Design, synthesis and biological activity determination of novel phenylpyrazole protoporphyrinogen oxidase inhibitor herbicides.

Protoporphyrinogen oxidase (PPO, EC 1.3.3.4) is the last common enzyme in the biosynthetic pathway in the synthesis of heme and chlorophyll. The high-frequency use of PPO inhibitor herbicides has led to the gradual exposure of pesticide damage and resistance problems. In order to solve this kind of problem, there is an urgent need to develop new PPO inhibitor herbicides. In this paper, 16 phenylpyrazole derivatives were designed by the principle of active substructure splicing through the electron isosterism of five-membered heterocycles. Greenhouse herbicidal activity experiments and in vitro PPO activity experiments showed that the inhibitory effect of compound 9 on weed growth was comparable to that of pyraflufen-ethyl. Crop safety experiments and cumulative concentration experiments in crops showed that when the spraying concentration was 300 g ai/ha, wheat, corn, rice and other cereal crops were more tolerant to compound 9, among which wheat showed high tolerance, which was comparable to the crop safety of pyraflufen-ethyl. Herbicidal spectrum experiments showed that compound 9 had inhibitory activity against most weeds. Molecular docking results showed that compound 9 formed one hydrogen bond interaction with amino acid residue ARG-98 and two π-π stacking interactions with amino acid residue PHE-392, indicating that compound 9 had better herbicidal activity than pyraflufen-ethyl. It shows that compound 9 is expected to be a lead compound of phenylpyrazole PPO inhibitor herbicide and used as a herbicide in wheat field.

Chemical preparation, degradation analysis, computational docking and biological activities of novel sulfonylureas with 2,5-disubstituted groups.

Based on the previous finding that a substitution at 5-position of the benzene ring is favorable to enhance the degradation rates of sulfonylurea herbicides, a total of 16 novel 2,5-disubsituted sulfonylurea compounds were chemically synthesized and fully characterized by means of 1H NMR, 13C NMR, HRMS and X-ray diffraction. By using HPLC analysis, the degradation behavior of M03, a compound belonging to this family, was studied and confirmed that chlorsulfuron itself is not a degraded product of the 2,5-disubstituted sulfonylureas. Inhibition constants against plant acetohydroxyacid synthase (AHAS) were determined for selected compounds, among which SU3 showed seven times stronger activity against the mutant W574L enzyme than chlorsulfuron. Molecular docking suggested that the substituted group at 5-position of benzene ring is likely to interact with the surrounding residues Met200 and Asp376 of AtAHAS. From the greenhouse herbicidal assay and crop safety test, SU5 and SU6 are considered as herbicide candidates to control dicotyledon weeds in corn, while SU3 is likely to be a promising candidate to control dicotyledon weed species and barnyard grass in wheat. The present research has therefore provided some new insights to understand the structure-activity relationships of herbicidal sulfonylureas with di-substitutions at benzene ring.

Synthesis, Herbicidal Activity, Crop Safety and Soil Degradation of Pyrimidine- and Triazine-Substituted Chlorsulfuron Derivatives.

Chlrosulfuron, a classical sulfonylurea herbicide that exhibits good safety for wheat but causes a certain degree of damage to subsequent corn in a wheat-corn rotation mode, has been suspended field application in China since 2014. Our previous study found that diethylamino-substituted chlorsulfuron derivatives accelerated the degradation rate in soil. In order to obtain sulfonylurea herbicides with good crop safety for both wheat and corn, while maintaining high herbicidal activities, a series of pyrimidine- and triazine-based diethylamino-substituted chlorsulfuron derivatives (W102-W111) were systematically evaluated. The structures of the synthesized compounds were confirmed with 1H NMR, 13C NMR, and HRMS. The preliminary biological assay results indicate that the 4,6-disubstituted pyrimidine and triazine derivatives could maintain high herbicidal activity. It was found that the synthesized compounds could accelerate degradation rates, both in acidic and alkaline soil. Especially, in alkaline soil, the degradation rate of the target compounds accelerated more than 22-fold compared to chlorsulfuron. Moreover, most chlorsulfuron analogs exhibited good crop safety for both wheat and corn at high dosages. This study provided a reference for the further design of new sulfonylurea herbicides with high herbicidal activity, fast degradation rates, and high crop safety.

