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BACKGROUND: Pesticide exposure has consistently been associated with Parkinsons disease (PD) onset. Yet, fewer epidemiologic studies have examined whether pesticides influence PD motor and non-motor symptom progression. OBJECTIVES: Using a geographic information system tool that integrates agricultural pesticide use reports and land use records to derive ambient exposures at residences and workplaces, we assessed associations between specific pesticides previously related to PD onset with PD symptom progression in two PD patient cohorts living in agricultural regions of California. METHODS: We calculated the pounds of pesticide applied agriculturally near each participants residential or occupational addresses from 1974 to the year of PD diagnosis, using a geographic information system tool that links the California Pesticide Use Reports database to land use data. We examined 53 pesticides selected a priori as they have previously been associated with PD onset. We longitudinally followed two PD patient cohorts (PEG1 N = 242, PEG2 N = 259) for an average of 5.0 years (SD ± 3.5) and 2.7 years (SD ± 1.6) respectively and assessed PD symptoms using the movement disorder specialist-administered Unified Parkinsons disease Rating Scale part III (UPDRS), Mini-Mental State Examination (MMSE), and Geriatric Depression Scale (GDS). Weighted time-to-event regression models were implemented to estimate effects. RESULTS: Ten agricultural pesticides, including copper sulfate (pentahydrate), 2-methyl-4-chlorophenoxyacetic acid (MCPA) dimethylamine salt, tribufos, sodium cacodylate, methamidophos, ethephon, propargite, bromoxynil octanoate, monosodium methanearsonate (MSMA), and dicamba, were associated with faster symptom progression. Among these pesticides, residential or workplace proximity to higher amounts of copper sulfate (pentahydrate) and MCPA (dimethylamine salt) was associated with all three progression endpoints (copper sulfate: HRs = 1.22-1.36, 95 % CIs = 1.03-1.73; MCPA: HRs = 1.27-1.35, 95 % CIs = 1.02-1.70). CONCLUSIONS: Our findings suggest that pesticide exposure may not only be relevant for PD onset but also PD progression phenotypes. We have implicated ten specific pesticide active ingredients in faster PD motor and non-motor decline.

Objective: A method was developed for the determination of chlorantraniliprole, flubendiamide and 2-methyl-4-chlorophenoxyacetic acid in milk by ultra performance liquid chromatography-tandemmass spectrometry (UPLC-MS/MS). Methods: The samples were extracted by acetonitrile, salted out by sodium chloride, degreased by n-hexane and purified by two-step cryogenic centrifugation. The analytes were separated by Waters Acquity UPLC BEH C18 chromatographic column. The mobile phase was eluted with a gradient of acetonitrile and 0.1% formic acid aqueous solution. The detection was carried out with electrospray ion source, positive and negative ion switching, scanning mode and the quantification was accomplished by external standard method of matrix standard curve. Results: The three pesticides showed a good linear relationship (R2>0.999) in the range of 10~150 ng/mL. With the addition of 5.0, 10.0 and 50.0 μg/kg in the standard recovery experiment, the recoveries were 73.3%~117.3% and the relative standard deviations were 1.0%~5.9% (n=6). The detection limits (S/N≥3) and the limit of quantification of the method (S/N≥10) were 1.0 and 5.0 μg/kg, respectively. Conclusion: This method is simple, accurate and sensitive, which is suitable for simultaneous determination of chlorfenoxamide, fluorofenoxamide and 2-methyl-4-chlorophenoxyacetic acid residues in milk.

It has been shown that 2-methyl-4-chlorophenoxyacetic acid (MCPA) forms an ionic associate (IA) with the polymethine dye Astrafloxin FF (AF). The energy efficiency of IA formation is substantiated by the method of mathematical modeling. The molecular modeling of MCPA– + AF+ systems and related calculations are performed by using the HyperChem 8.0 software package in various initial variants for the mutual arrangement of counterions ("single point" procedure). The geometric optimization of ions is carried out by the molecular mechanics method MM+. The obtained IA is quite well extracted by various aromatic hydrocarbons. The maximum IA extraction from the aqueous phase is attained at pH = 6–12. The effect of the dye concentration on the optical density of the toluene extracts of MCPA–AF ionic associates is studied. The IA extraction attains a maximum at a dye concentration of (1.6–2.8) × 10–4 M. Extraction equilibrium is reached for 50–60 s. The stoichiometry of the MCPA–AF ionic associate is established by the spectrophotometric methods of isomolar series and equilibrium shift; the ratio of components is 1 : 1. The IA formation and extraction scheme is proposed. The conditional molar absorption coefficient of the ionic associate is 1.1 × 105. The calibration dependence of the optical density of extracts on the MCPA concentration is described by the linear equation a = 0.0116 + 0.0613 within the MCPA concentration range of 0.9–45.6 μg/cm3. The MCPA detection limit calculated by the 3s criterion (n = 5, P = 0.95) is 0.8 μg/cm3. The disperancy of the plotted calibration curve for the detection of 2-methyl-4-chlorophenoxyacetic acid is estimated by using the Cochran test G. The calculated Cochran criterion (n = 5, P = 0.95) is lower than its tabular value, i.e., Gcalcd = 0.25 < Gtab = 0.64 to evidence variance homogeneity. The method for the photometric extraction detection of 2-methyl-4-chlorophenoxyacetic acid in water and bottom sediments has been developed. [ABSTRACT FROM AUTHOR]

