Regulatory potential of secondary metabolite DIMBOA and baicalein to imazethapyr-induced toxicity in wheat seedlings.

Controlling and mitigating the toxicity of herbicides to non-target plants is of significant importance in reducing ecological risks. The development of green and natural herbicide control technologies has become an urgent necessity. In this paper, how 2,4-dihydroxy-7-methoxy-2H-1,4-benzoxazine-3(4H)-one (DIMBOA) and baicalein alleviated oxidative stress induced by imazethapyr (IM) in wheat seedlings was investigated. We found that DIMBOA and baicalein enhanced the antioxidant enzyme activities in wheat seedlings exposed to IM and reduced the excessive reactive oxygen species due to IM stress by 21.3% and 23.5%, respectively. DIMBOA and baicalein also restored the iron content reduced by IM and effectively mitigated Fe2+ overload by alleviating the response of heme oxygenase 1 to IM stress. The antioxidant and iron homeostatic maintenance properties of DIMBOA and baicalein enhanced the defenses of wheat seedlings against IM stress. Our results highlight the potential implication of secondary metabolites as natural products to modulate herbicide toxicity to non-target plants.

Plasma Membrane (PM) H+-ATPase Mediates Rhizosphere Acidification and Regulates Herbicide Imazethapyr Toxicity in Wheat.

The plasma membrane (PM) H+-ATPase is crucial for a plant defense system. However, there is currently no consensus on whether the PM H+-ATPase plays a role in alleviating the toxic effects of herbicides on nontarget plants. We found that under the herbicide imazethapyr (IM) exposure, PM H+-ATPase activity in wheat roots increased by approximately 69.53%, leading to rhizosphere acidification. When PM H+-ATPase activity is inhibited, the toxicity of IM significantly increases: When exposed to IM alone, the total Fe content of wheat roots decreased by 29.07%, the relative Fe2+ content increased by 27.75%, and the ROS content increased by 27.74%. When the PM H+-ATPase activity was inhibited, the corresponding data under IM exposure were 37.36%, 215%, and 57.68%, respectively. This work delves into the role of PM H+-ATPase in mediating the detoxification mechanism in plants exposed to herbicides, offering new insights into enhancing crop resistance against herbicides.

Chiral herbicide imazethapy influences plant-soil feedback on nitrogen metabolism by shaping rhizosphere microorganisms.

Herbicides are known to affect the soil nitrogen cycle by shaping soil microorganisms. However, it is not clear how herbicides regulate diverse transformation processes of soil nitrogen cycling by altering rhizosphere microorganisms, subsequently influencing the feedback to plant nitrogen metabolism. Here, we investigated how imazethapyr (IM) enantiomers drive plant-soil feedback on nitrogen metabolism by altering the rhizosphere microorganisms. The results indicated that (R)- and (S)-IM significantly changed the composition and structure rhizosphere microbiome with enantioselectivity and functional changes in microbial communities were associated with soil nitrogen circulation. The determination of nitrogen-cycling functional genes further supported the above findings. The results revealed that (R)- and (S)-IM could change the abundance of nitrogen-cycling functional genes by changing specific bacteria abundances, such as Bacteroidetes, Proteobacteria, and Acidobacteria, thus resulting in diverse nitrogen transformation processes. The alternation of nitrogen transformation processes indicated (R)-IM exhibited a more notable tendency to form a nitrogen cycling pattern with lower energy cost and higher nitrogen retention than (S)-IM. Sterilization experiments demonstrated changes in soil nitrogen cycling drive plant nitrogen metabolism and rhizosphere microorganisms are responsible for the above process of plant-soil feedback for nitrogen metabolism. Under IM enantiomer treatments, rhizosphere microorganisms might stimulate glutamate synthesis by promoting NH4+ uptake and glutamine-glutamate synthesis cycling in roots, thus contributing to positive feedback, with (R)-IM treatments showing more pronounced positive feedback on nitrogen metabolism than (S)-IM treatments. Our results provide theoretical support for determining the mechanism by which IM enantiomers drive plant-soil nitrogen metabolism by changing the rhizosphere microbial communities.

Mechanisms Underlying Allelopathic Disturbance of Herbicide Imazethapyr on Wheat and Its Neighboring Ryegrass (Lolium perenne).

