Comprehensive toxicological, metabolomic, and transcriptomic analysis of the biodegradation and adaptation mechanism by Achromobacter xylosoxidans SL-6 to diuron.

Biodegradation was considered a promising and environmentally friendly method for treating environmental pollution caused by diuron. However, the mechanisms of biodegradation of diuron required further research. In this study, the degradation process of diuron by Achromobacter xylosoxidans SL-6 was systematically investigated. The results suggested that the antioxidant system of strain SL-6 was activated by adding diuron, thereby alleviating their oxidative stress response. In addition, degradation product analysis showed that diuron in strain SL-6 was mainly degraded by urea bridge cleavage, dehalogenation, deamination, and ring opening, and finally cis, cis-muconic acid was generated. The combined analysis of metabolomics and transcriptomics revealed the biodegradation and adaptation mechanism of strain SL-6 to diuron. Metabolomics analysis showed that after the strain SL-6 was exposed to diuron, metabolic pathways such as tricarboxylic acid cycle (cis, cis-muconic acid), glutathione metabolism (oxidized glutathione), and urea cycle (arginine) were reprogrammed in the cells. Furthermore, diuron could induce the production of membrane transport proteins in strain SL-6 cells and overexpress antioxidant enzyme genes, finally ultimately promoting the up-regulation of genes encoding amide hydrolases and dioxygenases, which was revealed by transcriptomics studies. This work enriched the biodegradation mechanism of phenylurea herbicides and provided guidance for the removal of diuron residues in the environment and promoting agriculture sustainable development.

The Fabrication and Property Characterization of a Ho2YSbO7/Bi2MoO6 Heterojunction Photocatalyst and the Application of the Photodegradation of Diuron under Visible Light Irradiation.

A novel photocatalytic nanomaterial, Ho2YSbO7, was successfully synthesized for the first time using the solvothermal synthesis technique. In addition, a Ho2YSbO7/Bi2MoO6 heterojunction photocatalyst (HBHP) was prepared via the hydrothermal fabrication technique. Extensive characterizations of the synthesized samples were conducted using various instruments, such as an X-ray diffractometer, a Fourier transform infrared spectrometer, a Raman spectrometer, a UV-visible spectrophotometer, an X-ray photoelectron spectrometer, and a transmission electron microscope, as well as X-ray energy dispersive spectroscopy, photoluminescence spectroscopy, a photocurrent test, electrochemical impedance spectroscopy, ultraviolet photoelectron spectroscopy, and electron paramagnetic resonance. The photocatalytic activity of the HBHP was evaluated for the degradation of diuron (DRN) and the mineralization of total organic carbon (TOC) under visible light exposure for 152 min. Remarkable removal efficiencies were achieved, with 99.78% for DRN and 97.19% for TOC. Comparative analysis demonstrated that the HBHP exhibited markedly higher removal efficiencies for DRN compared to Ho2YSbO7, Bi2MoO6, or N-doped TiO2 photocatalyst, with removal efficiencies 1.13 times, 1.21 times, or 2.95 times higher, respectively. Similarly, the HBHP demonstrated significantly higher removal efficiencies for TOC compared to Ho2YSbO7, Bi2MoO6, or N-doped TiO2 photocatalyst, with removal efficiencies 1.17 times, 1.25 times, or 3.39 times higher, respectively. Furthermore, the HBHP demonstrated excellent stability and reusability. The mechanisms which could enhance the photocatalytic activity remarkably and the involvement of the major active species were comprehensively discussed, with superoxide radicals identified as the primary active species, followed by hydroxyl radicals and holes. The results of this study contribute to the advancement of efficient heterostructural materials and offer valuable insights into the development of sustainable remediation strategies for addressing DRN contamination.

Interaction of different chloro-substituted phenylurea herbicides (diuron and chlortoluron) with bovine serum albumin: Insights from multispectral study.

