The promotion of the atrazine degradation mechanism by humic acid in a soil microbial electrochemical system.

The enhancing effects of anodes on the degradation of the organochlorine pesticide atrazine (ATR) in soil within microbial electrochemical systems (MES) have been extensively researched. However, the impact and underlying mechanisms of soil microbial electrochemical systems (MES) on ATR degradation, particularly under conditions involving the addition of humic acids (HAs), remain elusive. In this investigation, a soil MES supplemented with humic acids (HAs) was established to assess the promotional effects and mechanisms of HAs on ATR degradation, utilizing EEM-PARAFAC and SEM analyses. Results revealed that the maximum power density of the MES in soil increased by 150%, and the degradation efficiency of ATR improved by over 50% following the addition of HAs. Furthermore, HAs were found to facilitate efficient ATR degradation in the far-anode region by mediating extracellular electron transfer. The components identified as critical in promoting ATR degradation were Like-Protein and Like-Humic acid substances. Analysis of the microbial community structure indicated that the addition of HAs favored the evolution of the soil MES microbial community and the enrichment of electroactive microorganisms. In the ATR degradation process, the swift accumulation of Hydrocarbyl ATR (HYA) was identified as the primary cause for the rapid degradation of ATR in electron-rich conditions. Essentially, HA facilitates the reduction of ATR to HYA through mediated bonded electron transfer, thereby markedly enhancing the efficiency of ATR degradation.

Culture optimization of Streptomyces sp. KRA16-334 for increased yield of new herbicide 334-W4.

This study aimed to isolate actinomycetes that exhibit strong herbicidal activity, identify compounds active against weeds, and researching methods to improve the production of these compounds through culture optimization to establish a foundation for the development of environmentally friendly bioherbicides. 334-W4, one of the herbicidal active substances isolated from the culture broth of Streptomyces sp. KRA16-334, exhibited herbicidal activity against various weeds. The molecular formula of 334-W4 was determined to be C16H26N2O6, based on ESI-MS (m/z) and 1H and 13C NMR spectral data. It had molecular weight 365.1689 [M+Na] and 343.1869 [M+H], indicating the presence of the epoxy-ß-aminoketone moiety based on HMBC correlations. Additionally, selective culture was possible depending on the addition of trifluoroacetic acid (TFA) during culture with GSS medium. Experiments confirmed that exposure of the KRA16-334 strain to UV irradiation (254 nm, height 17 cm) for 45 seconds improved the yield of the active substance (334-W4) by over 200%. As a result of examining yields of active materials of four mutants selected through optimization of culture conditions such as temperature, agitation, and initial pH, the yield of one mutant 0723-8 was 264.7 ± 12.82 mg/L, which was 2.8-fold higher than that of wild-type KRA16-334 at 92.8 ± 5.48 mg/L.

Understanding the Effects of Ligand Configuration on Protoporphyrinogen IX Oxidase with Rationally Designed 3-(N-Phenyluracil)but-2-enoates.

Protoporphyrinogen IX oxidase (PPO, EC 1.3.3.4) is a promising target for green herbicide discovery. However, the ligand configuration effects on PPO activity were still poorly understood. Herein, we designed 3-(N-phenyluracil)but-2-enoates using our previously developed active fragments exchange and link (AFEL) approach and synthesized a series of novel compounds with nanomolar ranges of Nicotiana tabacum PPO (NtPPO) inhibitory potency and promising herbicidal potency. Our systematic structure-activity relationship investigations showed that the E isomers of 3-(N-phenyluracil)but-2-enoates displayed improved bioactivity than their corresponding Z isomers. Using molecular simulation studies, we found that the E isomers showed a relatively lower entropy change and could sample more stable binding conformation to the receptor than the Z isomers. Our density functional theory (DFT) calculations showed that the E isomers showed higher chemical reactivity and lower electronic chemical potential than their corresponding Z isomers. Compound E-Ic emerged as the optimal compound with a Ki value of 3.0 nM against NtPPO, exhibiting a broader spectrum of weed control than saflufenacil at 37.5-75 g ai/ha and also safe to maize at 75 g ai/ha, which could be considered as a promising lead herbicide for further development.