2-Methyl-4-chlorophenoxyacetic acid (MCPA) is one of the most widely used herbicides, so adsorption and detection of MCPA in the environment is critical. Blue fluorescent carbon dot (CD) was synthesized from citric acid and urea, which could be quenched by MCPA. Herein, bifunctional molecularly imprinted polymer (CD@MIP) was prepared on monodisperse poly (glycidyl methacrylate- co -ethylene glycol dimethacrylate) microspheres, with 4-vinylpyridine as the functional monomer, ethylene glycol dimethacrylate as the cross-linking agent, and doped with CD. The enrichment ability of CD@MIP for MCPA and fluorescence detection performance were determined. The maximum adsorption amount of MCPA was 93.9 mg g−1 as determined by isothermal adsorption experiments and was in accordance with the Langmuir adsorption model. The results of the kinetic experiments showed that the adsorption equilibrium reached within 30 min, which possessed a relatively fast adsorption rate and was in accordance with the pseudo-second-order adsorption model. Both MIP without CD and non-imprinted polymers were also fabricated and tested as references. Fluorescence experiments showed good linearity of CD@MIP in the range of 0–80 μmol. The cabbage samples were analyzed by high performance liquid chromatography with a linear range of 0.02–15 μg mL−1, recoveries of 90.5%–98% and low relative standard deviations (RSD, n = 3) of 1.5%–5.9%. CD@MIP with excellent performance provides a feasible practical application in the detection and enrichment of MCPA. [Display omitted] • Surface imprinted polymer prepared based on SI-ATRP improves the traditional method. • Molecularly imprinted polymers doped with carbon dots combine their advantages. • The dual-function MIP allows simultaneous adsorption and detection of MCPA. [ABSTRACT FROM AUTHOR]

Herbicides are widely used to control weeds in agriculture filed, however, the excessive use of the conventional formulation causes harmful side effects on the environment. To relieve this problem, natural polymer nanoparticles as herbicide carrier were rapidly developed and applied in recent years. In the present study, chitosan/tripolyphosphate (CS/TPP) nanoparticles were synthesized as nanocarrier to load herbicide 4-chloro-2-methylphenoxyacetate sodium salt (MCPA-Na). The encapsulation efficiency (EE) of 51.32% was obtained through measuring indirectly by high performance liquid chromatography (HPLC). The free and MCPA-Na-loaded CS/TPP nanoparticles were characterized by using dynamic light scattering (DLS), zeta potential, Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM). The encapsulation of MCPA-Na in CS/TPP nanoparticles resulted in the change of MCPA-Na release profile in different pH media and displayed effective sustained-release under neutral condition. The evaluation of herbicidal activity against Bidens pilosa L. showed that the efficacy enhancement of MCPA-Na was realized after encapsulation in CS/TPP nanoparticles. The proposed herbicide nanoformulation presented a good potential as a sustainable alternative for weed control in agriculture., (© 2024. The Author(s).)

2-Methyl-4-chlorophenoxyacetic acid (MCPA) is a pervasive phenoxyacetic acid herbicide, frequently identified in environmental matrices. This study undertakes a systematic investigation of the atmospheric environmental transformation behavior and potential ecological risks of hydroxyl radical (HO•) induced MCPA for the first time, employing computational chemistry and computational toxicology methodologies. Our findings indicate that the initial degradation of MCPA can be triggered by both HO•-addition and hydrogen-abstraction reactions, with the latter being more likely to occur. The primary reaction pathways were identified as R2, R3, R8, and R13. The total rate constant for the gas-phase reaction of MCPA with HO• was calculated as 8.59 × 10−12 cm3 molecule −1 s−1 at 298 K. This total rate constant displayed a distinct positive temperature dependence within the temperature range of 250–375 K. Structures of 25 transformation products, which include 7 experimentally observed compounds, were determined from further reactions of crucial intermediates. The toxicity assessment of MCPA and its transformation products indicated that most of the hydroxyl oxidation products exhibit toxicity to aquatic organisms and possess mutagenic, developmental toxic, non-genotoxic carcinogenic, and skin irritating or corrosive properties. This research contributes to a comprehensive understanding of the transformation mechanisms, kinetics, and environmental repercussions of gas-phase MCPA, enhancing our ability to predict and mitigate its ecological impact. • H-abstraction occurring on the methyl group is the most favorable initial pathway. • Rate constants and branching ratios were determined for the MCPA+HO • reaction. • Ecological risk assessment of MCPA and its products were conducted. [ABSTRACT FROM AUTHOR]

In response to the growing ethical and environmental concerns associated with animal testing, numerous in vitro tools of varying complexity and biorelevance have been developed and adopted in pharmaceutical research and development. In this work, we present one of these tools, i.e., the Meso-fluidic Chip for Permeability Assessment (MCPA), for the first time. The MCPA combines an artificial barrier (PermeaPad®) with an organ-on-chip device (MIVO®) and real-time automated concentration measurements, to yield a sustainable, yet effortless method for permeation testing. The system offers three major physiological aspects, i.e., a biomimetic membrane, an optimal membrane interfacial area-to-donor-volume-ratio (A/V) and a physiological flow on the acceptor/basolateral side, which makes the MPCA an ideal candidate for mechanistic studies and excellent in vivo bioavailability predictions. We validated the method with a handful of assorted drug compounds in unstirred and stirred donor conditions, before exploring its applicability as a tool for dissolution/permeation testing on a BCS class III/I drug (pyrazinamide) crystalline adducts and BCS class II/IV (hydrocortisone) amorphous solid dispersions. The results were highly reproducible and clearly displayed the method's potential for evaluating the performance of enabling formulations, and possibly even predicting in vivo performance. We believe that, upon further development, the MCPA will serve as a useful in vitro tool that could push sustainability into pharmaceutics by refining, reducing and replacing animal testing in early-stage drug development., Competing Interests: Declaration of Competing Interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Associate Professor Massimiliano Pio Di Cagno, leading author of this paper, is the inventor of the PermeaPad® barrier and scientific consultant (5% position) for Phabioc GmbH, the manufacturer of PermeaPad®. Dr. Silvia Scaglione is the founder of React4life S.p.A., the manufacturer of MIVO®., (Copyright © 2023 The Authors. Published by Elsevier Inc. All rights reserved.)