In this work, the interaction between different chloro-substituted phenylurea herbicides (diuron (DIU) and chlortoluron (CHL)) and BSA were investigated and compared at three different temperatures (283 K, 298 K and 310 K) adopting UV-vis, fluorescence, and circular dichroism spectra. The quenching mechanism of the interaction was also proposed. The energy transfer between BSA and DIU/CHL was investigated. The binding sites of DIU/CHL and BSA and the variations in the microenvironment of amino acid residues were studied. The changes of the secondary structure of BSA were analyzed. The results indicate that both DIU and CHL can significantly interact with BSA, and the degree of the interaction between DIU/CHL and BSA increases with the increase of the DIU/CHL concentration. The fluorescence quenching of BSA by DIU/CHL results from the combination of static and dynamic quenching. The DIU/CHL has a weak to moderate binding affinity for BSA, and the binding stoichiometry is 1:1. Their binding processes are spontaneous, and hydrophobic interaction, hydrogen bonds and van der Waals forces are the main interaction forces. DIU/CHL has higher affinity for subdomain IIA (Site I) of BSA than subdomain IIIA (Site II), and also interacts with tryptophan more than tyrosine residues. The energy transfer can occur from BSA to DIU/CHL. By comparison, the strength of the interaction of DIU-BSA is always greater than that of CHL-BSA, and DIU can destroy the secondary structure of BSA molecules greater than CHL and thus the potential toxicity of DIU is higher due to DIU with more chlorine substituents than CHL. It is expected that this study on the interaction can offer in-depth insights into the toxicity of phenylurea herbicides, as well as their impact on human and animal health at the molecular level.

Performance evaluation of Trichoderma reseei in tolerance and biodegradation of diuron herbicide in agar plate, liquid culture and solid-state fermentation.

The present study evaluated the performance of the fungus Trichoderma reesei to tolerate and biodegrade the herbicide diuron in its agrochemical presentation in agar plates, liquid culture, and solid-state fermentation. The tolerance of T. reesei to diuron was characterized through a non-competitive inhibition model of the fungal radial growth on the PDA agar plate and growth in liquid culture with glucose and ammonium nitrate, showing a higher tolerance to diuron on the PDA agar plate (inhibition constant 98.63 mg L-1) than in liquid culture (inhibition constant 39.4 mg L-1). Diuron biodegradation by T. reesei was characterized through model inhibition by the substrate on agar plate and liquid culture. In liquid culture, the fungus biotransformed diuron into 3,4-dichloroaniline using the amide group from the diuron structure as a carbon and nitrogen source, yielding 0.154 mg of biomass per mg of diuron. A mixture of barley straw and agrolite was used as the support and substrate for solid-state fermentation. The diuron removal percentage in solid-state fermentation was fitted by non-multiple linear regression to a parabolic surface response model and reached the higher removal (97.26%) with a specific aeration rate of 1.0 vkgm and inoculum of 2.6 × 108 spores g-1. The diuron removal in solid-state fermentation by sorption on barley straw and agrolite was discarded compared to the removal magnitude of the biosorption and biodegradation mechanisms of Trichoderma reesei. The findings in this work about the tolerance and capability of Trichoderma reesei to remove diuron in liquid and solid culture media demonstrate the potential of the fungus to be implemented in bioremediation technologies of herbicide-polluted sites.

Assessing the spatiotemporal occurrence and ecological risk of antifouling biocides in a Brazilian estuary.

Diuron and Irgarol are common antifouling biocides used in paints to prevent the attachment and growth of fouling organisms on ship hulls and other submerged structures. Concerns about their toxicity to non-target aquatic organisms have led to various restrictions on their use in antifouling paints worldwide. Previous studies have shown the widespread presence of these substances in port areas along the Brazilian coast, with a concentration primarily in the southern part of the country. In this study, we conducted six sampling campaigns over the course of 1 year to assess the presence and associated risks of Diuron and Irgarol in water collected from areas under the influence of the Maranhão Port Complex in the Brazilian Northeast. Our results revealed the absence of Irgarol in the study area, irrespective of the sampling season and site. In contrast, the mean concentrations of Diuron varied between 2.0 ng L-1 and 34.1 ng L-1 and were detected at least once at each sampling site. We conducted a risk assessment of Diuron levels in this area using the risk quotient (RQ) method. Our findings indicated that Diuron levels at all sampling sites during at least one campaign yielded an RQ greater than 1, with a maximum of 22.7, classifying the risk as "high" based on the proposed risk classification. This study underscores the continued concern regarding the presence of antifouling biocides in significant ports and marinas in Brazilian ports, despite international bans.

