in the ODT solution. This simple-to-prepare, easy-to-repair, robust membrane with switchable wettability shows great potential in the field of oil/water separation.

The insecticidal activity and mechanism of tebuconazole on Nilaparvata lugens (Stål).

BACKGROUND: Previous studies have shown that fungicides have insecticidal activity that can potentially be used as an insecticide resistance management strategy in the brown planthopper Nilaparvata lugens (Stål). However, the mechanism that induces mortality of N. lugens remains elusive. RESULTS: In the present study, the insecticidal activities of 14 fungicides against N. lugens were determined, of which tebuconazole had the highest insecticidal activity compared with the other fungicides. Furthermore, tebuconazole significantly inhibited the expression of the chitin synthase gene NlCHS1; the chitinase genes NlCht1, NlCht5, NlCht7, NlCht9, and NlCht10; and the ß-N-acetylhexosaminidase genes NlHex3, NlHex4, NlHex5 and NlHex6; it significantly suppressed the expression of ecdysteroid biosynthetic genes as well, including SDR, CYP307A2, CYP307B1, CYP306A2, CYP302A1, CYP315A1 and CYP314A1 of N. lugens. Additionally, tebuconazole affected the diversity, structure, composition, and function of the symbiotic fungi of N. lugens, as well as the relative abundance of saprophytes and pathogens, suggesting that tebuconazole reshapes the diversity and function of symbiotic fungi of N. lugens. CONCLUSION: Our findings illustrate the insecticidal mechanism of tebuconazole, possibly by inhibiting normal molting or disrupting microbial homeostasis in N. lugens, and provide an important rationale for developing novel insect management strategies to delay escalating insecticide resistance. © 2023 Society of Chemical Industry.

Metal-Organic Framework-Based Insecticide and dsRNA Codelivery System for Insecticide Resistance Management.

Targeted silencing of resistance-associated genes by specific double-stranded RNA (dsRNA) is an attractive strategy for overcoming insecticide resistance in insect pests. However, silencing target genes of insect pests by feeding on dsRNA transported via plants remains challenging. Herein, a codelivery system of insecticide and dsRNA is designed by encapsulating imidacloprid and dsNlCYP6ER1 within zeolitic imidazolate framework-8 (ZIF-8) nanoparticles to improve the susceptibility of Nilaparvata lugens (Stål) to imidacloprid. With an average particle size of 195 nm and a positive surface charge, the derived imidacloprid/dsNlCYP6ER1@ZIF-8 demonstrates good monodispersity. Survival curve results showed that the survival rates of N. lugens treated with imidacloprid and imidacloprid@ZIF-8 were 82 and 62%, respectively, whereas, in the imidacloprid/dsNlCYP6ER1@ZIF-8 treatment group, the survival rate of N. lugens is only 8%. Pot experiments demonstrate that the survival rate in the imidacloprid/dsNlCYP6ER1@ZIF-8 treatment group was much lower than that in the imidacloprid treatment group, decreasing from 54 to 24%. The identification of NlCYP6ER1 expression and the fluorescence tracking of ZIF-8 demonstrate that ZIF-8 can codeliver dsRNA and insecticide to insects via rice. Safety evaluation results showed that the dsNlCYP6ER1@ZIF-8 nanoparticle had desirable biocompatibility and biosafety to silkworm. This dsRNA and insecticide codelivery system may be extended to additional insecticides with potential resistance problems in the future, greatly enhancing the development of pest resistance management.

Redox and Near-Infrared Light-Responsive Nanoplatform for Enhanced Pesticide Delivery and Pest Control in Rice: Construction, Efficacy, and Potential Mechanisms.

The brown planthopper, Nilaparvata lugens (Stål), is a major rice pest in various Asian countries, causing significant negative impacts on rice yield and quality. In this study, we developed a novel nanoplatform (NIT@MON@CuS) for pesticide delivery that responds to redox and near-infrared light stimuli. The nanoplatform consisted of CuS nanoparticles with mesoporous organic silica (MON), loaded with nitenpyram (NIT). With an average size of 190 nm and a loading efficiency of 22%, NIT@MON@CuS exhibited remarkable thermal response in the near-infrared region, demonstrating excellent photothermal conversion ability and stability. In vitro release kinetics demonstrated the rapid release of nitenpyram under near-infrared light and glutathione conditions, facilitating a satisfactory temperature increase and accelerated drug release. The NIT@MON@CuS-treated group exhibited a higher mortality of N. lugens, increasing from 62 to 88% compared to the group treated with nitenpyram technical after 96 h. Bioassay revealed that NIT@MON@CuS significantly enhanced nitenpyram toxicity by more than 1.4-fold against both laboratory insecticide-resistant and field strains of N. lugens. Furthermore, RT-qPCR results demonstrated that MON@CuS had the capability to reduce P450 gene expression, thereby improving the sensitivity of N. lugens to insecticides. These findings suggest that MON@CuS holds great potential as an intelligent pest control platform, offering a sustainable and efficient approach to protect crops against pests.

Structural basis for ligand and substrate recognition by torovirus hemagglutinin esterases.

Hemagglutinin esterases (HEs), closely related envelope glycoproteins in influenza C and corona- and toroviruses, mediate reversible attachment to O-acetylated sialic acids (Sias). They do so by acting both as lectins and as receptor-destroying enzymes, functions exerted by separate protein domains. HE divergence was accompanied by changes in quaternary structure and in receptor and substrate specificity. The selective forces underlying HE diversity and the molecular basis for Sia specificity are poorly understood. Here we present crystal structures of porcine and bovine torovirus HEs in complex with receptor analogs. Torovirus HEs form homodimers with sialate-O-acetylesterase domains almost identical to corresponding domains in orthomyxo- and coronavirus HEs, but with unique lectin sites. Structure-guided biochemical analysis of the esterase domains revealed that a functionally, but not structurally conserved arginine-Sia carboxylate interaction is critical for the binding and positioning of glycosidically bound Sias in the catalytic pocket. Although essential for efficient de-O-acetylation of Sias, this interaction is not required for catalysis nor does it affect substrate specificity. In fact, the distinct preference of the porcine torovirus enzyme for 9-mono- over 7,9-di-O-acetylated Sias can be explained from a single-residue difference with HEs of more promiscuous specificity. Apparently, esterase and lectin pockets coevolved; also the porcine torovirus HE receptor-binding site seems to have been designed to use 9-mono- and exclude di-O-acetylated Sias, possibly as an adaptation to replication in swine. Our findings shed light on HE evolution and provide fundamental insight into mechanisms of substrate binding, substrate recognition, and receptor selection in this important class of virion proteins.