The aim of this study was to evaluate the response of Galinsoga parviflora to different doses of the herbicide Chwastox Turbo 340 SL [2-methyl-4- chlorophenoxyacetic acid (MCPA) + dicamba] used alone and with an adjuvant. The study was conducted on the spring barley cultivar ‘Suweren.’ During the tillering stage of spring barley, a weed control treatment was applied using Chwastox Turbo 340 SL at a rate of 100% and at rates reduced by 33% and 50%, and was applied either alone or with an oil adjuvant. Plots without herbicide and adjuvant application were the control treatment. The present study showed that in spring barley the largest plants of G. parviflora, which produced the highest number of branches, flower heads, and achenes, occurred in the control treatment where no herbicide and adjuvant were applied. Morphology, productivity, and biomass were not found to vary greatly between G. parviflora plants occurring in the plots where the reduced rates of Chwastox Turbo 340 SL and in those where the manufacturer’s recommended rate were applied. The number of achenes produced by G. parviflora was positively correlated with plant height and negatively with plant biomass. The germination capacity of G. parviflora diaspores was not significantly different between the herbicide protection treatments.

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The aim of this study was to evaluate the response of Galinsoga parviflora to different doses of the herbicide Chwastox Turbo 340 SL [2-methyl-4- chlorophenoxyacetic acid (MCPA) + dicamba] used alone and with an adjuvant. The study was conducted on the spring barley cultivar 'Suweren.' During the tillering stage of spring barley, a weed control treatment was applied using Chwastox Turbo 340 SL at a rate of 100% and at rates reduced by 33% and 50%, and was applied either alone or with an oil adjuvant. Plots without herbicide and adjuvant application were the control treatment. The present study showed that in spring barley the largest plants of G. parviflora, which produced the highest number of branches, flower heads, and achenes, occurred in the control treatment where no herbicide and adjuvant were applied. Morphology, productivity, and biomass were not found to vary greatly between G. parviflora plants occurring in the plots where the reduced rates of Chwastox Turbo 340 SL and in those where the manufacturer's recommended rate were applied. The number of achenes produced by G. parviflora was positively correlated with plant height and negatively with plant biomass. The germination capacity of G. parviflora diaspores was not significantly different between the herbicide protection treatments. [ABSTRACT FROM AUTHOR]

Pesticide contamination of drinking water is of high concern due to their hazardous effects on ecosystems. Several detection methods are available which are associated with many drawbacks, e.g. slow response time and laborious procedural techniques. This limits their practicability. Therefore, there is a dire need to develop quick, simpler but equally sensitive and practical methods for pesticide detection. Herein, we report a highly sensitive assay using fluorescent AuNCs for the detection of a pesticide i.e., 2-methyl-4-chlorophenoxyacetic acid (MCPA). For this purpose, three different fluorescent Au nanoclusters stabilized by histidine (His-AuNCs), lysozyme (Lys-AuNCs) and RNase (RNase-AuNCs) were systematically studied as optical probes for the detection of MCPA using a turn-on assay. The fluorescence of these AuNCs was initially quenched with Cu2+ ions followed by the quantitative recovery of their fluorescent signals in the presence of MCPA. The sensitivity and selectivity of these clusters for MCPA were in a linear dynamic range, i.e., 110–180 nM, 100–170 nM and 90–160 nM in case of His-AuNCs, Lys-AuNCs and RNase-AuNCs, respectively. Also, the aforesaid clusters were having a different limit of detection (LOD) by each type, i.e., highest by His-AuNCs (21.87), intermediate by Lys-AuNCs (12.97) and lowest by RNase-AuNCs (9.26 nM). Hence, the RNase-AuNCs are found to be the most sensitive, whereas His-AuNCs are least sensitive for the detection of MCPA. These findings offer a rapid, sensitive and selective assay for MCPA detection and have potential implications for the on-site, real-time monitoring of noxious pollutants. [ABSTRACT FROM AUTHOR]

MCPA is a post-emergence herbicide for control of wild oats and annual grassy weeds found among several economically important crops. In the present work, the Eigen values and Eigen functions of the MCPA have been calculated using two basis sets of DFT. The Global DFT descriptors for the compound have also been calculated. The Fukui functions, local softness, and atomic charges for each center of MCPA have also been calculated It has been found that all the reactivity centers of MCPA are not equal in chemical reactivity. The differences in chemical reactivity of different sites have been investigated in detail in this work. [ABSTRACT FROM AUTHOR]