Hormonal and haematological biomarkers as indicators of stress induced by Diuron herbicide toxicity on Clarias gariepinus (Burchell, 1822) sub-adults.

Diuron is a globally used herbicide for weed control but has anti-androgenic effects on androgens (testosterone and androstenedione), antagonist effects on thyroid hormone signaling, and haematological effects due to their biotransformation in fish. Endocrine-disrupting biomarkers such as thyroid hormones, sex hormones, and haematological indices of Clarias gariepinus sub-adults exposed to sub-lethal diuron concentrations were studied over a 28-day period. C. gariepinus (n = 200) sub-adults were exposed to sub-lethal concentrations (0.00, 0.09, 0.18, 0.26, and 0.35 mg/L) of diuron. Changes in the hormonal and haematological profiles of the exposed fish were concentration and exposure duration-dependent. The thyroxine (T4), tri-iodothyronine (T3), and 17ß-estradiol (E2) profiles decreased with an increase in concentration and exposure duration. The haemoglobin, pack cell volume, red blood cell, white blood cell, mean cell volume, and mean corpuscular haemoglobin cell decreased, while the mean corpuscular haemoglobin increased with an increase in concentration and exposure duration. Diuron induced stress and altered the physiological mechanisms of fish, and its application in farmlands should be regulated so as to enable a sustainable aquatic eco-system and fishery resources.

Diuron and its metabolites induce mitochondrial dysfunction-mediated cytotoxicity in urothelial cells.

In the environment, or during mammalian metabolism, the diuron herbicide (3-(3,4-dichlorophenyl)-1,1-dimethylurea) is transformed mainly into 3-(3,4-dichlorophenyl)-1-methylurea (DCPMU) and 3,4-dichloroaniline (DCA). Previous research suggests that such substances are toxic to the urothelium of Wistar rats where, under specific exposure conditions, they may induce urothelial cell degeneration, necrosis, hyperplasia, and eventually tumors. However, the intimate mechanisms of action associated with such chemical toxicity are not fully understood. In this context, the purpose of the current in vitro study was to analyze the underlying mechanisms involved in the urothelial toxicity of those chemicals, addressing cell death and the possible role of mitochondrial dysfunction. Thus, human 1T1 urothelial cells were exposed to six different concentrations of diuron, DCA, and DCPMU, ranging from 0.5 to 500 µM. The results showed that tested chemicals induced oxidative stress and mitochondrial damage, cell cycle instability, and cell death, which were more expressive at the higher concentrations of the metabolites. These data corroborate previous studies from this laboratory and, collectively, suggest mitochondrial dysfunction as an initiating event triggering urothelial cell degeneration and death.

A review of novel methods for Diuron removal from aqueous environments.

Runoff from intensive agriculture, which contains many sources of pollutants, including herbicides, for instance, Diuron, has threatened the environment and human health. The intrusion of these toxins into water sources poses a serious challenge to human society, and the rising release of these toxins has always been of concern to water researchers. The consequences of the release of these toxins into water sources are destructive and debilitating to human life. Today, the contamination of surface water and wastewater by pesticide residues, especially from agricultural activities and pesticide factories, has grown significantly. One of the pesticides commonly applied around the world is Diuron. There are various techniques for removing Diuron, the most important of which are adsorption and advanced oxidation. This review presents the characteristics, mechanisms, and emerging methods of removing Diuron. The use of absorbents, such as sludge-derived modified biochar (SDMBC600) and bottom ash waste (BAW-200), is discussed in detail. Additionally, the main features, benefits, and limitations of new technologies like hydrodynamic cavitation are enumerated. The effectiveness of novel adsorbents in Diuron removal is also discussed.

Pesticides in the Great Barrier Reef catchment area: Plausible risks to fish populations.