Prediction of atrazine degradation in soil based on XGBoost model.

We established the optimal model by using the automatic machine learning method to predict the degradation efficiency of herbicide atrazine in soil, which could be used to assess the residual risk of atrazine in soil. We collected 494 pairs of data from 49 published articles, and selected seven factors as input features, including soil pH, organic matter content, saturated hydraulic conductivity, soil moisture, initial concentration of atrazine, incubation time, and inoculation dose. Using the first-order reaction rate constant of atrazine in soil as the output feature, we established six models to predict the degradation efficiency of atrazine in soil, and conducted comprehensive analysis of model performance through linear regression and related evaluation indicators. The results showed that the XGBoost model had the best performance in predicting the first-order reaction rate constant (k). Based on the prediction model, the feature importance ranking of each factor was in an order of soil moisture > incubation time > pH > organic matter > initial concentration of atrazine > saturated hydraulic conductivity > inoculation dose. We used SHAP to explain the potential relationship between each feature and the degradation ability of atrazine in soil, as well as the relative contribution of each feature. Results of SHAP showed that time had a negative contribution and saturated hydraulic conductivity had a positive contribution. High values of soil moisture, initial concentration of atrazine, pH, inoculation dose and organic matter content were generally distributed on both sides of SHAP=0, indicating their complex contributions to the degradation of atrazine in soil. The XGBoost model method combined with the SHAP method had high accuracy in predicting the performance and interpretability of the k model. By using machine learning method to fully explore the value of historical experimental data and predict the degradation efficiency of atrazine using environmental parameters, it is of great significance to set the threshold for atrazine application, reduce the residual and diffusion risks of atrazine in soil, and ensure the safety of soil environment.

Discovery of Novel Pyrazole Acyl Thiourea Skeleton Analogue as Potential Herbicide Candidates.

To discover novel transketolase (TKL, EC 2.2.1.1) inhibitors with potential herbicidal applications, a series of pyrazole acyl thiourea derivatives were designed based on a previously obtained pyrazolamide acyl lead compound, employing a scaffold hopping strategy. The compounds were synthesized, their structures were characterized, and they were evaluated for herbicidal activities. The results indicate that 7a exhibited exceptional herbicidal activity against Digitaria sanguinalis and Amaranthus retroflexus at a dosage of 90 g ai/ha, using the foliar spray method in a greenhouse. This performance is comparable to that of commercial products, such as nicosulfuron and mesotrione. Moreover, 7a showed moderate growth inhibitory activity against the young root and stem of A. retroflexus at 200 mg/L in the small cup method, similar to that of nicosulfuron and mesotrione. Subsequent mode-of-action verification experiments revealed that 7a and 7e inhibited Setaria viridis TKL (SvTKL) enzyme activity, with IC50 values of 0.740 and 0.474 mg/L, respectively. Furthermore, they exhibited inhibitory effects on the Brassica napus acetohydroxyacid synthase enzyme activity. Molecular docking predicted potential interactions between these (7a and 7e) and SvTKL. A greenhouse experiment demonstrated that 7a exhibited favorable crop safety at 150 g ai/ha. Therefore, 7a is a promising herbicidal candidate that is worthy of further development.

Design, Synthesis, and Mode of Action of Thioacetamide Derivatives as the Algicide Candidate Based on Active Substructure Splicing Strategy.