As representatives of allelopathy, weeds consistently coexist with crops, exhibiting mutual growth inhibition. At the same time, herbicides are usually employed to control weeds. However, few studies have investigated how herbicides will affect allelopathy between crops and their neighboring weeds. Our findings suggested that allelopathic-induced phenotypic variations in ryegrass were reduced in the presence of the herbicide imazethapyr (IM), consistent with the antioxidant system analysis results. Additionally, IM affected the levels of allelochemical hydroxamic acid (Hx) in both plants. Hydroponic experiments revealed that this impact was due to the accelerated transportation of Hx from wheat to ryegrass, driven by ryegrass-secreted jasmonic acid. This study holds paramount significance for comprehending the effects of herbicides on the allelopathic interactions between nontargeted crops and neighboring weeds, contributing to an enhanced understanding of herbicides on plant species interactions.

Phytotoxicity alleviation of imazethapyr to non-target plant wheat: active regulation between auxin and DIMBOA.

Effectively controlling target organisms while reducing the adverse effects of pesticides on non-target organisms is a crucial scientific inquiry and challenge in pesticide ecotoxicology research. Here, we studied the alleviation of herbicide (R)-imazethapyr [(R)-IM] to non-target plant wheat by active regulation between auxin and secondary metabolite 2,4-dihydroxy-7-methoxy-2H-1,4-benzoxazine-3(4H)-one (DIMBOA). We found (R)-IM reduced 32.4% auxin content in wheat leaves and induced 40.7% DIMBOA accumulation compared to the control group, which effortlessly disrupted the balance between wheat growth and defense. Transcriptomic results indicated that restoration of the auxin level in plants promoted the up-regulation of growth-related genes and the accumulation of DIMBOA up-regulated the expression of defense-related genes. Auxin and DIMBOA alleviated herbicide stress primarily through effects in the two directions of wheat growth and defense, respectively. Additionally, as a common precursor of auxin and DIMBOA, indole adopted a combined growth and defense strategy in response to (R)-IM toxicity, i.e., restoring growth development and enhancing the defense system. Future regulation of auxin and DIMBOA levels in plants may be possible through appropriate methods, thus regulating the plant growth-defense balance under herbicide stress. Our insight into the interference mechanism of herbicides to the plant growth-defense system will facilitate the design of improved strategies for herbicide detoxification.

Polystyrene microplastic attenuated the toxic effects of florfenicol on rice (Oryza sativa L.) seedlings in hydroponics: From the perspective of oxidative response, phototoxicity and molecular metabolism.

Antibiotics and microplastics (MPs) are two emerging pollutants in agroecosystems, however the effects of co-exposure to antibiotics and MPs remain unclear. The toxicity of florfenicol (FF) and polystyrene microplastics (PS-MPs) on rice seedlings was investigated. FF and PS-MPs caused colloidal agglomeration, which changed the environmental behavior of FF. FF inhibited rice growth and altered antioxidant enzyme (superoxide dismutase, peroxidase, and catalase) activities, leading to membrane lipid peroxidation; impaired photosynthetic systems, decreased photosynthetic pigments (Chlorophyll a, Chlorophyll b, and carotene), chlorophyll precursors (Proto IX, Mg-Proto IX, and Pchlide), photosynthetic and respiratory rates. The key photosynthesis related genes (PsaA, PsaB, PsbA, PsbB, PsbC, and PsbD) were significantly down-regulated. The ultrastructure of mesophyll cells was destroyed with chloroplast swelling, membrane surface blurring, irregular thylakoid lamellar structure, and number of peroxisomes increased. PS-MPs mitigated FF toxicity, and the IBR index values showed that 10 mg∙L-1 PS-MPs were more effective. Metabolomic analysis revealed that the abundance of metabolites and metabolic pathways were altered by FF, was greater than the combined "MPs-FF" contamination. The metabolism of amino acids, sugars, and organic acids were severely interfered. Among these, 15 metabolic pathways were significantly altered, with the most significant effects on phenylalanine metabolism and the citric acid cycle (p < 0.05).

Comparative study of the toxicity mechanisms of quinolone antibiotics on soybean seedlings: Insights from molecular docking and transcriptomic analysis.

