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We fabricated flexible, three-dimensional (3D) ordered silicon nanowire (SiNW) arrays decorated with high-density silver nanoparticles (AgNPs) for the sensitive and reproducible detection of pesticide residues. These sensors demonstrated a detection limit of 10−9 M for methyl parathion (MPT) on curved surfaces. [ABSTRACT FROM AUTHOR]

TiO2 thin film coatings significantly improve catalyst separation in photocatalytic processes. They can be applied in heterogeneous photocatalysis under sunlight by mixing TiO2 with other oxides, such as CeO2, for the removal of pollutants in water. Here, TiO2-CeO2 thin films deposited on borosilicate slides were analyzed and applied in solar heterogeneous photocatalysis for the oxidation of pesticides. The films were synthesized by the sol-gel method with spin coating. The waste solutions from the synthesis were used to prepare TiO2 and TiO2-CeO2 powders. These were analyzed by XRD and XPS to explain the behavior of the films. The thin films were characterized by UV-Vis spectroscopy with transmittance, UV-Vis spectroscopy with RDS, profilometry, AFM and SEM. The addition of CeO2 to TiO2 caused a decrease in the average crystal size and an increase in the strain index. The addition of a second layer made the TiO2-CeO2 thin films thinner. The CeO2 created surface and electronic defects in the titania films, which enhanced their photocatalytic properties under sunlight in the mineralization of diuron and methyl parathion. The TiO2-CeO2-5.0% single-layer thin film samples were the most active in this study and will undoubtedly be applied in larger-scale reaction systems. [ABSTRACT FROM AUTHOR]

In this work, we prepared a sensing platform by utilising the nanocomposite of Vulcan XC-72 R carbon nanoparticles and β-cyclodextrin (β-CD/VXC-72 R) to decorate glassy carbon electrode for detecting MP sensitively. For the β-CD/VXC-72 R composite, VXC-72 R possesses high electroactive area and exceptional electrical conductivity, which is conducive to the generation of interwoven carbon conductive structures. β-CD can effectually facilitate the homogeneous dispersion of VXC-72 R and also enhance the accumulate of MP at the sensing interface. Furthermore, the presence of VXC-72 R compensates for the inherent inferior conductivity of β-CD. The collaborative interaction of VXC-72 R and β-CD enabled the prepared sensor to obtain excellent MP detection properties with a low limit of detection (LOD) of 6.7 nM in MP concentration range of 0.1–10 μM. In addition, the β-CD/VXC-72 R modified glassy carbon electrode (GCE) displayed satisfactory repeatability and reproducibility. [ABSTRACT FROM AUTHOR]

A pre-treatment and analytical procedure for parathion-methyl (PM) in food samples was developed using cyclodextrin-based dispersive liquid-liquid microextraction (CD-DLLME) accompanied by a smartphone digital image colorimetry (SDIC). The extractant used was a green deep eutectic solvent synthesised from hexanoic acid and menthol. Cyclodextrin aqueous solutions were used as the green dispersion solvents to complete the dispersion and extraction process. Thus, a simple, fast, and environmentally friendly pre-treatment method was proposed. PM that was hydrolysed to a yellow product under an alkaline environment, and the colour intensity could be obtained using a smartphone for analysis. PM showed linearity ranging from 0.0020 to 1.0000 mg L−1, with limits of quantification and detection of 0.0020 and 0.0006 mg L−1. This method has been successfully applied in water, juice, tea, and vinegar, with recoveries ranging from 80.4 to 105.7% and relative standard deviation between 1.3 and 3.6%. This method can determine the concentration of PM in different food samples. [ABSTRACT FROM AUTHOR]

Industrial fermentation applications typically require enzymes that exhibit high stability and activity at high temperatures. However, efforts to simultaneously improve these properties are usually limited by a trade‐off between stability and activity. This report describes a computational strategy to enhance both activity and thermal stability of the mesophilic organophosphate‐degrading enzyme, methyl parathion hydrolase (MPH). To predict hotspot mutation sites, we assembled a library of features associated with the target properties for each residue and then prioritized candidate sites by hierarchical clustering. Subsequent in silico screening with multiple algorithms to simulate selective pressures yielded a subset of 23 candidate mutations. Iterative parallel screening of mutations that improved thermal stability and activity yielded, MPHase‐m5b, which exhibited 13.3 °C higher Tm and 4.2 times higher catalytic activity than wild‐type (WT) MPH over a wide temperature range. Systematic analysis of crystal structures, molecular dynamics (MD) simulations, and quantum mechanics/molecular mechanics (QM/MM) calculations revealed a wider entrance to the active site that increased substrate access with an extensive network of interactions outside the active site that reinforced αβ/βα sandwich architecture to improve thermal stability. This study thus provides an advanced, rational design framework to improve efficiency in engineering highly active, thermostable biocatalysts for industrial applications. [ABSTRACT FROM AUTHOR]