Lakes and reservoirs worldwide are experiencing a growing problem with harmful cyanobacterial blooms (HCBs), which have significant implications for ecosystem health and water quality. Algaecide is an effective way to control HCBs effectively. In this study, we applied an active substructure splicing strategy for rapid discovery of algicides. Through this strategy, we first optimized the structure of the lead compound S5, designed and synthesized three series of thioacetamide derivatives (series A, B, C), and then evaluated their algicidal activities. Finally, compound A3 with excellent performance was found, which accelerated the process of discovering and developing new algicides. The biological activity assay data showed that A3 had a significant inhibitory effect on M. aeruginosa. FACHB905 (EC50 = 0.46 µM) and Synechocystis sp. PCC6803 (EC50 = 0.95 µM), which was better than the commercial algicide prometryn (M. aeruginosa. FACHB905, EC50 = 6.52 µM; Synechocystis sp. PCC6803, EC50 = 4.64 µM) as well as better than lead compound S5 (M. aeruginosa. FACHB905, EC50 = 8.80 µM; Synechocystis sp. PCC6803, EC50 = 7.70 µM). The relationship between the surface electrostatic potential, chemical reactivity, and global electrophilicity of the compounds and their activities was discussed by density functional theory (DFT). Physiological and biochemical studies have shown that A3 might affect the photosynthesis pathway and antioxidant system in cyanobacteria, resulting in the morphological changes of cyanobacterial cells. Our work demonstrated that A3 might be a promising candidate for the development of novel algicides and provided a new active skeleton for the development of subsequent chemical algicides.

Synthesis and Herbicidal Activity of 2-(2-Oxo-3-pyridyl-benzothiazol-6-yloxy)hexanoic Acids.

The discovery of a lead compound is fundamental to herbicide innovation, but the limited availability of valuable lead compounds has hindered their development in recent years. By utilizing the structural diversity-oriented inactive group strategy, 3-(2-pyridyl)-benzothiazol-2-one was identified as a promising lead scaffold for herbicides, starting from benzothiazole which is an inactive moiety commonly found in herbicides such as mefenacet, benazolin, benzthiazuron, and fenthiaprop-ethyl. To investigate the structure-activity relationship (SAR) of these chemicals, a series of 2-(2-oxo-3-pyridyl-benzothiazol-6-yloxy)hexanoic acid derivatives (VI01 ∼ VI28) were synthesized through classical nucleophilic SNAr reaction using halogenated pyridines and 6-methoxybenzothiazole-2-one. The chemical structures of all the title compounds were confirmed by NMR and MS analysis. Petri dish assays indicated that many compounds exhibited potent herbicidal activity against both broad-leaf weeds and grass weeds at 1.0 mg/L. The SAR analysis revealed that the presence of a trifluoromethyl group at the 5-position of pyridine is essential for herbicidal activity. Furthermore, carboxylic esters exhibit higher herbicidal activity compared to carboxylic amides and free acids, and the activity decreased with the extension of the carbon chain. The postemergence herbicidal activity of VI03 against 16 species of weeds was tested by pot experiments in a greenhouse. VI03 demonstrated comparable efficacy in controlling broadleaf weeds and superior efficacy in controlling grass weeds compared to carfentrazone ethyl. The present study has unveiled a novel molecular scaffold exhibiting remarkably potent herbicidal activity. These findings are anticipated to provide valuable insights for the advancement of new herbicides and offer an alternative approach for managing resistant weeds.

Design, Synthesis, and Biological Activity of Novel Phenyltriazolinone PPO Inhibitors Containing Five-Membered Heterocycles.