The ecological effects of quinolone antibiotics (QNs) on non-target organisms have received widespread attention. The toxicological mechanisms of three common QNs, that is, enrofloxacin, levofloxacin, and ciprofloxacin, on soybean seedlings were investigated in this study. Enrofloxacin and levofloxacin caused significant growth inhibition, ultrastructural alterations, photosynthetic suppression, and stimulation of the antioxidant system, with levofloxacin exhibiting the strongest toxic effects. Ciprofloxacin (<1 mg·L-1) did not have a significant effect on the soybean seedlings. As the concentrations of enrofloxacin and levofloxacin increased, antioxidant enzyme activities, malondialdehyde content, and hydrogen peroxide levels also increased. Meanwhile, the chlorophyll content and chlorophyll fluorescence parameters decreased, indicating that the plants underwent oxidative stress and photosynthesis was suppressed. The cellular ultrastructure was also disrupted, which was manifested by swollen chloroplasts, increased starch granules, disintegration of plastoglobules, and mitochondrial degradation. The molecular docking results suggested that the QNs have an affinity for soybean target protein receptors (4TOP, 2IUJ, and 1FHF), with levofloxacin having the highest binding energy (-4.97, -3.08, -3.8, respectively). Transcriptomic analysis has shown that genes were upregulated under the enrofloxacin and levofloxacin treatments were mainly involved in ribosome metabolism and processes to synthesize oxidative stress-related proteins. Downregulated genes in the levofloxacin treatment were primarily enriched in photosynthesis-related pathways, indicating that levofloxacin significantly inhibited gene expression for photosynthesis. Genes expression level by quantitative real-time PCR analysis was consistent with the transcriptomic results. This study confirmed the toxic effect of QNs on soybean seedlings, and provided new insights into the environmental risks of antibiotics.

Role of Heme Oxygenase-1 in Dual Stress Response of Herbicide and Micronutrient Fe in Arabidopsis thaliana.

Increasingly intensive agricultural practices are leading not only to herbicide contamination but also to nutritional stress on nontarget plants. This study evaluated the role of heme oxygenase-1 (HO-1) in the dual stress response of herbicide dichlorprop and micronutrient Fe in Arabidopsis thaliana. Our results revealed that co-treatment with 20 µM zinc protoporphyrin (a specific inhibitor of HO-1) reduced the activity of HO-1 by 21.6%, Fe2+ content by 19.8%, and MDA content by 20.0%, reducing abnormal iron aggregation and oxidative stress in response to the herbicide compared to treatment with (R)-dichloroprop alone, which has herbicidal activity. Thus, free Fe2+ released from HO-1 mediated dichlorprop-induced oxidative stress in the Fenton reaction and affected aberrant Fe aggregation, which also had an enantioselective effect. This study contributes to an in-depth understanding of the toxicity mechanism of herbicides under nutrient stresses, thus providing new strategies to control the environmental risks of herbicides.

Enantioselective Response of Wheat Seedlings to Imazethapyr: From the Perspective of Fe and the Secondary Metabolite DIMBOA.

The responses of trace elements and secondary metabolites to stress can reflect plant adaptation to the environment. If and how the imperative trace element Fe and the defensive secondary metabolite 2,4-dihydroxy-7-methoxy-2H-1,4-benzoxazine-3(4H)-one (DIMBOA) mediate the toxicity of chiral herbicides to nontarget plants remains inconclusive. We found that the herbicidal-active imazethapyr enantiomer [(R)-IM] stimulated heme oxygenase-1 activity, triggered the release of the catalytic product Fe2+, increased reactive oxygen species production, decreased the DIMBOA content, and increased the DIMBOA-Fe content. XAFS analyses and in vitro Fenton assays demonstrated that DIMBOA could relieve phytotoxicity by chelating excessive Fe3+ to restore Fe homeostasis. The free radical scavenging ability of the chelate of DIMBOA and Fe was also involved. This work refines the dual role of DIMBOA and Fe in mediating the enantioselective phytotoxicity of chiral herbicides, which provides a new direction for improving the herbicide resistance of crops.

Effect of trace elements in the toxicity of copper to Chlamydomonas reinhardtii.