Waterways that drain the Great Barrier Reef catchment area (GBRCA) transport pollutants to marine habitats, provide a critical corridor between freshwater and marine habitats for migratory fish species, and are of high socioecological value. Some of these waterways contain concentrations of pesticide active ingredients (PAIs) that exceed Australian ecotoxicity threshold values (ETVs) for ecosystem protection. In this article, we use a "pathway to harm" model with five key criteria to assess whether the available information supports the hypothesis that PAIs are or could have harmful effects on fish and arthropod populations. Strong evidence of the first three criteria and circumstantial weaker evidence of the fourth and fifth criteria are presented. Specifically, we demonstrate that exceedances of Australian and New Zealand ETVs for ecosystem protection are widespread in the GBRCA, that the PAI contaminated water occurs (spatially and temporally) in important habitats for fisheries, and that there are clear direct and indirect mechanisms by which PAIs could cause harmful effects. The evidence of individuals and populations of fish and arthropods being adversely affected species is more circumstantial but consistent with PAIs causing harmful effects in the freshwater ecosystems of Great Barrier Reef waterways. We advocate strengthening the links between PAI concentrations and fish health because of the cultural values placed on the freshwater ecosystems by relevant stakeholders and Traditional Owners, with the aim that stronger links between elevated PAI concentrations and changes in recreationally and culturally important fish species will inspire improvements in water quality. Integr Environ Assess Manag 2024;00:1-24. © 2023 Commonwealth of Australia and The Commonwealth Scientific and Industrial Research Organisation. Integrated Environmental Assessment and Management published by Wiley Periodicals LLC on behalf of Society of Environmental Toxicology & Chemistry (SETAC).

Expression analyses of stress-responsive genes in the hermatypic coral Acropora tenuis and its symbiotic dinoflagellates after exposure to the herbicide Diuron.

Diuron is one of the most frequently applied herbicides in sugarcane farming in southern Japan, and Australia. In addition, it is used as a booster substance in copper-based antifouling paints. Due to these various uses, Diuron is released into the marine environment; however, little information is available on gene expression in corals and their symbiotic algae exposed to Diuron. We investigated the effects of Diuron on stress-responsive gene expression in the hermatypic coral Acropora tenuis and its symbiotic dinoflagellates. After seven days of exposure to 1 µg/L and 10 µg/L Diuron, no significant changes in the body colour of corals were observed. However, quantitative reverse transcription-polymerase chain reaction analyses revealed that the expression levels of stress-responsive genes, such as heat shock protein 90 (HSP90), HSP70, and calreticulin (CALR), were significantly downregulated in corals exposed to 10 µg/L of Diuron for seven days. Moreover, aquaglyceroporin was significantly downregulated in corals exposed to environmentally relevant concentrations of 1 µg/L Diuron. In contrast, no such effects were observed on the expression levels of other stress-responsive genes, such as oxidative stress-responsive proteins, methionine adenosyltransferase, and green/red fluorescent proteins. Diuron exposure had no significant effect on the expression levels of HSP90, HSP70, or HSP40 in the symbiotic dinoflagellates. These results suggest that stress-responsive genes, such as HSPs, respond differently to Diuron in corals and their symbiotic dinoflagellates and that A. tenuis HSPs and CALRs may be useful molecular biomarkers for predicting stress responses induced by the herbicide Diuron. Supplementary Information: The online version contains supplementary material available at 10.1007/s42995-023-00183-0.

Electrochemical Determination of Hazardous Herbicide Diuron Using MWCNTs-CS@NGQDs Composite-Modified Glassy Carbon Electrodes.

Diuron (DU) abuse in weed removal and shipping pollution prevention always leads to pesticide residues and poses a risk to human health. In the current research, an innovative electrochemical sensor for DU detection was created using a glassy carbon electrode (GCE) that had been modified with chitosan-encapsulated multi-walled carbon nanotubes (MWCNTs-CS) combined with nitrogen-doped graphene quantum dots (NGQDs). The NGQDs were prepared by high-temperature pyrolysis, and the MWCNTs-CS@NGQDs composite was further prepared by ultrasonic assembly. TEM, UV-Vis, and zeta potential tests were performed to investigate the morphology and properties of MWCNTs-CS@NGQDs. CV and EIS measurements revealed that the assembly of MWCNTs and CS improved the electron transfer ability and effective active area of MWCNTs. Moreover, the introduction of NGQDs further enhanced the detection sensitivity of the designed sensor. The MWCNTs-CS@NGQDs/GCE electrochemical sensor exhibited a wide linear range (0.08~12 µg mL-1), a low limit of detection (0.04 µg mL-1), and high sensitivity (31.62 µA (µg mL-1)-1 cm-2) for DU detection. Furthermore, the sensor demonstrated good anti-interference performance, reproducibility, and stability. This approach has been effectively employed to determine DU in actual samples, with recovery ranges of 99.4~104% in river water and 90.0~94.6% in soil. The developed electrochemical sensor is a useful tool to detect DU, which is expected to provide a convenient and easy analytical technique for the determination of various bioactive species.