This research provides information about combinations of several amino acids, including l-proline (Pro), l-arginine (Arg), and l-histidine (His), with phenoxyacetic acid herbicides (MCPA and 2,4-D). Five amino acid ionic liquids (AAILs), one amino acid higher-melting salt (AAHMS), and two amino acid liquid cocrystals (AALCs) were obtained in high yields (>90%). The ionization of the six new structures was confirmed by NMR, IR, and molecular modeling. X-ray crystallography was used to definitively confirm the binding location of the mobile hydrogen. Furthermore, we propose a computational method for estimating the energy of specific hydrogen bond(s) in AAIL crystals based on the NBO and QTAIM hydrogen bond parameters obtained by model calculations. An in-depth analysis of the structures allowed to answer the question posed in the title, ionic liquids or liquid cocrystals? AAILs based on arginine and histidine were obtained. In contrast, combining proline with MCPA and 2,4-D led to AALCs. Finally, the compounds were analyzed to measure their herbicidal activity. These studies proved that the novel form of MCPA or 2,4-D improved its ability to control weeds compared to commercial formulations containing the same active ingredients.

Pilocytic astrocytomas (PA) typically exhibit distinct clinical, radiological, histopathological, and genetic features. DNA-methylation profiling distinguishes PA according to their location (infratentorial, midline, hemispheric, or spinal). In the hemispheric location, distinguishing PA from glioneuronal tumors remains a common diagnostic challenge for neuropathologists. Furthermore, the current version of the DKFZ classifier seems to have difficulty separating them from gangliogliomas. In this study, after central radiological review, we identified a histopathologically defined set of PA (histPA, n = 11) and a cohort of DNA-methylation defined PA (mcPA, n = 11). Nine out of the 11 histPA matched the methylation class of hemispheric PA, whereas 2 cases were classified at the end of the study as dysembryoplastic neuroepithelial tumors. Similarly, the mcPA cohort contained tumors mainly classified as PA (7/11), but 4 cases were classified as glioneuronal. The analysis of the 16 tumors with an integrated diagnosis of PA revealed that they affect mainly children with a wide spectrum of radiological, histopathological (i.e. a predominantly diffuse growth pattern), and genetic characteristics (large range of mitogen-activated protein kinase alterations). Based on these results, we consider hemispheric PA to be different from their counterparts in other locations and to overlap with other glioneuronal tumors, reinforcing the necessity of interpreting all data to obtain an accurate diagnosis., (© The Author(s) 2024. Published by Oxford University Press on behalf of American Association of Neuropathologists, Inc. All rights reserved. For permissions, please email: journals.permissions@oup.com.)

Current knowledge about how biochars affect the fate of pesticides in soil is based on studies that used pure biochars. After finding that an additional biological post-pyrolysis treatment, such as co-composting or lactic fermentation, is required for biochars for superior performance in temperate arable soils, a knowledge gap formed of how such further processed biochar products would affect the fate of pesticides in soil. This study compared the effects of a novel fermented biochar alone or mixed with biogas residues on the fate of two pesticides, 4-chloro-2-methylphenoxyacetic acid (MCPA) and metalaxyl-M, in a temperate arable soil to the traditional organic amendments wheat straw and compost. The fate of 14 C-labeled MCPA was markedly affected in different ways. Fermented biochar effectively reduced the water-extractability and mineralization due to adsorption that was comparable to adsorption strengths reported for pure biochars. However, this effect was weak for the biochar mixed with biogas residues. Straw reduced water-extractable amounts due to increased biodegradation and formation of likely biogenic non-extractable residues of MCPA. In contrast, compost decelerated mineralization and increased the water solubility of the MCPA residues due to released dissolved organic matter. The amendments' effects were minor regarding 14 C-metalaxyl-M, except for the fermented biochar which again reduced water-extractability and delayed degradation due to adsorption. Thus, the effects of the organic amendments differed for the two pesticide compounds with only the fermented biochar's effect being similar for both. However, this effect was no longer present in the mixed product containing 20% biochar. Our findings clearly show that biologically treated biochar-containing products can affect the fate of pesticides in soil very differently, also when compared to traditional organic amendments. Such impacts and their desirable and undesirable ecotoxicological implications need to be considered before the large-scale application of biochars to temperate arable soils., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Adding herbicides to sewer lines, a common practice for controlling root intrusion in sewer pipes, may adversely impact downstream wastewater treatment by inhibiting nitrification and denitrification performance. This study investigated the effects of herbicides, namely diquat, triclopyr, and 2-methyl-4-chlorophenoxyacetic acid (MCPA)-dicamba, on these processes. Various parameters were monitored, including oxygen uptake rate (OUR), nutrients (NH 3 -N, TP, NO 3 -N, and NO 2 -N), chemical oxygen demand (COD), and herbicide concentrations. It was found that nitrification was not affected by OUR in the presence of each herbicide at various concentrations (1, 10, and 100 mg L -1 ). Additionally, MCPA-dicamba at various concentrations demonstrated minimal inhibition in the nitrification process compared to diquat and triclopyr. COD consumption was not affected by the presence of these herbicides. However, triclopyr significantly inhibited NO 3 -N formation in the denitrification process at various concentrations. Similar to nitrification process, both COD consumption and herbicide reduction concentration were not affected by the presence of herbicides during the denitrification process. Adenosine triphosphate measurements showed minimal impact on nitrification and denitrification processes when herbicides were present in the solution up to a concentration of 10 mg L -1 . Tree root kill efficiency experiments were performed on Acacia melanoxylon. Considering the performance on nitrification and denitrification process, diquat emerged as the best herbicide option (concentration of 10 mg L -1 ), with a 91.24% root kill efficiency., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier Ltd.. All rights reserved.)