Copper sulfate (CuSO4) is widely used in the control of algal blooms. Cu can promote or inhibit algal growth, while also affecting trace element uptake, therefore, the response mechanisms of algae cells under Cu2+ interference should be studied. In this study, wild-type Chlamydomonas reinhardtii (C. reinhardtii) and wall-less mutant C. reinhardtii were selected as the research objects. Except for the cell wall, these two algae were physiologically the same. While manipulating the concentration of Cu, the accumulation of Cu, Fe, Zn, and Mn by the two algal cell types was studied. The cell wall hindered the accumulation of Cu by cells and alleviated the toxicity of Cu to C. reinhardtii. The addition of Cu increased the accumulation of Fe by both cell types. In an environment with excess Cu, the total amount of Zn and Mn accumulated by cells also increased. On the one hand, this may be due to the synergistic and antagonistic effects of trace elements in the adsorption and uptake process, and on the other hand, it may be due to the changes in metal speciation in the culture medium. In addition, the difference in the total accumulation of various trace elements between wild-type and wall-less-type C. reinhardtii may be due to the structure and function differences between cell wall and cell membrane. At the same time, by measuring the changes in the levels of glutathione (GSH) in algal cells, the relevant mechanisms underlying the algae's uptake of trace elements by algae were further explored.

The strong promoting effects of thin layer Al2O3 on FeCu Fenton-like components: Enhanced electron transfer.

The Fe(III)/Fe(II) redox cycle is the main factor limiting the effectiveness of Fe-mediated advanced oxidation processes (AOPs) for the degradation of organic pollutants. In this study, the promoting effects of thin-layer Al2O3 (t-Al2O3) between the frequently used FeCu components and the mesoporous silica support were studied to reduce Fe(III) to promote the activity of the Fenton-like catalyst. After modification by t-Al2O3, the mesoporous silicon-loaded FeCu catalyst removed 97% of Rhodamine B at pH 7, which was superior to the unmodified sample with a removal rate of 62.4% under the same conditions. Morphological characterization and X-ray diffraction patterns indicated that the Fe-Cu/t-Al2O3 active components were highly dispersed. Pyridine infrared spectra suggested that all of the acid sites were Lewis acids, and the t-Al2O3-loaded samples provided moderate/strong Lewis acids. The loading of t-Al2O3 between the FeCu complex and mesoporous silica support facilitated electron transfer during the Fe(III)/Fe(II) redox cycle by enhancing the dispersion of Fe-Cu/t-Al2O3 and the Lewis acidity. The results of this study provide insight into how t-Al2O3 promoted the interactions between the active components and silica support and how it can be used to aid in the selection of suitable wastewater treatment technologies.

New Target in an Old Enemy: Herbicide (R)-Dichlorprop Induces Ferroptosis-like Death in Plants.

Iron is an essential microelement in plants that is involved in several growth processes. The use of herbicides may cause the abnormal aggregation of iron in leaves, but the regulatory mechanisms underlying this phenomenon remain unclear. Here, we show that chiral herbicide (R)-dichlorprop ((R)-DCPP) triggers ferroptosis-like death in Arabidopsis thaliana. (R)-DCPP led to reactive oxygen species (ROS) accumulation and iron aggregation, and these processes were iron dependent. Under (R)-DCPP treatment, ROS, lipid hydrogen peroxides, and malondialdehyde were significantly accumulated. In addition, (R)-DCPP induced the depletion of glutathione, ascorbic acid, and glutathione peroxidase as well as the accumulation of toxic lipid peroxides. Thus, oxidation imbalance led to cell death, and this mode of action could be inhibited by the ferroptosis inhibitor ferrostatin-1 or ciclopirox olamine. NADPH oxidases were found to be involved in herbicide-induced ROS accumulation, and lipoxygenase and NADPH cytochrome P450 oxidase were shown to positively regulate (R)-DCPP-induced lipid peroxidation. Overall, these results indicate that the iron- and ROS-dependent signaling cascades were involved in the (R)-DCPP-induced phytotoxicity pathway, which disrupted the structure of plant cell membranes and triggered ferroptosis. Generally, this study provides new insight into the mechanisms of pesticide phytotoxicity and suggests new therapeutic directions to protect nontarget plants.

