Nitrogen and fluoride co-doped graphdiyne with metal-organic framework (MOF)-derived NiCo2O4-Co3O4 nanocages as sensing layers for ultra-sensitive pesticide detection.

Heteroatom doped graphdiyne (GDY) has been demonstrated to be an effective strategy for achieving outstanding electrochemical properties, including improved electrocatalytic activity, tunable electronic properties and high electronic conductivity, by producing numerous heteroatomic defects as well as active sites. Extensive efforts have been devoted to the issue of single element doping of GDY. Introducing two or more kinds of heteroatoms into GDY materials may create a synergic effect between the co-dopants, thus generating superior electrochemical performance. Nevertheless, little research on multiple elements co-doped GDY, especially in the application of constructing electrochemical biosensor. Herein, nitrogen and fluoride co-doped GDY (N-F-GDY) has been synthesized and employed to combine with NiCo2O4-Co3O4 hollow multishelled nanocages to establish an ultrasensitive electrochemical biosensor for the assay of pesticide residue. The as-prepared electrochemical biosensor possesses a wide linear range of 0.448 pM-44.8 nM for monocrotophos detection and a low detection limit of 0.0166 fM (S/N = 3).

Oriented Design of Transition-Metal-Oxide Hollow Multishelled Micropolyhedron Derived from Bimetal-Organic Frameworks for the Electrochemical Detection of Multipesticide Residues.

Transition-metal oxides (TMOs) with a hollow multishelled structure have emerged as highly potential materials for high-performance electrochemical sensing, benefiting from their superior electronic conductivity, exceptionally large specific surface area, excellent stability, and electrochemistry properties. In particular, binary TMOs are expected to outperform unitary TMOs due to the synergistic effect of the different metals. Herein, MnCo2O4.5 hollow quadruple-shelled porous micropolyhedrons (MnCo2O4.5 HoQS-MPs) were prepared and employed to construct an ultrasensitive sensing platform for a multipesticide assay. Profiting from complex hollow interior structures and abundant active sites, the MnCo2O4.5 HoQS-MPs manifest outstanding electrochemical properties as electrode materials for the pesticide assay. The MnCo2O4.5 HoQS-MP-based biosensor demonstrated remarkable performance for monocrotophos, methamidophos, and carbaryl detection, with wide linear ranges, as well as low detection limits. This work unveils a new pathway for the ultrasensitive detection of pesticides and demonstrates tremendous potential for detecting other environmentally deleterious chemicals.

Cyclophilin effector Al106 of mirid bug Apolygus lucorum inhibits plant immunity and promotes insect feeding by targeting PUB33.

Apolygus lucorum (Meyer-Dur; Heteroptera: Miridae) is a major agricultural pest infesting crops, vegetables, and fruit trees. During feeding, A. lucorum secretes a plethora of effectors into its hosts to promote infestation. However, the molecular mechanisms of these effectors manipulating plant immunity are largely unknown. Here, we investigated the molecular mechanism underlying the effector Al106 manipulation of plant-insect interaction by RNA interference, electrical penetration graph, insect and pathogen bioassays, protein-protein interaction studies, and protein ubiquitination experiment. Expression of Al106 in Nicotiana benthamiana inhibits pathogen-associated molecular pattern-induced cell death and reactive oxygen species burst, and promotes insect feeding and plant pathogen infection. In addition, peptidyl-prolyl cis-trans isomerase (PPIase) activity of Al106 is required for its function to inhibit PTI.Al106 interacts with a plant U-box (PUB) protein, PUB33, from N. benthamiana and Arabidopsis thaliana. We also demonstrated that PUB33 is a positive regulator of plant immunity. Furthermore, an in vivo assay revealed that Al106 inhibits ubiquitination of NbPUB33 depending on PPIase activity. Our findings revealed that a novel cyclophilin effector may interact with plant PUB33 to suppress plant immunity and facilitate insect feeding in a PPIase activity-dependent manner.

Characterization of Salivary Secreted Proteins That Induce Cell Death From Riptortus pedestris (Fabricius) and Their Roles in Insect-Plant Interactions.

Riptortus pedestris (Fabricius) is a polyphagous hemipteran crop pest that mainly feeds on the leguminous plants, resulting in shriveled and dimpled seeds. With recent several outbreaks in the Huang-Huai-Hai region of China, as well as in South Korea and Japan, this species has caused enormous economic losses to soybean crops. In the present study, we found that R. pedestris feeding results in local lesions at the infestation sites. To identify the key effectors that induce plant damage during feeding, the salivary glands of R. pedestris were dissected for transcriptome sequencing, and 200 putative secreted proteins were transiently expressed in N. benthamiana. Among them, three intracellular effectors (RP191, RP246, and RP302) and one apoplastic effector (RP309) were identified as necrosis-inducing proteins (NIPs), which also triggered the reactive oxidative burst. Yeast signal sequence trap and qRT-PCR analysis suggested that these proteins might be secreted into plant tissue during R. pedestris infestation. Pathogenicity assays revealed that RP191, 246, and 302 promote Phytophthora capsici infection or induce Spodoptera litura feeding by inhibiting plant immunity. RP302 is localized to the cytoplasm and nuclei, while RP191 and 246 are endoplasmic reticulum (ER) resident proteins. RP309 stimulates the expression of PTI marker genes, and its induced cell death depends on co-receptors NbBAK1 and NbSOBIR1, indicating that it is a HAMP. Bioinformatics analysis demonstrated that four NIPs are recently evolved effectors and only conserved in the Pentatomidae. In this study, saliva-secreted proteins were used as the starting point to preliminarily analyze the harm mechanism of R. pedestris, which might provide a new idea and theoretical basis for this species control.