Selectivity and control of Euphorbia heterophylla in sugarcane by herbicide in post-emergence.

To obtain good control of wild poinsettia (Euphorbia heterophylla) in post-emergence in sugarcane crop, we evaluate the herbicides association on post-emergence of E. heterophylla and the ratoon cane selectivity. The experimental scheme was in randomized blocks with 6 treatments and 4 replications. The treatments were: control; ametryn + mesotrione + sulfentrazone (1,500 + 144 + 800 g i.a ha-1); ametryn + mesotrione + diclosulan (1,500 + 144 + 200 g i.a ha-1); ametryn + mesotrione (2,500 + 144 g i.a ha-1: Highest dose); ametryn + mesotrione (2,000 + 144 g i.a ha-1: Lowest dose) and ametryn + mesotrione + diuron (1,000 + 144 + 1,250 g i.a ha-1). The percentage of control, dry mass, height and percentage of germination of E. heterophylla and injury level, yield and technological quality of sugarcane were evaluated. The best control of E. heterophylla was: ametryn + mesotrione +sulfentrazone; ametryn + mesotrione + diclosulan and ametryn + mesotrione (Lowest dose). As for the ratoon cane selectivity the best yield was achieved with the association ametryn + mesotrione +diclosulan. An appropriate association of herbicide molecules provides successful control of E. heterophylla, especially the association of sulfentrazone or diclosulan together with ametryn and mesotrione.

Eco-friendly synthesis of a novel adsorbent from sugarcane and high-pressure boiler water.

The development of industrial process in line with the circular economy and the environmental, social and corporate governance (ESG) is the foundation for sustainable economic development. Alternatives that make feasible the transformation of residues in added value products are promising and contribute to the repositioning of the industry towards sustainability, due to financial leverage obtained from lesser operational costs when compared with conventional processes, therefore increasing the company competitivity. In this study, it is presented a promising and innovative technology for the recycling of agro-industrial residues, the sugarcane bagasse and the high-pressure water boiler effluent, in the development of a low-cost adsorbent (HC-T) using the hydrothermal carbonization processes and its application in the adsorption of herbicide Diuron and Methylene Blue dye from synthetic contaminated water. The hydrothermal carbonization was performed in a Teflon contained inside a sealed stainless-steel reactor self-pressurized at 200°C, biomass-to-effluent (m/v) ratio of 1:3 and 24 h. The synthesized material (HC) was activated in an oven at 450°C for 10 min, thus being named adsorbent (HC-T) and characterized by textural, structural and spectroscopic analyses. The low-cost adsorbent HC-T presented an 11-time-fold increase in surface area and ∼40% increase in total pore volume in comparison with the HC material. The kinetic and isotherm adsorption experiment results highlighted that the HC-T was effective as a low-cost adsorbent for the removal of herbicide Diuron and Methylene Blue dye from synthetic contaminated waters, with an adsorption capacity of 35.07 (63.25% removal) and 307.09 mg g-1 (36,47% removal), respectively.

A Stable Fe-Zn Modified Sludge-Derived Biochar for Diuron Removal: Kinetics, Isotherms, Mechanism, and Practical Research.