2-Methyl-4-chlorophenoxyacetic acid (MCPA) is a highly mobile herbicide that is frequently detected in global potable water sources. One potential mitigation strategy is the sorption on biochar to limit harm to unidentified targets. However, irreversible sorption could restrict bioefficacy thereby compromising its usefulness as a vital crop herbicide. This research evaluated the effect of pyrolysis temperatures (350, 500 and 800°C) on three feedstocks; poultry manure, rice hulls and wood pellets, particularly to examine effects on the magnitude and reversibility of MCPA sorption. Sorption increased with pyrolysis temperature from 350 to 800°C. Sorption and desorption coefficients were strongly corelated with each other (R2 = 0.99; P < .05). Poultry manure and rice hulls pyrolyzed at 800°C exhibited irreversible sorption while for wood pellets at 800°C desorption was concentration dependent. At higher concentrations some desorption was observed (36% at 50 ppm) but was reduced at lower concentrations (1-3% at < 5 ppm). Desorption decreased with increasing pyrolysis temperature. Sorption data were analyzed with Langmuir, Freundlich, Dubinin-Radushkevich and Temkin isotherm models. Freundlich isotherms were better predictors of MCPA sorption (R2 ranging from 0.78 to 0.99). Poultry manure and rice hulls when pyrolyzed at higher temperatures (500 and 800°C) could be used for remediation efforts (such as spills or water filtration), due to the lack of desorption observed. On the other hand, un-pyrolyzed feedstocks or biochars created at 350°C could perform superior for direct field applications to limit indirect losses including runoff and leaching, since these materials also possess the ability to release MCPA subsequently to potentially allow herbicidal action., Competing Interests: The authors have declared that no competing interests exist., (Copyright: This is an open access article, free of all copyright, and may be freely reproduced, distributed, transmitted, modified, built upon, or otherwise used by anyone for any lawful purpose. The work is made available under the Creative Commons CC0 public domain dedication.)

Herbicide resistance is rapidly emerging in Cyperus difformis in rice fields across China. The response of a C. difformis population GX-35 was tested against five acetolactate synthase (ALS)-inhibiting herbicides, auxin herbicide MCPA and photosynthesis II (PSII)-inhibitor bentazone. Population GX-35 evolved multiple resistance to ALS-inhibiting herbicides (penoxsulam, bispyribac‑sodium, pyrazosulfuron-ethyl, halosulfuron-methly and imazapic) and auxin herbicide MCPA, with resistance levels of 140-, 1253-, 578-, 18-, 13-, and 21-fold, respectively, compared to the susceptible population. In this population, ALS gene expression was similar to that of the susceptible population. However, an Asp376Glu mutation in ALS gene was observed, leading to reduced inhibition of in-vitro ALS activities by five ALS-inhibiting herbicides. Furthermore, CYP71D8, CYP77A3, CYP78A5 and three ABC transporter genes (cluster-14412.23067, cluster-14412.25321, and cluster-14412.24716) over-expressed in absence of penoxsulam. On the other hand, an UGT73C1 and an ABC transporter (cluster-14412.25038) were induced by penoxsulam. Additionally, both over-expression and induction were observed for CYP74, CYP71A1, UGT88A1 and an ABC transporter (cluster-14412.21723). The GX-35 population has indeed evolved multiple herbicide resistance in China. Therefore, a diverse range of weed control tactics should be implemented in rice field., Competing Interests: Declaration of Competing Interest The authors declare no conflict of interest., (Copyright © 2023 Elsevier Inc. All rights reserved.)

Toxicity of accumulating substrates is a significant problem in several disorders of valine and isoleucine degradation notably short-chain enoyl-CoA hydratase (ECHS1 or crotonase) deficiency, 3-hydroxyisobutyryl-CoA hydrolase (HIBCH) deficiency, propionic acidemia (PA), and methylmalonic aciduria (MMA). Isobutyryl-CoA dehydrogenase (ACAD8) and short/branched-chain acyl-CoA dehydrogenase (SBCAD, ACADSB) function in the valine and isoleucine degradation pathways, respectively. Deficiencies of these acyl-CoA dehydrogenase (ACAD) enzymes are considered biochemical abnormalities with limited or no clinical consequences. We investigated whether substrate reduction therapy through inhibition of ACAD8 and SBCAD can limit the accumulation of toxic metabolic intermediates in disorders of valine and isoleucine metabolism. Using analysis of acylcarnitine isomers, we show that 2-methylenecyclopropaneacetic acid (MCPA) inhibited SBCAD, isovaleryl-CoA dehydrogenase, short-chain acyl-CoA dehydrogenase and medium-chain acyl-CoA dehydrogenase, but not ACAD8. MCPA treatment of wild-type and PA HEK-293 cells caused a pronounced decrease in C3-carnitine. Furthermore, deletion of ACADSB in HEK-293 cells led to an equally strong decrease in C3-carnitine when compared to wild-type cells. Deletion of ECHS1 in HEK-293 cells caused a defect in lipoylation of the E2 component of the pyruvate dehydrogenase complex, which was not rescued by ACAD8 deletion. MCPA was able to rescue lipoylation in ECHS1 KO cells, but only in cells with prior ACAD8 deletion. SBCAD was not the sole ACAD responsible for this compensation, which indicates substantial promiscuity of ACADs in HEK-293 cells for the isobutyryl-CoA substrate. Substrate promiscuity appeared less prominent for 2-methylbutyryl-CoA at least in HEK-293 cells. We suggest that pharmacological inhibition of SBCAD to treat PA should be investigated further., (© 2023 SSIEM.)