Protoporphyrinogen oxidase (PPO, EC 1.3.3.4) catalyzes the oxidation of protoporphyrinogen IX to protoporphyrin IX, which is a key step in the synthesis of porphyrins in vivo. PPO inhibitors use protoporphyrinogen oxidase as the target and block the biosynthesis process of porphyrin by inhibiting the activity of the enzyme, eventually leading to plant death. In this paper, phenyl triazolinone was used as the parent structure, and the five-membered heterocycle with good herbicidal activity was introduced by using the principle of substructure splicing. According to the principle of bioisosterism, the sulfur atoms on the thiophene ring were replaced with oxygen atoms. Finally, 33 phenyl triazolinones and their derivatives were designed and synthesized, and their characterizations and biological activities were investigated. The in vitro PPO inhibitory activity and greenhouse herbicidal activity of 33 target compounds were determined, and compound D4 with better activity was screened out. The crop safety determination, field weeding effect determination, weeding spectrum determination, and crop metabolism study were carried out. The results showed that compound D4 showed good safety to corn, soybean, wheat, and peanut but poor selectivity to cotton. The field weeding effect of this compound is comparable to that of the commercial herbicide sulfentrazone. The herbicidal spectrum experiment showed that compound D4 had a wide herbicidal spectrum and a good growth inhibition effect on dicotyledonous weeds. Molecular docking results showed that compound D4 forms a hydrogen bond with amino acid residue Arg-98 in the tobacco mitochondria (mtPPO)-active pocket and forms two π-π stacking interactions with Phe-392. This indicates that compound D4 has stronger PPO inhibitory activity. This indicates that compound D4 has wide prospects for development.

Potential Candidate Molecule of Photosystem II Inhibitor Herbicide-Brassicanate A Sulfoxide.

Brassicanate A sulfoxide, a secondary metabolite of broccoli, exhibited the inhibition of weed growth, but its mechanism of action on weeds remains unclear. To elucidate the mechanism by which brassicanate A sulfoxide suppresses weeds, this study explores the interaction between brassicanate A sulfoxide and the photosystem II D1 protein through molecular docking and molecular dynamics simulations. This research demonstrates that brassicanate A sulfoxide interacts with the photosystem II D1 protein by forming hydrogen bonds with Phe-261 and His-214. The successful expression of the photosystem II D1 protein in an insect cell/baculovirus system validated the molecular docking and dynamics simulations. Biolayer interferometry experiments elucidated that the affinity constant of brassicanate A sulfoxide with photosystem II was 2.69 × 10-3 M, suggesting that brassicanate A sulfoxide can stably bind to the photosystem II D1 protein. The findings of this study contribute to the understanding of the mode of action of brassicanate A sulfoxide and also aid in the development of natural-product-based photosynthesis-inhibiting herbicides.

Discovery of Tetrazolamide-benzimidazol-2-ones as Novel 4-Hydroxyphenylpyruvate Dioxygenase Inhibitors.

4-Hydroxyphenylpyruvate dioxygenase (HPPD, EC 1.13.11.27) is one of the most valuable herbicide targets due to its unique biological functions. In search of HPPD inhibitors with promising biological performance, we designed and synthesized a series of novel tetrazolamide-benzimidazol-2-ones using a structure-based drug design strategy. Among the synthesized compounds, 1-(2-chlorobenzyl)-3-methyl-N-(1-methyl-1H-tetrazol-5-yl)-2-oxo-2,3-dihydro-1H-benzo[d]imidazole-4-carboxamide, 25, IC50 = 10 nM, was identified to be the most outstanding HPPD inhibitor, which showed more than 36-fold increased Arabidopsis thaliana HPPD (AtHPPD) inhibition potency than mesotrione (IC50 = 363 nM). Our AtHPPD-25 complex indicated that one nitrogen atom on the tetrazole ring and the oxygen atom on the amide group formed a classical bidentate chelation interaction with the metal ion, the benzimidazol-2-one ring created a tight π-π stacking interaction with Phe381 and Phe424, and some hydrophobic interactions were also found between the ortho-Cl-benzyl group and surrounding residues. Compound 32 showed more than 80% inhibition against all four tested weeds at 150 g ai/ha by the postemergence application. Our results indicated that the tetrazolamide-benzimidazol-2-one scaffold may be a new lead structure for herbicide discovery.

Synthesis and Evaluation of New Phytotoxic Fluorinated Chalcones as Photosystem II and Seedling Growth Inhibitors.