The diverse functional genes of maize rhizosphere microbiota assessed using shotgun metagenomics.

BACKGROUND: The geographical diversification in chemical, biological and physical properties of plant biospheres instigates heterogenicity in the proliferation of important soil microbiome. Controlling functions and structure of plant rhizosphere from a better understanding and prediction of a plant's immediate environment will help assess plant-microbe interplay, improve the productivity of plant ecosystems and improve plant response to adverse soil conditions. Here we characterized functional genes of the microbial community of maize rhizosphere using a culture-independent method. RESULTS: Our metadata showed microbial genes involved in nitrogen fixation, phosphate solubilization, quorum sensing molecules, trehalose, siderophore production, phenazine biosynthesis protein, daunorubicin resistance, acetoin, 1-aminocyclopropane-1-carboxylate deaminase, 4-hydroxybenzoate, disease control and stress-reducing genes (superoxidase dismutase, catalase, peroxidase, etc.). ß-Diversity showed that there is a highly significant difference between most of the genes mined from rhizosphere soil samples and surrounding soils. CONCLUSIONS: The high relative abundance of stress-reducing genes mined from this study showed that the sampling sites harbor not only important plant-beneficial organisms but also a hotspot for developing bio-fertilizers. Nevertheless, since most of these organisms are unculturable, mapping cultivation strategies for their growth could make them readily available as bio-inoculants and possible biotechnological applications in the future. © 2020 Society of Chemical Industry.

Evaluation of the use of untargeted metabolomics in the safety assessment of genetically modified crops.

BACKGROUND: The safety assessment of foods and feeds from genetically modified (GM) crops includes the comparison of key characteristics, such as crop composition, agronomic phenotype and observations from animal feeding studies compared to conventional counterpart varieties that have a history of safe consumption, often including a near isogenic variety. The comparative compositional analysis of GM crops has been based on targeted, validated, quantitative analytical methods for the key food and feed nutrients and antinutrients for each crop, as identified by Organization of Economic Co-operation and Development (OCED). As technologies for untargeted metabolomic methods have evolved, proposals have emerged for their use to complement or replace targeted compositional analytical methods in regulatory risk assessments of GM crops to increase the number of analyzed metabolites. AIM OF REVIEW: The technical opportunities, challenges and strategies of including untargeted metabolomics analysis in the comparative safety assessment of GM crops are reviewed. The results from metabolomics studies of GM and conventional crops published over the last eight years provide context to enable the discussion of whether metabolomics can materially improve the risk assessment of food and feed from GM crops beyond that possible by the Codex-defined practices used worldwide for more than 25 years. KEY SCIENTIFIC CONCEPTS OF REVIEW: Published studies to date show that environmental and genetic factors affect plant metabolomics profiles. In contrast, the plant biotechnology process used to make GM crops has little, if any consequence, unless the inserted GM trait is intended to alter food or feed composition. The nutritional value and safety of food and feed from GM crops is well informed by the quantitative, validated compositional methods for list of key analytes defined by crop-specific OECD consensus documents. Untargeted metabolic profiling has yet to provide data that better informs the safety assessment of GM crops than the already rigorous Codex-defined quantitative comparative assessment. Furthermore, technical challenges limit the implementation of untargeted metabolomics for regulatory purposes: no single extraction method or analytical technique captures the complete plant metabolome; a large percentage of metabolites features are unknown, requiring additional research to understand if differences for such unknowns affect food/feed safety; and standardized methods are needed to provide reproducible data over time and laboratories.

Calcium Plays a Double-Edged Role in Modulating Cadmium Uptake and Translocation in Rice.