Introduction: Intestinal toxicity can occur following ingestion of various drugs, chemicals, and toxins. Intestinal fatty acid binding protein is a cytosolic protein specific to intestinal epithelial cells released into the systemic circulation following intestinal injury. Understanding intestinal toxicity in poisoning has the potential to explain mechanisms of toxicity and gastrointestinal symptoms., Methods: Plasma samples were retrospectively analysed for intestinal fatty acid binding protein in 25 healthy controls and in those poisoned with Gloriosa superba ( n  = 18), Thevetia peruviana ( n  = 26), organophosphates (in various solvents) ( n  = 17), paracetamol ( n  = 14), glyphosate ( n  = 20), 2-methyl-4-chlorophenoxyacetic acid ( n  = 18) and propanil ( n  = 19)., Results: Median peak plasma intestinal fatty acid binding protein concentrations were significantly higher in patients poisoned with Gloriosa superba (2,994.1 µg/L; interquartile range 600.0-5,158.2, P  < 0.001), Thevetia peruviana (1,292.5 µg/L; interquartile range 760.3 - 2,076.2; P  < 0.001), glyphosate (1,803.6 µg/L; interquartile range 225.7-8,927.7; P  < 0.001), 2-methyl-4-chlorophenoxyacetic acid (1,236.2 µg/L; interquartile range 192.6 - 1,709.7; P  = 0.010), paracetamol (1,066.5 µg/L; interquartile range 512.9 - 1,336.9; P  = 0.035), and organophosphate poisoning (729.8 µg/L; interquartile range 431.5 - 1,588.2; P  = 0.046) than in healthy controls (221.6 µg/L; interquartile range 134.8 - 460.1). Median intestinal fatty acid binding protein was not statistically significantly increased compared to controls after propanil poisoning (630.0 µg/L; interquartile range 23.5 - 1,390.3; P  = 0.423)., Conclusions: Our pilot study describes intestinal injury assessed by elevated plasma intestinal fatty acid binding protein concentrations following the ingestion of several poisons. This serves as a foundation for further exploration into enterocyte damage in toxicology.

The ECL properties and application of a novel luminescent material molybdenum disulfide-graphene quantum dots (MoS 2 -GQDs) hybrid nanocomposite was reported for the first time. The hybridization of MoS 2 and GQDs endowed nanocomposite with structural and compositional advantages for boosting the ECL performance of GQDs. Impressively, the ECL could be remarkable enhanced using MoS 2 -GQDs hybrid nanocomposite, which was ∼13, ∼185 and ∼596-folds larger than the ECL intensity of GQDs, MoS 2 modified electrodes and bare electrode, respectively. Subsequently, as a sensing platform, the MoS 2 -GQDs hybrid nanocomposite was applied to fabricate molecularly imprinted electrochemiluminescence sensor for the ultrasensitive and selective determination of 2-methyl-4-chlorophenoxyacetic acid. Under optimal conditions, the detection limit of the prepared sensor was 5.5 pmol L −1 (S/N = 3) within a linear concentration range of 10 pmol L −1 –0.1 μmol L −1 . The developped sensor exhibited high sensitivity, good selectivity, reproducibility and stability, suggesting the potential for detecting pesticides and veterinary drugs at trace levels in food safety and environmental control. [ABSTRACT FROM AUTHOR]

4-Chloro-2-methylphenoxyacetic acid (MCPA) is a widely used herbicide across the world. MCPA is persistent and easily transports into anoxic environment, such as groundwater, sediments and deep soils. However, little research on anaerobic microbial degradation of MCPA was carried out. The functional microorganisms as well as the catabolic pathway are still unknown. In this research, an anaerobic MCPA-degrading bacterial consortium was enriched from the river sediment near a pesticide-manufacturing plant. After about 6 months' acclimation, the MCPA transformation rate of the consortium reached 4.32 μmol g -1 day -1 , 25 times faster than that of the original sludge. 96% of added MCPA (2.5 mM) was degraded within 9 d of incubation. Three metabolites including 4-chloro-2-methylphenol (MCP), 2-methylphenol (2-MP) and phenol were identified during the anaerobic degradation of MCPA. An anaerobic catabolic pathway was firstly proposed: firstly, MCPA was transformed to MCP via the cleavage of the aryl ether, then MCP was reductively dechlorinated to 2-MP which was further demethylated to phenol. The 16S rRNA gene amplicon sequencing revealed a substantial shift in the bacterial community composition after the acclimation. SBR1031, Acidaminococcaceae, Aminicenantales, Syntrophorhabdus, Acidaminobacter, Bacteroidetes&#95;vadinHA17, Methanosaeta, Bathyarchaeia, KD4-96, Anaeromyxobacter, and Dehalobacter were significantly increased in the enriched consortium after acclimation, and positively correlated with the anaerobic degradation of MCPA as suggested by heat map correlation analysis. This study provides a basis for further elucidation of the anaerobic catabolism of MCPA, and contributes to developing efficient and low-cost anaerobic treatment technologies for MCPA pollution., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