Phytotoxicity of the chiral herbicide dichlorprop: Cross-talk between nitric oxide, reactive oxygen species and phytohormones.

Nitric oxide (NO), reactive oxygen species (ROS), and phytohormones in plants often initiate responses to sources of abiotic stress. However, we have a poor understanding of the cross-talk between NO, ROS, and phytohormones during exogenous chiral auxin-induced phytotoxicity. In this study, the toxicity of the chiral synthetic auxin herbicide dichlorprop (DCPP) to Arabidopsis thaliana, as well as the mutual regulation of NO, hydrogen peroxide (H2O2), superoxide anion (O2.-), and phytohormones at the enantiomeric level was investigated. The ROS production exhibited an enantioselective manner, further, that was positively correlated with the change of the morphological indicators. This confirmed that ROS played an important role in the enantioselective effect of DCPP. The distribution of ROS and NO was partially overlapped, indicating that the production of NO may be affected by ROS, and also related to the degree of plant damage. In terms of phytohormones, the level of salicylic acid (SA), jasmonic acid (JA), and abscisic acid (ABA) in the whole plant increased as the (R)-DCPP concentration applied increased, however, the trend has changed, when the data of leaves and roots was discussed separately. The results revealed that the redistribution of phytohormones may exist between leaves and roots, caused by the joint action of ROS and NO. The differences in the biological activity identified between the two enantiomers in this study enhance our understanding of the toxicity mechanism of exogenous auxin via their effects on phytohormones.

Enantioselective effects of imazethapyr on the secondary metabolites and nutritional value of wheat seedlings.

The secondary metabolism of plants is key for mediating responses to environmental stress, but few studies have examined how the relationship between secondary metabolism and the stress response of plants is affected by exposure to chiral herbicides. Here, we studied the enantioselective disturbance of the chiral herbicide imazethapyr (IM) on the secondary metabolism and nutrient levels of wheat seedlings. The bioactive enantiomer R-IM significantly increased the contents of major secondary metabolites, including phenolic acids, flavonoids, and carotenoids but greatly inhibited the production of benzoxazine. The antioxidant system also responded strongly to R-IM; specifically, the activities of SOD, CAT, and GPX enzymes were all significantly induced, and the GSH content initially increased but then decreased. Furthermore, the nutrient levels of wheat seedlings were also affected; dietary fiber content decreased, while the contents of the microelements Fe, Mn, and Zn increased. In sum, this study provides new insight into the phytotoxic effects of IM and raises new questions on the role of secondary metabolites and nutrients in mediating enantioselective effects.

A sandwich model of Cr(VI) adsorption and detoxification by Fenton modified chitosan.

The Fenton reaction has the advantages of short reaction time, low cost, no toxicity, and straightforward application and control. The Fenton reaction generates highly reactive HO•, which has been applied effectively. However, the effect of the generated Fe3+ has not been investigated widely. In this study, the Fenton reaction was used to improve the Cr(VI) adsorption and detoxification capacities of chitosan. After the Fenton modification, chitosan efficiently adsorbed Cr(VI) and transformed it into the less toxic Cr(III) in a wide pH range as a result of layer formation, which was described by a sandwich model. The adsorption of Cr(VI) onto the Fenton modified chitosan was in good agreement with the Freundlich adsorption model, and the adsorption capacity exceeded 120 mg/g. During the Fenton reaction, H2 O2 and HO• with high oxidative activity broke the hydrogen bonds in the chitosan structure, resulting in the release of free amine groups for Fe3+ to form metal-binding biopolymers. The distance between the chitosan polymers increased, and additional adsorption sites were created. HCrO4 - entered the gap between the chitosan polymer and was adsorbed on the newly created adsorption sites. The sandwich adsorption model indicated that the Fenton modified chitosan provided a high concentration of active sites for Cr(VI) capture and detoxification. PRACTITIONER POINTS: Fenton reaction was used to improve the adsorption ability of chitosan. The formed Fe3+ in Fenton reaction was utilized. HO· broke the hydrogen bonds and Fe3+ ions chelated with chitosan in modification. Cr(VI) could be adsorbed and reduced efficiently by Fenton modified chitosan. The Fenton modified chitosan provided a high concentration of active sites for Cr(VI) capture and detoxification.