The development of novel phytotoxic compounds has been an important aim of weed control research. In this study, we synthesized fluorinated chalcone derivatives featuring both electron-donating and electron-withdrawing groups. These compounds were evaluated both as inhibitors of the photosystem II (PSII) electron chain as well as inhibitors of the germination and seedling growth of Amaranthus plants. Chlorophyll a (Chl a) fluorescence assay was employed to evaluate their effects on PSII, while germination experiments were conducted to assess their impact on germination and seedling development. The results revealed promising herbicidal activity for (E)-3-(4-bromophenyl)-1-(4-fluorophenyl)prop-2-en-1-one (7 a) and (E)-1-(4-fluorophenyl)-3-phenylprop-2-en-1-one (7 e). Compounds 7 a and 7 e exhibited a reduction in Chl a parameters associated with performance indexes and electron transport per reaction center. This reduction suggests a decrease in PSII activity, attributed to the blockage of electron flow at the quinone pool. Molecular docking analyses of chalcone derivatives with the D1 protein of PSII revealed a stable binding conformation, wherein the carbonyl and fluorine groups interacted with Phe265 and His215 residues, respectively. Additionally, at a concentration of 100 µM, compound 7 e demonstrated pre- and post-emergent herbicidal activity, resulting in a reduction of the seed germination index, radicle and hypocotyl lengths of Amaranthus weeds.

Herbicide contamination of Batak plain agricultural soils and risk assessment.

Herbicide residue levels were analyzed in agricultural soils of Batak plain and health risk assessments were made for relevant pesticides. Herbicide contamination levels were analyzed with the use of Quick-Easy-Cheap-Efficient-Rugged-Safe (QuEChERS)-liquid chromatography/tandem mass spectrometry (LC-MS/MS) procedure. Herbicide-free soil samples were spiked at two different levels. Overall recovery of the method was 87.32%. Present findings were parallel to SANTE recovery limits. About 50% of collected samples from the study sites contained herbicides at different concentrations. Totally, eight herbicides were detected, and herbicide concentrations ranged between 1.085 and 1724.23 µg kg-1. Metolachlor had the highest concentration (1724.23 µg kg-1) in a sample taken close to the pesticide waste disposal area. Six herbicides were detected at different concentrations in the same sample. Persistent herbicides (terbuthylazine and pendimethalin) were detected in 35 samples. Risk assessments revealed that hazard index (HI) and hazard quotient (HQ) were less than 1. The greatest HQ values were identified for terbuthylazine as 2772.48 × 10-7 and 20793.61 × 10-7 for adults and children, respectively. The HI for all herbicides were 3916.05 × 10-7 for adult and 29370.39 × 10-7 for children.

Ecotoxicity studies reveal that organic cations in dicamba-derived ionic liquids can pose a greater environmental risk than the herbicide itself.

The following research provides novel and relevant insights into potential environmental consequences of combination of various organic cations with commercial systemic herbicide (dicamba), in accordance with a 'herbicidal ionic liquids' (HILs) strategy. Toxicity assays of five dicamba-based HILs comprising different hydrophobic and hydrophilic cations, namely choline [CHOL][DIC], ethyl betainate [BETC2][DIC], decyl betainate [BETC10][DIC], hexadecyl betainate [BETC16][DIC] and didecyldimethylammonium [DDA][DIC]), have been tested towards bacteria (Pseudomonas putida, Escherichia coli, Bacillus subtilis), algae (Chlorella vulgaris), fresh and marine water crustaceans (Daphnia magna, Artemia franciscana). The structure of respective substituents in the cation emerged as a decisive determinant of toxicity in the case of tested species. In consequence, small ions of natural origin ([CHOL] and [BETC2]) demonstrated toxicity numerous orders of magnitude lower compared to fully synthetic [DDA]. These results emphasize the role of cations' hydrophobicity, as well as origin, in the observed acute toxic effect. Time-dependent toxicity assays also indicated that betaine-type cations comprising an ester bond can rapidly transform into less harmful substances, which can generally result in a reduction in toxicity by even several orders of magnitude. Nonetheless, these findings challenge the concept of ionic liquids with herbicidal activity and give apparent parallels to adjuvant-dependent toxicity issues recently noted in typical herbicidal formulations.