To screen out suitable herbicides for peach nurseries, we treated the potted seedlings of the peach rootstock 'Nemaguard' with eleven herbicides under recommended doses to investigate the changes of physiological indices and comprehensively evaluate the safety of different herbicides using principal component analysis (PCA). The results showed that soil application of quizalofop-p exhibited no detectable phytotoxicity on rootstock seedlings, while the remaining herbicides generated multiple symptoms, including green loss, wilting, spot, and withering. Starane caused rapid wilting and death, with a 100.0% phytotoxicity index (PI). Soil application of n-(phosphonomethyl)glycine, glufosinate-ammonium, acetochlor, and MCPA-Na showed a PI＞65.0%. As compared with the control, all herbicides inhibited leaf area growth to varying degrees, with a 10.0%-56.2% and 5.8%-44.4% reduction in young leaf area and mature leaf area, respectively. All herbicides, except quizalofop-p, increased the electrolyte permeability of leaf and root tip cells by 21.2%-145.0% and 36.9%-291.4%, respectively, and significantly inhibited root growth. The total root length, root surface area, root volume, and the number of root tips significantly decreased by 37.3%-75.3%, 35.7%-83.0%, 44.3%-89.9%, and 42.6%-73.7%, respectively. Although net photosynthetic rate ( P n ) and transpiration rate ( T r ) of leaves were not significantly affected by quizalofop-p, mesotrione-atrazine, MCPA-Na·bentazone, bensulfuron-methyl·quinclorac, and bensulfuron-methyl·acetochlor, there was significant reduction of 29.6%, 28.9%, 28.4% and 27.9% in P n and 21.9%, 29.2%, 26.4%, and 19.7% in T r post soil application of n-(phosphonomethyl)glycine, glufosinate-ammonium, acetochlor, and MCPA-Na. The overall safety ranking of the 11 examined herbicides is as follows: quizalofop-p>bensulfuron-methyl·acetochlor>bensulfuron-methyl·quinclorac>esotrione·atrazine> auizalofop-p·fluoroglycofen>acetochlor>MCPA-Na·bentazone>MCPA-Na>n-(phosphonomethyl)glycine>glufosinate-ammonium>sterane.

A novel polymeric herbicide based on phenoxyacetic acid derivatives was prepared by the reaction of epoxidised liquid natural rubber (ELNR) with 2,4-dichlorophenoxyacetic acid (2,4-D) or 2-methyl-4-chlorophenoxyacetic acid(MCPA). The liquid natural rubber (LNR) was firstly obtained from the degradation of natural rubber latex with tert-butyl hydroperoxide and cobalt acetylacetonate at 65oC for 72 hrs. The epoxidised liquid natural rubber was prepared from thereaction of LNR with formic acid and hydrogen peroxide at 50oC for 6 hrs. The reaction of epoxidised liquid natural rubber with 2,4-D or MCPA using triethylamine as a catalyst in toluene was performed at 70, 80, and 90oC for 6, 9, 12, 18, and 24hrs. The polymeric herbicides obtained were characterized and the grafting percentage of 2,4-D or MCPA onto liquid natural rubber were also determined by FT-IR and 1H-NMR spectroscopy. It was found that the grafting percentage increased with increasing amount of reactants, temperature, and reaction time. The release of 2,4-D and MCPA from polymeric herbicides was investigated in pH 6, 7, and 8 buffers at room temperature. The results show that the slowest release of 2,4-D and MCPA was found to be constant at pH 7 for 14 and 10 days, respectively.

Background: Pesticide exposure has consistently been associated with Parkinson's disease (PD) onset. Yet, fewer epidemiologic studies have examined whether pesticides influence PD motor and non-motor symptom progression., Objectives: Using a geographic information system tool that integrates agricultural pesticide use reports and land use records to derive ambient exposures at residences and workplaces, we assessed associations between specific pesticides previously related to PD onset with PD symptom progression in two PD patient cohorts living in agricultural regions of California., Methods: We calculated the pounds of pesticide applied agriculturally near each participant's residential or occupational addresses from 1974 to the year of PD diagnosis, using a geographic information system tool that links the California Pesticide Use Reports database to land use data. We examined 53 pesticides selected a priori as they have previously been associated with PD onset. We longitudinally followed two PD patient cohorts (PEG1 N = 242, PEG2 N = 259) for an average of 5.0 years (SD ± 3.5) and 2.7 years (SD ± 1.6) respectively and assessed PD symptoms using the movement disorder specialist-administered Unified Parkinson's disease Rating Scale part III (UPDRS), Mini-Mental State Examination (MMSE), and Geriatric Depression Scale (GDS). Weighted time-to-event regression models were implemented to estimate effects., Results: Ten agricultural pesticides, including copper sulfate (pentahydrate), 2-methyl-4-chlorophenoxyacetic acid (MCPA) dimethylamine salt, tribufos, sodium cacodylate, methamidophos, ethephon, propargite, bromoxynil octanoate, monosodium methanearsonate (MSMA), and dicamba, were associated with faster symptom progression. Among these pesticides, residential or workplace proximity to higher amounts of copper sulfate (pentahydrate) and MCPA (dimethylamine salt) was associated with all three progression endpoints (copper sulfate: HRs = 1.22-1.36, 95 % CIs = 1.03-1.73; MCPA: HRs = 1.27-1.35, 95 % CIs = 1.02-1.70)., Conclusions: Our findings suggest that pesticide exposure may not only be relevant for PD onset but also PD progression phenotypes. We have implicated ten specific pesticide active ingredients in faster PD motor and non-motor decline., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 The Authors. Published by Elsevier B.V. All rights reserved.)