To remove typical herbicide diuron effectively, a novel sludge-derived modified biochar (SDMBC600) was prepared using sludge-derived biochar (SDBC600) as raw material and Fe-Zn as an activator and modifier in this study. The physico-chemical properties of SDMBC600 and the adsorption behavior of diuron on the SDMBC600 were studied systematically. The adsorption mechanisms as well as practical applications of SDMBC600 were also investigated and examined. The results showed that the SDMBC600 was chemically loaded with Fe-Zn and SDMBC600 had a larger specific surface area (204 m2/g) and pore volume (0.0985 cm3/g). The adsorption of diuron on SDMBC600 followed pseudo-second-order kinetics and the Langmuir isotherm model, with a maximum diuron adsorption capacity of 17.7 mg/g. The biochar could maintain a good adsorption performance (8.88-12.9 mg/g) under wide water quality conditions, in the pH of 2-10 and with the presence of humic acid and six typical metallic ions of 0-20 mg/L. The adsorption mechanisms of SDMBC600 for diuron were found to include surface complexation, π-π binding, hydrogen bonding, as well as pore filling. Additionally, the SDMBC600 was tested to be very stable with very low Fe and Zn leaching concentration ≤0.203 mg/L in the wide pH range. In addition, the SDMBC600 could maintain a high adsorption capacity (99.6%) after four times of regeneration and therefore, SDMBC600 could have a promising application for diuron removal in water treatment.

Room-temperature ultrasonic-assisted self-assembled synthesis of silkworm cocoon-like COFs@GCNTs composite for sensitive detection of diuron in food samples.

Diuron (DU) exhibits good weed control effect but possesses strong hazard to human health, thereby designing a fast and sensitive method to detect DU is highly urgent. Herein, we report the ultrasonic-assisted self-assembly synthesis of porous covalent organic frameworks (COFs) spheres@graphitized multi-walled carbon nanotubes (GCNTs) composite based on π-π conjugation effect at room temperature, which was employed for DU determination. For the COFs@GCNTs composite, COFs with ultrahigh specific surface area shows strong adsorption ability towards DU, whereas GCNTs with favorable conductivity help to form the 3D interconnected conductive network around COFs spheres, thereby effectively compensating for the poor conductivity of COFs. Because of the synergistic effect between COFs and GCNTs, the developed sensor presented a low detection limit of 0.08 µM in the concentration range of 0.30-18.00 µM. Moreover, the actual sample analysis in the tomato and cucumber yielded satisfactory recoveries (96.40%-103.20%), proving reliable practicability of the developed sensor.

Dispersal of the pesticide diuron in the Great Barrier Reef.

Pesticides from urban and agricultural runoff have been detected at concentrations above current water quality guidelines in the Great Barrier Reef (GBR) marine environment. We quantify the load of the pesticide diuron entering GBR waters using the GBR-Dynamic SedNet catchment model. After comparison of simulated distributions with observations at 11 monitoring sites we determined a half-life of diuron in GBR marine waters of 40 days. We followed diuron dispersal in the GBR (2016-2018) using the 1 km resolution eReefs marine model. The highest diuron concentrations in GBR waters occurred in the Mackay-Whitsunday region with a spike in January and March 2017, associated with 126 and 118 kg d-1 diuron loads from Plane Creek and the O'Connell River respectively. We quantify areas of GBR waters exposed to potentially ecotoxic concentrations of diuron. Between 2016 and 2018, 400 km2 and 1400 km2 of the GBR were exposed to concentrations exceeding ecosystem threshold values of 0.43 and 0.075 µg L-1 respectively. Using observed mapped coral and seagrass habitat, 175 km2 of seagrass beds and 50 km2 of coral habitats had peak diuron concentrations above 0.075 µg L-1 during this period. While the highest concentrations are localised to river plumes and inshore environments, non-zero diuron concentrations extend along the Queensland coast. These simulations provide new knowledge for the understanding of pesticide dispersal and management-use in GBR catchments and the design of in-water monitoring systems.

Molecular Responses and Degradation Mechanisms of the Herbicide Diuron in Rice Crops.

Diuron [DU; 3-(3,4-dichlorophenyl)-1,1-dimethylurea], a widely used herbicide for weed control, arouses ecological and health risks due to its environment persistence. Our findings revealed that DU at 0.125-2.0 mg L-1 caused oxidative damage to rice. RNA-sequencing profiles disclosed a globally genetic expression landscape of rice under DU treatment. DU mediated downregulated gene encoding photosynthesis and biosynthesis of protein, fatty acid, and carbohydrate. Conversely, it induced the upregulation of numerous genes involved in xenobiotic metabolism, detoxification, and anti-oxidation. Furthermore, 15 DU metabolites produced by metabolic genes were identified, 7 of which include two Phase I-based and 5 Phase II-based derivatives, were reported for the first time. The changes of resistance-related phytohormones, like JA, ABA, and SA, in terms of their contents and molecular-regulated signaling pathways positively responded to DU stress. Our work provides a molecular-scale perspective on the response of rice to DU toxicity and clarifies the biotransformation and degradation fate of DU in rice crops.