Cadmium (Cd) contamination in soils poses great risks to both agricultural production and human health. Calcium (Ca) is an essential element playing a significant role in protecting plants against Cd toxicity. However, how Ca affects Cd uptake and translocation in rice is still not fully elucidated. In this study, the regulatory role of Ca in Cd uptake and upward translocation was investigated in rice at different growth stages. Our results showed that the supplement of 5 mM Ca significantly reduced Cd uptake by rice roots, because of their competition for Ca-permeable channels as an absorption site and Ca-induced downregulation of OsNRAMP1 and OsNRAMP5. However, Ca application facilitated the upward translocation of Cd by both upregulating OsHMA2 to induce xylem loading of Cd and downregulating OsHMA3 to reduce vacuolar sequestration of Cd. Such contrary results suggested a double-edged role of Ca in regulating root Cd uptake and root-to-shoot Cd translocation in rice. Although it increased Cd content in the aboveground vegetative tissues during the whole growth period, the addition of 5 mM Ca eventually decreased Cd content in rice grains at the ripening stage. All these results suggest that Ca-based amendments possess great potential for the production of low-Cd rice grains.

Natural attenuation of toxic metal phytoavailability in 35-year-old sewage sludge-amended soil.

Toxic heavy metals persist in agricultural soils and ecosystem for many decades after their application as contaminants in sewage sludge and fertilizer products This study assessed the potential long-term risk of cadmium (Cd), lead (Pb), zinc (Zn), and copper (Cu) in land-applied sewage sludge to food crop contamination. A sewage sludge-amended soil (SAS) aged in the field more than 35 years was used in a greenhouse pot experiment with leafy vegetables (lettuce and amaranth) having strong Cd and Zn accumulation tendencies. Soil media with variable levels of available Cd, Zn, and Cu (measured using 0.01 M CaCl2 extraction) were prepared by diluting SAS with several levels of uncontaminated control soil. Despite long-term aging in the field, the sludge site soil still retains large reserves of heavy metals, residual organic matter, phosphorus, and other nutrients, but its characteristics appear to have stabilized over time. Nevertheless, lettuce and amaranth harvested from the sludge-treated soil had undesirable contents of Cd and Zn. The high plant uptake efficiency for Cd and Zn raises a concern regarding the quality and safety of leafy vegetables in particular, when these crops are grown on soils that have been amended heavily with sewage sludge products at any time in their past.

Design, Synthesis and Proteomics-Based Analysis of Novel Triazinone Derivatives Containing Amide Structures as Safer Protoporphyrinogen IX Oxidase Inhibitors.

Resistant weeds severely threaten crop yields as they compete with crops for resources required for survival. Trifludimoxazin, a protoporphyrinogen IX oxidase (PPO) inhibitor, can effectively control resistant weeds. However, its crop safety record is unsatisfactory. Consequently, a scaffold-hopping strategy is employed in this study to develop a series of new triazinone derivatives featuring an amide structure. Most compounds depicted excellent herbicidal activity across a broad spectrum at 37.5-150 g ai/ha, among which (R)-I-5 was equivalent to flumioxazin. (R)-I-5 demonstrated significant crop tolerance to rice and wheat, even at 150 g ai/ha. (R)-I-5 exhibited superior pharmacokinetic features compared to flumioxazin and trifludimoxazin. This was depicted by the absorption, distribution, metabolism, excretion, and toxicity predictions. Notably, proteomics-based analysis was applied for the first time to investigate variations among plant proteins before and after herbicide application, shedding light on the conservative and divergent roles of PPO.

Evaluation of Bipolaris yamadae as a bioherbicidal agent against grass weeds in arable crops.

BACKGROUND: Weeds are among the most damaging pests of agriculture, causing ≈10% worldwide reduction in crop productivity each year. Over-reliance on synthetic chemical herbicides has caused weeds around the world to evolve resistance. Bioherbicides may be an alternative. However, among their many constraints including strict environmental requirements, complicated mass-production and high product costs, limited pathogenicity and a narrow spectrum of activity are frequently encountered and are major barriers to commercialization. RESULTS: We isolated a pathogenic fungus, HXDC-1-2, from diseased leaves of a gramineous weed, stiltgrass [Microstegium vimineum (Trin.) A. Camus], from the edge of farmland in Guizhou province, China. HXDC-1-2 was identified as the fungal species Bipolaris yamadae based on the morphological characteristics and ITS-GPDH-EF1α multiple primer analysis. Its potential as a bioherbicide was evaluated by determining its weed control efficacy and crop safety. The ED50 and ED90 values of HXDC-1-2 on Echinochloa crus-galli were 3.22 × 103 and 1.32 × 105 conidia mL-1 , respectively. Host range tests revealed that 20 gramineous weeds including Setaria viridis, Leptochloa chinensis, Eleusine indica, Pseudosorghum zollingeri, Leptochloa panicea, Bromus catharticus, E. crus-galli plants, were extremely susceptible whereas 77 crop species from 27 plant families including rice, wheat, barley, corn, soybean and cotton (excluding cowpea and sorghum) were unaffected. CONCLUSION: Bipolaris yamadae strain HXDC-1-2 has great potential to be developed as a commercial broad-spectrum bioherbicidal agent for controlling grass weeds in arable crops. © 2023 Society of Chemical Industry.