In this study, a fixed bed flow through UVA-LED photoreactor was used to compare the efficiency of ozone, photocatalysis and photocatalysis-ozone degradation, and mineralization of two pure pesticides, 2,4-dichlorophenoxyacetic acid (2,4-D) and 2-methyl-4-chlorophenoxyacetic acid (MCPA), and a commercial one, Killex®. For the degradation of the parent compounds, ozone-based processes were more effective. While for mineralization, photocatalytic processes were more effective. Photocatalytic ozonation was the most efficient process for both the degradation and mineralization of the parent compounds. The degradation rates and mineralization by photocatalytic ozonation were higher than the summation of the corresponding rates by ozonation and photocatalysis, indicating a symbiotic relationship. Overall, the photocatalytic ozonation process with the fixed bed TiO reduces the time needed for the degradation and mineralization of the pesticides, reduces the costs of powder catalyst separation and overcomes the reduced efficiency of immobilized catalysts, which makes the process quite attractive for practical applications. [ABSTRACT FROM AUTHOR]

A novel strategy is reported for the fabrication of bis-aniline-crosslinked Au nanoparticles (NPs)-CdSe/ZnS quantum dots (QDs) array composite by facil one-step co-electropolymerization of thioaniline-functionalized AuNPs and thioaniline-functionalized CdSe/ZnS QDs onto thioaniline-functionalized Au elctrodes (AuE). Stable and enhanced cathodic electrochemiluminescence (ECL) of CdSe/ZnS QDs is observed on the modified electrode in neutral solution, suggesting promising applications in ECL sensing. An advanced ECL sensor is explored for detection of 2-methyl-4-chlorophenoxyacetic acid (MCPA) which quenches the ECL signal through electron-transfer pathway. The sensitive determination of MCPA with limit of detection (LOD) of 2.2 nmol L −1 (S/N=3) is achieved by π-donor–acceptor interactions between MCPA and the bis-aniline bridging units. Impressively, the imprinting of molecular recognition sites into the bis-aniline-crosslinked AuNPs–CdSe/ZnS QDs array yields a functionalized electrode with an extremely sensitive response to MCPA in a linear range of 10 pmol L −1 –50 μmol L −1 with a LOD of 4.3 pmol L −1 ( S/N=3). The proposed ECL sensor with high sensitivity, good selectivity, reproducibility and stability has been successfully applied for the determination of MCPA in real samples with satisfactory recoveries. In this study, ECL sensor combined the merits of QDs-ECL and molecularly imprinting technology is reported for the first time. The developed ECL sensor holds great promise for the fabrication of QDs-based ECL sensors with improved sensitivity and furthermore opens the door to wide applications of QDs-based ECL in food safety and environmental monitoring. [ABSTRACT FROM AUTHOR]

Recently, there has been growing concern over the potential impact of CO 2 concentration and temperature on herbicide efficacy. The aim of the study was to examine the influence of single elevated CO 2 (400 vs. 800 ppm) and elevated CO 2 in combination with temperature (21 °C vs. 25 °C) on the effects of auxin herbicide 4-chloro-2-methylphenoxyacetic acid (MCPA) (0.5-2 × field recommended rate) to wild mustard (Sinapis arvensis L.) grown in mixed-culture with spring barley (Hordeum vulgare L.). MCPA had a detrimental effect on aboveground and belowground biomass, content of chlorophylls, enzymatic and non-enzymatic antioxidants and induced oxidative stress. The significant decline in photosynthetic rate, stomatal conductance and transpiration with MCPA dose was detected. Elevated CO 2 reinforced MCPA efficacy on S. arvensis: sharper decline in biomass, photosynthetic rate and antioxidant enzymes and more pronounced lipid peroxidation were detected. Under elevated CO 2 and temperature, MCPA efficacy to control S. arvensis dropped due to herbicide dilution because of increased root:shoot ratio, higher activity of antioxidants and less pronounced oxidative damage. Reinforced MCPA impact on weeds under elevated CO 2 resulted in higher H. vulgare biomass, while decreased MCPA efficacy under elevated CO 2 and temperature reduced H. vulgare biomass., (© 2022. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Diagnosis of calcified nodules (CNs) is critical in the proper management of coronary artery disease, but CNs can be detected only using intracoronary imaging modalities. This study aimed to investigate the ability of coronary computed tomography angiography (CCTA) in predicting CNs detected using optical coherence tomography (OCT). From 138 patients who underwent OCT-guided percutaneous coronary intervention (PCI) after CCTA evaluation, 141 PCI target vessels were retrospectively enrolled and classified into CN (12 vessels/11 patients; CNs in the PCI culprit lesion) and non-CN (129 vessels/127 patients; without CNs) groups based on the OCT analysis. Retrospective CCTA analysis revealed significantly higher coronary artery calcification score (CACS), calcified plaque volume (CPV), and maximum calcified plaque area (MCPA) of the target vessel in the CN group than in the non-CN group. Receiver operating characteristic curve indicated that CACS ≥ 162 (area under the ROC curve (AUC 0.76, sensitivity 83.3%, specificity 54.2%), CPV ≥ 20.1 mm 3 (AUC 0.83, sensitivity 100%, specificity 57.3%), and MCPA ≥ 4.51 mm 2 (AUC 0.87, sensitivity 91.7%, specificity 78.3%) were the best cutoff values for predicting CNs. MCPA showed the highest AUC among all the CCTA parameters. In conclusion, CCTA is useful for predicting OCT-detected CNs in PCI target vessels., (© 2022. The Author(s).)