Integrated Virtual Screening and Validation toward Potential HPPD Inhibition Herbicide.

4-Hydroxyphenylpyruvate dioxygenase (EC 1.13.11.27, HPPD) is one of the most widely studied herbicide targets and has gained significant attention. To identify potential effective HPPD inhibitors, a rational multistep virtual screening workflow was built, which included CBP models (based on the receptor-ligand interactions in the crystal complex), Hypogen models with activity prediction ability (according to the derivation of structure-activity relationships from a set of molecules with reported activity values), and a consensus docking procedure (consisting of LibDock, Glide, and CDOCKER). About 1 million molecules containing diketone or ß-keto-enol substructures were filtered by Lipinski's rules, CBP model, and Hypogen model. A total of 12 compounds with similar docking postures were generated by consensus docking. Eventually, four molecules were screened based on the specific binding pattern and affinity of the HPPD inhibitor. The biological evaluation in vivo displayed that compounds III-1 and III-2 exhibited comparable herbicidal activity to isoxaflutole and possessed superior safety on various crops (wheat, rice, sorghum, and maize). The ADMET prediction (absorption, distribution, metabolism, excretion, and toxicity) showed that compound III possessed relatively good toxicological results. This work provides a theoretical basis and valuable reference for the virtual screening and molecular design of novel HPPD inhibition herbicides.

Bioengineering of Cu2O structured macro-biotemplate for the ultra-efficient and selective hand-retrieval of glyphosate from agro-farms.

Glyphosate (Gly) is a massively utilized toxic herbicide exceeding its statutory restrictions, causing adverse environmental and health impacts. Engineered nanomaterials, even though are integral to remediate Gly, their practical use is limited due to time and energy driven purifications, and negative environmental impacts. Here, a 3D wide area (~1.6 ± 0.4 cm2) Cu2O nanoparticle supported biotemplate is designed using fish-scale wastes as a sustainable approach for the ultra-efficient and selective hand-remediation of Gly from real-time samples from agro-farms. While the innate metal binding and reducing ability of collagenous scales aided self-synthesis cum grafting of Cu2O, the selective binding potential of Cu2O to Gly facilitated its hand-retrieval; as assessed using optical characterizations, Fourier transform infrared spectroscopy, thermogravimetric analysis and liquid chromatography mass spectrometry. Optimization studies revealed extractions of diverse pay-loads of Gly between 0.1 µg/mL to 40 µg/mL per 80 mg biotemplate grafted with ~6.354 µg of sub-5 nm Cu2O and was exponential to the number of Cu2O@biotemplates. Even though pH and surfactant didn't have any impact on the adsorption of Gly to the Cu2O@biotemplates, increase in the ionic strength led to a drastic increase in the adsorption. Density function theory simulations unveiled the involvement of phosphonic and carboxylic groups of Gly for interaction with Cu2O with a bond length of 1.826 Å and 1.833 Å, respectively. Overall, our sustainably generated, cost-efficient, hand-retrievable Cu2O supported biotemplate can be generalized to extract diverse organophosphorus toxins from agro-farms and other sewage embodiments. SYNOPSIS: Glyphosate is an excessively applied herbicide with potent health hazards and carcinogenicity. Thus, a hand removable Cu2O-supported biotemplate to selectively and efficiently remediate glyphosate from irrigation water is developed.

Degradation of atrazine, glyphosate, and 2,4-D in soils collected from two contrasting crop rotations in Southwest Chaco, Argentina.