Comprehensive assessment of health and ecological risk of cadmium in agricultural soils across China: A tiered framework.

Soil cadmium (Cd) contamination has been increasingly serious in agricultural land across China, posing unexpected risks to human health concerning crop safety and terrestrial ecosystems. This study collected Cd concentration data from 3388 soil sites in agricultural regions. To assess the Cd risk to crop safety, a comprehensive sampling investigation was performed to develop reliable Soil Plant Transfer (SPT) model. Eco-toxicity tests with representative soils and organism was conducted to construct the Species Sensitivity Distribution (SSD) for ecological risk assessment. Then, a tiered framework was applied based on Accumulation index, deterministic method (Hazard quotient), and probabilistic assessment (Monte Carlo and Joint Probability Curve). The results revealed the widespread Cd enrichment in agricultural soils, mainly concentrated in Central, Southern, and Southwest China. Risk assessments demonstrated the greater risks related to crop safety, while the ecological risks posed by soil Cd were manageable. Notably, agricultural soils in southern regions of China exhibited more severe risks to both crop safety and soil ecosystem, compared to other agricultural regions. Furthermore, tiered methodology proposed here, can be adapted to other trace elements with potential risks to crop safety and terrestrial ecosystem.

Exceptional anti-toxic growth of water spinach in arsenic and cadmium co-contaminated soil remediated using biochar loaded with Bacillus aryabhattai.

Functionalized biochars are crucial for simultaneous soil remediation and safe agricultural production. However, a comprehensive understanding of the remediation mechanism and crop safety is imperative. In this work, the all-in-one biochars loaded with a Bacillus aryabhattai (B10) were developed via physisorption (BBC) and sodium alginate embedding (EBC) for simultaneous toxic As and Cd stabilization in soil. The bacteria-loaded biochar composites significantly decreased exchangeable As and Cd fractions in co-contaminated soil, with enhanced residual fractions. Heavy metal bioavailability analysis showed a maximum CaCl2-As concentration decline of 63.51% and a CaCl2-Cd decline of 50.96%. At a 3% dosage of composite, rhizosphere soil showed improved organic matter, cation exchange capacity, and enzyme activity. The aboveground portion of water spinach grown in pots was edible, with final As and Cd contents (0.347 and 0.075 mg·kg⁻¹, respectively) meeting food safety standards. Microbial analysis revealed the composite's influence on the rhizosphere microbial community, favoring beneficial bacteria and reducing plant pathogenic fungi. Additionally, it increased functional microorganisms with heavy metal-resistant genes, limiting metal migration in plants and favoring its growth. Our research highlights an effective strategy for simultaneous As and Cd immobilization in soil and inhibition of heavy metal accumulation in vegetables.

Discovery of Novel (5-Mercapto-4-phenyl-4H-1,2,4-triazol-3-yl)methyl Phenyl Carbamate as a Potent Phytoene Desaturase Inhibitor through Scaffold Hopping and Linker Modification.

Phytoene desaturase (PDS) is a key rate-limiting enzyme in the carotenoid biosynthesis pathway. Although commercial PDS inhibitors have been developed for decades, it remains necessary to develop novel PDS inhibitors with higher bioactivity. In this work, we used the scaffold hopping and linker modification approaches to design and synthesize a series of compounds (7a-7o, 8a-8l, and 14a-14d). The postemergence application assay demonstrated that 8e and 7e separately showed the best herbicidal activity at 750 g a.i./ha and lower doses (187.5 g, 375g a.i./ha) without no significant toxicity to maize and wheat. The surface plasmon resonance revealed strong binding affinity between 7e and Synechococcus PDS (SynPDS). The HPLC analysis confirmed that 8e at 750 g a.i./ha caused significant phytoene accumulation in Arabidopsis seedlings. This work demonstrates the efficacy of structure-guided optimization through scaffold hopping and linker modification to design potent PDS inhibitors with enhanced bioactivity and crop safety.