Fluorescent melamine-formaldehyde/polyamine coatings for microcapsules enabling their tracking in composites.

This study aimed the development of fluorescent melamine-formaldehyde (MF)/polyamine coatings for labelling of prefabricated microcapsules and their tracking in composites. The composition of the fluorescent MF coatings was studied by FTIR spectroscopy, thermogravimetric analysis, and elemental analysis. The characteristics of the coatings and its deposition on different surfaces were investigated using optical and fluorescence microscopy and fluorescence spectroscopy. MF prepolymers were polymerised with tri- and polyamines yielding in fluorescent coatings without addition of fluorescent dyes. Both, MF/poly(ethylene imine) and MF/poly(vinyl amine) (PVAm) coated glass beads showed maximum fluorescence at an excitation wavelength of λmax = 360 nm with the emission maxima at λmax = 490 nm and λmax = 410 nm, correspondingly. The MF/PVAm polymer was coated on diuron-poly(methyl methacrylate) microcapsules and tracked in highly filled composites (water-based plaster/paint) to show its applicability. MF/polyamine coatings were identified as promising materials for the fluorescent labelling of prefabricated microcapsules.

Toxic Effects Induced by Diuron and Its Metabolites in Caenorhabditis elegans.

The toxicity of diuron herbicide and its metabolites has been extensively investigated; however, their precise toxic mechanisms have yet to be fully appreciated. In this context, we evaluated the toxic mechanism of diuron, 3,4-dichloroaniline (DCA) and 3-(3,4-dichlorophenyl)-1-methylurea (DCPMU), using Caenorhabditis elegans (C. elegans) in the L1 larval stage. For this purpose, worms were acutely exposed to the test chemicals with a preliminary concentration range of 0.5 to 500 µM and first analyzed for lethality (%). Next, the highest concentration (500 µM) was considered for survival (%), reactive oxygen and nitrogen species (RONS), glutathione (GSH) and ATP levels, autophagy index, behavior, and dopaminergic neurodegeneration parameters. Interestingly, increased lethality (%) was found for all chemicals at the higher concentrations tested (100 and 500 µM), with significant differences at 500 µM DCA (p < 0.05). A decrease in the median survival was observed mainly for DCA. Although no changes were observed in RONS production, GSH levels were significantly increased upon diuron and DCA treatment, likely reflecting an attempt to restore the redox status. Moreover, diuron and its metabolites impaired ATP levels, suggesting an alteration in mitochondrial function. The latter may trigger autophagy as an adaptive survival mechanism, but this was not observed in C. elegans. Dopaminergic neurotoxicity was observed upon treatment with all the tested chemicals, but only diuron induced alterations in the worms' locomotor behavior. Combined, these results indicate that exposure to high concentrations of diuron and its metabolites elicit distinct adverse outcomes in C. elegans, and DCA in particular, plays an important role in the overall toxicity observed in this experimental model.

The DCMU Herbicide Shapes T-cell Functions By Modulating Micro-RNA Expression Profiles.

DCMU [N-(3,4-dichlorophenyl)-N-dimethylurea] or diuron is a widely used herbicide, which can cause adverse effects on human, especially on immune cells, due to their intrinsic properties and wide distribution. These cells are important for fighting not only against virus or bacteria but also against neoplastic cell development. We developed an approach that combines functional studies and miRNA and RNA sequencing data to evaluate the effects of DCMU on the human immune response against cancer, particularly the one carried out by CD8+ T cells. We found that DCMU modulates the expression of miRNA in a dose-dependent manner, leading to a specific pattern of gene expression and consequently to a diminished cytokine and granzyme B secretions. Using mimics or anti-miRs, we identified several miRNA, such as hsa-miR-3135b and hsa-miR-21-5p, that regulate these secretions. All these changes reduce the CD8+ T cells' cytotoxic activity directed against cancer cells, in vitro and in vivo in a zebrafish model. To conclude, our study suggests that DCMU reduces T-cell abilities, participating thus to the establishment of an environment conducive to cancer development.