Argentina stands as one of the leading consumers of herbicides. In a laboratory incubation experiment, the persistence and production of degradation metabolites of Atrazine, 2,4-D, and Glyphosate were investigated in a loamy clay soil under two contrasting agricultural practices: continuous soybean cultivation (T1) and intensified rotations with grasses and legumes (T2). The soils were collected from a long-term no-till trial replicating the influence of the meteorological conditions in the productive region. The soil was enriched with diluted concentrations of 6.71, 9.95, and 24 mg a.i./kg-1 of soil for the respective herbicides, equivalent to annual doses commonly used in the productive region. Samples were taken at intervals of 0, 0.5, 1, 2, 4, 6, 8, 16, 32, and 64 days, and analysis was conducted using high-resolution liquid chromatography UPLC MS/MS. An optimal fit to the first-order kinetic model was observed for each herbicide in both rotations, resulting in relatively short half-lives. Intensified crop sequences favored the production of biotic degradation metabolites. The impact of the high frequency of soybean cultivation revealed a trend of soil acidification and a reduced biological contribution to attenuation processes in soil contamination.

Polyoxyethylene tallow amine and glyphosate exert different developmental toxicities on human pluripotent stem cells-derived heart organoid model.

The early stage of heart development is highly susceptible to various environmental factors. While the use of animal models has aided in identifying numerous environmental risk factors, the variability between species and the low throughput limit their translational potential. Recently, a type of self-assembling cardiac structures, known as human heart organoids (hHOs), exhibits a remarkable biological consistency with human heart. However, the feasibility of hHOs for assessing cardiac developmental risk factors remains unexplored. Here, we focused on the cardiac developmental effects of core components of Glyphosate-based herbicides (GBHs), the most widely used herbicides, to evaluate the reliability of hHOs for the prediction of possible cardiogenesis toxicity. GBHs have been proven toxic to cardiac development based on multiple animal models, with the mechanism remaining unknown. We found that polyoxyethylene tallow amine (POEA), the most common surfactant in GBHs formulations, played a dominant role in GBHs' heart developmental toxicity. Though there were a few differences in transcriptive features, hHOs exposed to sole POEA and combined POEA and Glyphosate would suffer from both disruption of heart contraction and disturbance of commitment in cardiomyocyte isoforms. By contrast, Glyphosate only caused mild epicardial hyperplasia. This study not only sheds light on the toxic mechanism of GBHs, but also serves as a methodological demonstration, showcasing its effectiveness in recognizing and evaluating environmental risk factors, and deciphering toxic mechanisms.

Nitrogen-fertilizer addition to an agricultural soil enhances biogenic non-extractable residue formation from 2-13C,15N-glyphosate.

Glyphosate and nitrogen (N) or (P) phosphorus fertilizers are often applied in combination to agricultural fields. The additional P or N supply to microorganisms might drive glyphosate degradation towards sarcosine/glycine or aminomethylphosphonic acid (AMPA), and consequently determine the speciation of non-extractable residues (NERs): harmless biogenic NERs (bioNERs) or potentially hazardous xenobiotic NERs (xenoNERs). We therefore investigated the effect of P or N-fertilizers on microbial degradation of glyphosate and bioNER formation in an agricultural soil. Four different treatments were incubated at 20 °C for 75 days as follows; I: no fertilizer (2-13C,15N-glyphosate only, control), II: P-fertilizer (superphosphate + 2-13C,15N-glyphosate, effect of P-supply), III: N-fertilizer (ammonium nitrate + 2-13C,15N-glyphosate, effect of N-supply) and IV: 15N-fertilizer (15N-ammonium nitrate + 2-13C-glyphosate, differentiation between microbial assimilations of 15N: 15N-fertilizer versus 15N-glyphosate). We quantified 13C or 15N in mineralization, extractable residues, NERs and in amino acids (AAs). At the end, mineralization (36-41 % of the 13C), extractable 2-13C,15N-glyphosate/2-13C-glyphosate (0.42-0.49 %) & 15N-AMPA (1.2 %), and 13C/15N-NERs (40-43 % of the 13C, 40-50 % of the 15N) were comparable among treatments. Contrastingly, the 15N-NERs from 15N-fertlizer amounted to only 6.6 % of the 15N. Notably, N-fertilizer promoted an incorporation of 13C/15N from 2-13C,15N-glyphosate into AAs and thus the formation of 13C/15N-bioNERs. The 13C/15N-AAs were as follows: 16-21 % (N-fertilizer) > 11-13 % (control) > 7.2-7.3 % (P-fertilizer) of the initially added isotope. 2-13C,15N-glyphosate was degraded via the sarcosine/glycine and AMPA simultaneously in all treatments, regardless of the treatment type. The percentage share of bioNERs within the NERs in the N-fertilized soil was highest (13C: 80-82 %, 15N: 100 %) compared to 53 % (13C & 15N, control) and to only 30 % (13C & 15N, P-fertilizer). We thus concluded simultaneous N & glyphosate addition to soils could be beneficial for the environment due to the enhanced bioNER formation, while P & glyphosate application disadvantageous since it promoted xenoNER formation.