Chemical Synthesis, Herbicidal Activity, Crop Safety, and Molecular Basis of ortho-Fluoroalkoxy Substituted Sulfonylureas as Novel Acetohydroxyacid Synthase Inhibitors.

In the face of increasing resistance to the currently used commercial herbicides and the lack of success in identifying new herbicide targets, alternative herbicides need to be developed to control unwanted monocotyledon grasses in food crops. Here, a panel of 29 novel sulfonylurea-based compounds with ortho-fluoroalkoxy substitutions at the phenyl ring were designed and synthesized. Pot assays demonstrated that two of these compounds, 6d and 6u, have strong herbicidal activities against Echinochloa crus-galli, Eleusine indica, Alopecurus aequalis, and Alopecurus japonicus Steudel at a dosage of 15 g ha-1. Furthermore, these two compounds exhibited <5% inhibition against wheat at a dosage of 30 g ha-1 under post-emergence conditions. 6u also exhibited <5% inhibition against rice at a dosage of 30 g ha-1 under both post-emergence and pre-emergence conditions. A kinetics study demonstrated that 6d and 6u are potent inhibitors of Arabidopsis thaliana acetohydroxyacid synthase (AHAS; EC 2.2.1.6) with potent Ki values of 18 ± 1.1 and 11.9 ± 4.0 nM, respectively. The crystal structure of 6u in complex with A. thaliana (At)AHAS has also been determined at 2.7 Å resolution. These new compounds represent new alternative herbicide choices to protect wheat or rice from invading grasses.

Synthesis and Characterization of Mesoporous Silica Nanoparticles Loaded with P-Cymene against Rice Bacterial Blight.

Mesoporous silica nanoparticles (MSNs) can be used as carrier materials for the controlled release of pesticides while reducing their negative environmental impact. In this study, we screened an active ingredient, p-cymene (PC), with an excellent inhibitory effect on rice bacterial blight. Subsequently, the PC was successfully loaded onto MSNs via physisorption (PC@MSNs). PC@MSNs, characterized by a regular spherical shape, smooth surface, and an MSN average size of 262.9 nm, achieved an 8.6% drug loading capacity. The release kinetics of the PC from the PC@MSNs demonstrated a sustained release (288 h) pattern influenced by drug diffusion. The efficacy of the PC@MSNs against Xanthomonas oryzae pv. Oryzae paralleled those of PC. Acute toxicity assays revealed that the PC@MSNs were less toxic to aquatic life (LC50 = 257.867 mg/L) and that the formulation showed no adverse effects on rice seedling growth. In summary, these results suggest that PC@MSNs can broaden PC's scope of application in managing rice diseases.

Structure-Based Design of 4-Hydroxyphenylpyruvate Dioxygenase Inhibitor as a Potential Herbicide for Cotton Fields.

4-Hydroxyphenylpyruvate dioxygenase (HPPD, EC 1.13.11.27) is one of the most promising herbicide targets for the development of agricultural chemicals owing to its unique mechanism of action in plants. We previously reported on the co-crystal structure of Arabidopsis thaliana (At) HPPD complexed with methylbenquitrione (MBQ), an inhibitor of HPPD that we previously discovered. Based on this crystal structure, and in an attempt to discover even more effective HPPD-inhibiting herbicides, we designed a family of triketone-quinazoline-2,4-dione derivatives featuring a phenylalkyl group through increasing the interaction between the substituent at the R1 position and the amino acid residues at the active site entrance of AtHPPD. Among the derivatives, 6-(2-hydroxy-6-oxocyclohex-1-ene-1-carbonyl)-1,5-dimethyl-3-(1-phenylethyl)quinazoline-2,4(1H,3H)-dione (23) was identified as a promising compound. The co-crystal structure of compound 23 with AtHPPD revealed that hydrophobic interactions with Phe392 and Met335, and effective blocking of the conformational deflection of Gln293, as compared with that of the lead compound MBQ, afforded a molecular basis for structural modification. 3-(1-(3-Fluorophenyl)ethyl)-6-(2-hydroxy-6-oxocyclohex-1-ene-1-carbonyl)-1,5-dimethylquinazoline-2,4(1H,3H)-dione (31) was confirmed to be the best subnanomolar-range AtHPPD inhibitor (IC50 = 39 nM), making it approximately seven times more potent than MBQ. In addition, the greenhouse experiment showed favorable herbicidal potency for compound 23 with a broad spectrum and acceptable crop selectivity against cotton at the dosage of 30-120 g ai/ha. Thus, compound 23 possessed a promising prospect as a novel HPPD-inhibiting herbicide candidate for cotton fields.