Disturbance of chiral ionic liquids to phototaxis of Chlamydomonas reinhardtii: regular analysis and mechanism attempt.

Given the recent extensive synthesis and application of ionic liquids (ILs), finding a sensitive and visual indicator to provide a fast-initial risk assessment of IL use has become a pressing issue. In this study, we verified that the phototaxis of Chlamydomonas reinhardtii is a valid indicator of the environmental risk associated with chiral ILs L-(+)- and D-(-)-1-butyl-3-methylimidazolium lactate (BMIM L). Briefly, C. reinhardtii was exposed to a 4000-lx side light source for varying lengths of time. Following the allotted exposure time, the algae aggregation was photographed, and then quantitative analysis was conducted using Image-J software to obtain the corresponding relationship between IL stimulation and C. reinhardtii phototaxis. The gray areas from each treatment were measured and the percentage was calculated. After 16 h of side lighting, for control, the percentage of gray areas was - 22%, while for L-(+)- and D-(-)- BMIM L were 17% and 33%, respectively. Then, after 8 h of darkness, where D-(-)-BMIM L and the control showed the positive phototaxis, but the L-(+)-BMIM L-treated group showed virtually no change. This phenomenon is consistent with excessive production of reactive oxygen species (ROS). Moreover, atomic force microscope (AFM) results indicated distinct aggregation between D-(-)- and L-(+)-BMIM L, which caused changes in cell permeability that induced a change in ROS transfer. Furthermore, relationship between phototaxis and changes in cell ultrastructure and photosynthetic efficiency was also investigated. This work demonstrates the potential of phototaxis to serve as a sensitive, convenient, and cost effective qualitative assessment of ILs' toxic impact, with the understanding that quantitative evaluation requires further improvement.

Effects of ketoprofen on rice seedlings: Insights from photosynthesis, antioxidative stress, gene expression patterns, and integrated biomarker response analysis.

Pharmacologically active compounds found in reclaimed wastewater irrigation or animal manure fertilizers pose potential risks for agriculture. The mechanism underlying the effects of ketoprofen on rice (Oryza sativa L.) seedlings was investigated. The results showed that low concentrations (0.5 mg L-1) of ketoprofen slightly stimulate growth of rice seedlings, while high concentrations can significantly inhibit growth by reducing biomass and causing damage to roots. Ketoprofen affects photosynthetic pigment content (Chla, Chlb, and carotenoids) and chlorophyll synthesis gene (HEMA, HEMG, CHLD, CHLG, CHLM, and CAO) expression. Fluorescence parameters such as minimum fluorescence (F0), maximum fluorescence (Fm), variable fluorescence (Fv), potential photosynthetic capacity (Fv/F0), maximum quantum efficiency of PSII photochemistry (Fv/Fm), electron transfer rate (ETR), and Y(II), Y(NPQ), Y(NO) values were affected, showing photosynthetic electron transfer was blocked. Active oxygen radical (O2•-and H2O2), malondialdehyde and proline content increased. Superoxide dismutase, catalase and ascorbate peroxidase activities, glutathione content and antioxidant-related gene (FSD1, MSD1, CSD1, CSD2, CAT1, CAT2, CAT3, APX1, APX2) expression were induced. Higher integrated biomarker response values of eight oxidative stress response indexes were obtained at higher ketoprofen concentrations. Ultrastructure observation showed that ketoprofen causes cell structure damage, chloroplast swelling, increase in starch granules, and reduction in organelles. This study provides some suggested toxicological mechanisms and biological response indicators in rice due to stress from pharmacologically active compounds.

Enantioselective Phytotoxic Disturbances of Fatty Acids in Arabidopsis thaliana by Dichlorprop.