Design, Synthesis, and Herbicidal Activity of Pyrazole Amide Derivatives as Potential Transketolase Inhibitors.

The design and synthesis of new herbicidal active compounds based on a new target are of great significance for the development of new herbicides. Transketolase (TK) plays a key role in the Calvin cycle of plant photosynthesis and has been confirmed as a potential candidate target to develop and discover new herbicides. To obtain compounds with ultraefficient targeting of TK, a series of pyrazole amide derivatives were designed and synthesized through structural optimization for lead compound 4u based on TK as the new target. The bioassay results showed that compounds 6ba and 6bj displayed a highly inhibitory effect with the root inhibition of about 90% against Digitaria sanguinalis (DS) and 80% against Amaranthus retroflexus (AR) and Setaria viridis (SV) by the small cup method, which was better than the positive control mesotrione and nicosulfuron. Furthermore, compounds 6ba and 6bj exhibited an excellent inhibitory effect with the inhibition of about 80% (against DS) and over 80% (against SV) at the dosage of 150 g of active ingredient/ha by the foliar spray method. The TK enzyme activity inhibition test showed that the inhibition effect of target compounds against TK was consistent with the results of herbicidal activities. Also, molecular docking analysis showed that compounds 6ba and 6bj went deep into the active cavity of TK, bound to TK by a strong interaction, and might act on the enzyme TK. Above of all, compounds 6ba and 6bj are promising herbicide lead compounds targeting TK. Hence, they could be developed into more efficient herbicides by further structural optimization.

Physiological effects of maize stressed by HPPD inhibitor herbicides via multi-spectral technology and two-dimensional correlation spectrum technology.

Understanding the physiological effects of herbicides on crops is crucial for crop production and environmental management. The effects of 4-hydroxyphenylpyruvate dioxygenase inhibitor (HPPDi) herbicides at different concentrations on chlorophyll content in maize leaves, fresh weight of roots, stems and leaves, and fluorescence substances and functional groups in root exudates (REs) were studied by UV-Vis absorption spectroscopy, fluorescence spectroscopy, Fourier transform infrared spectroscopy (FTIR) and two-dimensional correlation analysis (2D-COS). The results showed that 5 mg/L and 10 mg/L HPPDi herbicides inhibited the synthesis of chlorophyll in maize leaves. The weight of roots, stems and leaves of maize after application was lighter than that of the control group. HPPDi herbicides affected the early growth of maize seedlings, and the effect was most obvious at high concentration. Synchronous fluorescence spectrum and three-dimensional (3D) fluorescence spectrum revealed that the fluorescence intensity of protein, fulvic acid and humic acid in maize REs changed prominently. With the increase of HPPDi herbicides concentration, the fluorescence intensity decreased gradually. Through FTIR and 2D-COS, functional groups such as C-H, CO, Cl, NO3-, C-O and O-H were found to participate in the interaction between HPPDi herbicides and maize REs as binding sites. C-O, C-Cl and C-C have the strongest binding ability, while CC and CO of aromatic rings, quinones or ketones first take part in the binding between HPPDi herbicides and maize REs. The results can provide a theoretical basis for evaluating the safety of HPPDi herbicides on maize and a method for discovering the effects of pesticides on environmental media and plant physiological effects.