Designing New Protoporphyrinogen Oxidase-Inhibitors Carrying Potential Side Chain Isosteres to Enhance Crop Safety and Spectrum of Activity.

There are several methods to control weeds, which impose particular challenges for farmers in all parts of the world, although applying small molecular compounds still remains the most efficient technology to date. However, plants can evolve to become resistant toward active ingredients which is also the case for protoporphyrinogen oxidase (PPO) inhibitors, a class of highly effective herbicides in use for more than 50 years. Hence, it is essential to continuously discover and develop new herbicidal PPO inhibitors with enhanced intrinsic activity, an improved resistance profile, enhanced crop safety, favorable physicochemical properties, and a clean toxicological profile. By modifying structural key features from known PPO inhibitors such as tiafenacil, inspired by isostere and mix&match concepts in combination with modeling investigations based on a wild-type Amaranthus crystal structure, we have found new promising lead structures showing strong activity in vitro and in vivo against several notorious dicotyledon and monocotyledon weeds with emerging resistance (e.g., Amaranthus palmeri, Amaranthus tuberculatus, Lolium rigidum, and Alopecurus myosuroides). While several phenyl uracils carrying an isoxazoline motif in their thio-linked side chain showed promising resistance-breaking potential against different Amaranthus species, introducing a thioacrylamide side chain afforded outstanding efficacy against resistant grass weeds.

Integrative effects of microbial inoculation and amendments on improved crop safety in industrial soils co-contaminated with organic and inorganic pollutants.

Soils co-contaminated by organic and inorganic pollutants usually pose major ecological risks to soil ecosystems including plants. Thus, effective strategies are needed to alleviate the phytotoxicity caused by such co-contamination. In this study, microbial agents (a mixture of Bacillus subtilis, Sphingobacterium multivorum, and a commercial microbial product named OBT) and soil amendments (ß-cyclodextrin, rice husk, biochar, calcium magnesium phosphate fertilizer, and organic fertilizer) were evaluated to determine their applicability in alleviating toxicity to crops (maize and soybean) posed by polycyclic aromatic hydrocarbon (PAHs) and potentially toxic metals co-contaminated soils. The results showed that peroxidase, catalase, and superoxide dismutase activity levels in maize or soybean grown in severely or mildly contaminated soils were significantly enhanced by the integrative effects of amendments and microbial agents, compared with those in single plant treatments. The removal rates of Zn, Pb, and Cd in severely contaminated soils were 49 %, 47 %, and 51 % and 46 %, 45 %, and 48 %, for soybean and maize, respectively. The total contents of Cd, Pb, Zn, and PAHs in soil decreased by day 90. Soil organic matter content, levels of nutrient elements, and enzyme activity (catalase, urease, and dehydrogenase) increased after the amendments and application of microbial agents. Moreover, the amendments and microbial agents also increased the diversity and distribution of bacterial species in the soil. These results suggest that the amendments and microbial agents were beneficial for pollutant purification, improving the soil environment and enhancing both plant resistance to pollutants and immune systems of plants.

Discovery of Novel Pyrazole Derivatives with Improved Crop Safety as 4-Hydroxyphenylpyruvate Dioxygenase-Targeted Herbicides.