Plant fatty acids have indispensable physiological functions and nutritional value. However, the overuse of herbicides may cause phytotoxic disturbances of fatty acids in nontarget plants while spraying for weeds. Evidence has shown that the herbicide dichlorprop can inhibit the activity of acetyl-CoA carboxylase (ACCase), a key enzyme involved in fatty acid synthesis. However, the enantioselective phytotoxic effects of dichlorprop enantiomers ((R)-dichlorprop and (S)-dichlorprop) on fatty acids and their related mechanisms remain unclear. To solve this issue, the enantioselective phytotoxicity of dichlorprop in the model plant species Arabidopsis thaliana (A. thaliana) with a focus on fatty acids was evaluated for the first time. The results indicated a significant difference in enantioselectivity and that exposure to (R)-dichlorprop can cause marked fatty acid disturbances in nontarget plant species. Specifically, (R)-dichlorprop decreased the content of three fatty acids by more than 50% by inhibiting the activity of ACCase. In addition, increased malondialdehyde (MDA) and lipid hydroperoxides (LOOHs) contents and membrane permeability reflected herbicide-induced lipid peroxidation, which decreased the unsaturation of fatty acids in membranes and further influenced membrane composition and function. Moreover, an increased level of glutathione peroxidase (GPX) and cytochrome P450 (CYP450) reflected a plant stress-induced response. To summarize, fatty acids represent a new perspective for evaluating the toxicity of chiral pesticides, contributing to a better understanding of the enantioselective phytotoxicity and mechanisms of dichlorprop, and providing evidence for herbicide security and risk assessments.

Stable cuprous active sites in Cu+-graphitic carbon nitride: Structure analysis and performance in Fenton-like reactions.

Cu+-based catalysts have great potential in Fenton reactions under neutral pH conditions. However, cuprous (Cu+) materials are instable in the aqueous environment. Herein, using the cheap precursors, a Cu+-graphitic carbon nitride complex with an efficient Fenton-like activity as well as relative stability was prepared. 99.2% removal of Rhodamine B with an initial concentration of 50 mg/L could be attained in 1 h. Several experimental techniques are employed to study the structure of this catalyst. Results show that after the addition of Cu, the graphitic carbon nitride (g-C3N4) network is partially destroyed and the reduced Cu is therefore firmly embedded in the fragmentary g-C3N4 sheet. The X-ray adsorption fine spectra illustrates the chemical state and the local structure of the bonded Cu. Due to the strong orbital hybridization, Cu+ could be stabilized through the coordination with pyridinic N. A two-coordinate structure with a bond length of 1.90 Šis confirmed and this structure is not changed even after the Fenton-like reaction. Singlet oxygen (1O2) and hydroxyl radicals (HO•) are produced by the rapid interaction of bonded Cu+ with H2O2 and the resulting Cu2+ can be easily reduced to its cuprous state due to its structure stability, leading to its high activity in the Fenton-like reaction.

Enantioselective Toxicity of Chiral Herbicide Metolachlor to Microcystis aeruginosa.

The enantioselective effects of chiral herbicides on aquatic organisms have received increasing attention. As one kind of freshwater algae responsible for most algal blooms, Microcystis aeruginosa can produce hepatotoxic microcystin and cause serious health concerns for drinking water. Thus, the effects of chiral herbicides on M. aeruginosa are of vital significance but poorly understood, especially as the structures of chiral herbicides become more complex. In this study, the enantioselective effects of four metolachlor enantiomers based on carbon center and axis chirality on M. aeruginosa were investigated for the first time at an enantiomeric level. The results of the investigation into algal growth inhibition, chlorophyll a content, and cell integrity indicated that ( S)-metolachlor [( S)-Met] was significantly more toxic than any other isomer. The toxicity ranking of different enantiomers at the highest concentration (15 mg/L) against M. aeruginosa was ( S)-Met > (α R,1' S)-Met > (α S,1' S)-Met > (α S,1' R)-Met > (α R,1' R)-Met, with (α S,1' S)-Met and (α R,1' S)-Met displaying a synergistic effect. Additionally, the Fe distribution in M. aeruginosa presented distinct enantioselectivity, which may contribute to the enantioselective toxicity of metolachlor. Furthermore, metolachlor upregulated the expression of genes mcyD and mcyH in an enantioselective manner, indicating that this herbicide can potentially promote the synthesis and efflux of microcystin, thus aggravating agricultural water contamination to different extents. Overall, this study will help to understand the ecotoxicity of metolachlor at a deeper level and provide theoretical insights into the enantioselective behaviors of metolachlor.