As one of the essential herbicide targets, 4-hydroxyphenylpyruvate dioxygenase (HPPD) has recently been typically used to produce potent new herbicides. In continuation with the previous work, several pyrazole derivatives comprising a benzoyl scaffold were designed and synthesized, and their inhibitory effects on Arabidopsis thaliana hydroxyphenylpyruvate dioxygenase (AtHPPD) and herbicidal activities were comprehensively evaluated in this study. Compound Z9 showed top-rank inhibitory activity to AtHPPD with an half-maximal inhibitory concentration (IC50) value of 0.05 µM, which was superior to topramezone (1.33 µM) and mesotrione (1.76 µM). Compound Z21 exhibited superior preemergence inhibitory activity against Echinochloa crusgalli, with stem and root inhibition rates of 44.3 and 69.6%, respectively, compared to topramezone (16.0 and 53.0%) and mesotrione (12.8 and 41.7%). Compounds Z5, Z15, Z20, and Z21 showed excellent postemergence herbicidal activities at a dosage of 150 g ai/ha, along with distinct bleaching symptoms and higher crop safety than topramezone and mesotrione, and they all were safe for maize, cotton, and wheat with injury rates of 0 or 10%. In addition, the molecular docking analysis also revealed that these compounds formed hydrophobic π-π interactions with Phe360 and Phe403 to AtHPPD. This study suggests that pyrazole derivatives containing a benzoyl scaffold could be used as new HPPD inhibitors to develop pre- and postemergence herbicides and be applied to additional crop fields.

Design, Synthesis, and Biological Activity Determination of Novel Phenylpyrazole Protoporphyrinogen Oxidase Inhibitor Herbicides Containing Five-Membered Heterocycles.

Protoporphyrinogen oxidase (PPO, EC 1.3.3.4) inhibitor herbicides have attracted widespread attention in recent years as ideal herbicides due to their high efficiency, low toxicity, and low pollution. In this article, 30 phenylpyrazole derivatives containing five-membered heterocycles were designed and synthesized according to the principle of bioelectronic isoarrangement and active substructure splicing. A series of structural characterizations were performed on the synthesized compounds. The herbicide activity in greenhouse was evaluated to determine their growth inhibition effect on weeds, their IC50 value through in vitro PPO enzyme activity measurement was calculated, and target compounds 2i and 3j that have herbicide effects comparable to pyraflufen-ethyl were selected. Crop safety experiments have shown that when the spraying concentration is 300 g of ai/ha, gramineous crops such as wheat, corn, and rice are more tolerant to compound 2i, with wheat exhibiting high tolerance, which is equivalent to the crop safety of pyraflufen-ethyl. Compound 2i can be used as a candidate herbicide for wheat, corn, and paddy fields, and the results are consistent with the cumulative concentration experiment. Molecular docking results showed that compound 2i interacted with the amino acid residue ARG-98 by forming two hydrogen bonds and interacted with the amino acid residue PHE-392 by forming two π-π stacking interactions, indicating that compound 2i has more excellent herbicidal activity than pyraflufen-ethyl and is expected to become a potential lead compound of phenylpyrazole PPO inhibitor herbicides.

Modeling banana uptake of pesticides by incorporating a peel-pulp interaction system into a multicompartment fruit tree model.

According to field research, banana peels have a significant impact on the uptake of pesticide residues by banana pulps. To predict pesticide residue concentrations in harvested bananas, however, current modeling approaches did not take into consideration the banana peel as a single simulating compartment. To address the problem, we incorporated a peel-pulp interaction system into a modified multicompartment fruit tree model in order to simulate pesticide residue concentrations in banana plants. The simulation results revealed that lipophilicity played a crucial role in regulating pesticide bioaccumulation in banana plants, showing that moderately- or highly-lipophilic compounds had a high potential for bioaccumulation in banana pulps and peels. Some model inputs, such as peel thickness, degradation rates in plant tissues, and dissipation rates in the soil, had a substantial impact on the bioaccumulation of pesticides in banana pulps and peels. Even if more aspects (such as dynamically morphological properties of banana plants and ionizable chemical compounds) must be considered for in future research, the proposed modeling approach can aid in the comprehension of the pesticide bioaccumulation mechanism in banana plants.