Organophosphate pesticides are widely used; however, their use is limited due to neurotoxicity and, to a lesser extent, cardiotoxicity in humans. Given the high energy demands of cardiac muscle, which is characterized by a dense population of mitochondria, any damage to these organelles can exacerbate cardiotoxicity. This study aims to elucidate whether the cardiotoxic effects of organophosphate pesticides originate from mitochondrial dysfunction. To investigate this, in silico toxicogenomic analyses were performed using various tools, such as the Comparative Toxicogenomic Database, GeneMANIA, STRING, and Cytoscape. Results revealed that 11 out of the 13 WHO-recommended Class Ia organophosphate pesticides target genes associated with cardiotoxicity. Notably, three of these genes were mitochondrial, with catalase (CAT) being the common differentially expressed gene among parathion, methyl parathion, and phorate. Furthermore, protein-protein interaction analysis indicated a strong association between CAT and superoxide dismutase 2, mitochondrial (SOD2). Subsequently, isolated heart mitochondria were utilized to assess CAT and superoxide dismutase (SOD) activities in vitro. The findings demonstrated that at a concentration of 7.5 ng/µL, both methyl parathion and phorate significantly decreased CAT activity by approximately 35%. Moreover, phorate reduced total SOD and SOD2 activities by 17% and 19%, respectively, at the same concentration. In contrast, none of the three organophosphate pesticides induced the opening of the mitochondrial permeability transition pore. These results suggest that the reduction in CAT and SOD2 activities, critical antioxidant enzymes, leads to the accumulation of reactive oxygen species within mitochondria, ultimately resulting in mitochondrial damage. This mechanism likely underlies the observed cardiotoxicity induced by these organophosphate pesticides. [ABSTRACT FROM AUTHOR]

In this study, type-II heterojunction WO 3 /BaTiO 3 and Z-scheme WO 3 /SrTiO 3 or WO 3 /Ba 0.5 Sr 0.5 TiO 3 nanocomposite photocatalysts were constructed for photodegradation of organic pollutants in wastewater under visible light. The photocatalytic performance of three WO 3 /titanate systems were estimated. Some influencing factors such as molar ratio of WO 3 and titanates, light irradiation time, catalyst dose, and initial concentration of organic pollutants on the photocatalytic activity were investigated. The stability and reusability of three WO 3 /titanates systems were examined. Moreover, the production of some radicals in the three WO 3 /titanates photocatalytic systems was demonstrated, and the three WO 3 /titanates photocatalytic reaction mechanisms were compared. The results reveal that the configurations of WO 3 /titanates photocatalytic systems are transformed from type-II heterojunction WO 3 /BaTiO 3 with lower activity to Z-scheme WO 3 /SrTiO 3 and WO 3 /Ba 0.5 Sr 0.5 TiO 3 with higher activity via the change of titanates. The WO 3 /titanate nanocomposites show higher photocatalytic activity at 3.0:1.0 M ratio of WO 3 and titanates, and WO 3 /Ba 0.5 Sr 0.5 TiO 3 nanoparticles have superior photocatalytic activity. The order of photocatalytic activity is as follows: WO 3 /Ba 0.5 Sr 0.5 TiO 3 > WO 3 /SrTiO 3 > WO 3 /BaTiO 3. Several organic pollutants, such as rhodamine B, methyl parathion, direct brilliant yellow-4R, and methylene blue, can be efficiently degraded using WO 3 /Ba 0.5 Sr 0.5 TiO 3 under visible light, and the RhB has higher degradation rate. After four cycles, WO 3 /titanate nanocomposites still have relatively high stability and reusability. •OH plays a major role in three WO 3 /titanates photocatalytic degradation. It is expected that the Z-scheme WO 3 /Ba 0.5 Sr 0.5 TiO 3 photocatalytic technology creates a good foreground for disposing of dyes and pesticides in water and wastewater. [ABSTRACT FROM AUTHOR]

In this study, we tested the insectistatic and insecticidal effects of the ethanolic extract of stems and bark of Ficus petiolaris Kunth (Moraceae) in laboratory bioassays with an artificial diet against newly hatched larvae of the fall armyworm, Spodoptera frugiperda Smith (Lepidoptera: Noctuidae). The extract was evaluated at five different concentrations (500, 1000, 1500, 2000, and 2500 ppm). The 2500 ppm extract had the strongest inhibitory effects on larval (89%) and pupal (20%) weight as well as the highest mortality (80%). The positive control, methyl parathion (Methyl Parathion®) at 1%, eliminated 100% of the fall armyworm, and the negative control (artificial diet) had a mortality of only 5%. Chemical fractionation of F. petiolaris stem and bark extract produced five fractions of FpR1-5, each of which was evaluated at 250, 500, 750, 1000, and 1250 ppm. FpR4 presented the strongest inhibitory effect, reducing the weight of the larva and pupa by 35% and 18%, while FpR2 had the strongest insecticidal effect, with 90% mortality at 1250 ppm. The pure 8-Methoxypsoralen compound extracted from this fraction was even more effective, with 100% S. frugiperda mortality at 100 ppm. The 50% lethal concentration (LC50) of 8-Methoxypsoralen was 67.68 ppm. Our results indicate that the F. petiolaris extract showed toxic activity against the fall armyworm, and its compound 8-Methoxypsoralen showed strong insecticidal activity at low concentrations. [ABSTRACT FROM AUTHOR]

There is still much to learn with respect to the potential for microplastics (MPs) to interact with environmental toxins and biota. In the present study, we investigated the effect of MPs on the toxicity of copper (Cu) to rice seeds (Oryza sativa L.). The 7‐day median effective concentration (EC50) value of MPs on rice seed germination was 864 mg/L (95% confidence interval [CI] 839 to 897 mg/L). We found that MPs slightly reduced Cu toxicity to rice seeds. The 7‐day EC50 of Cu on rice seed germination increased from 7.29 mg/L (95% CI 7.10–7.52 mg/L) to 7.93 mg/L (95% CI 7.58–8.08 mg/L) in the presence of 20 mg/L MPs. We examined this toxicity reduction phenomenon by investigating the role of MPs in the process of Cu transport, Cu accumulation, and metabolic responses. Further investigation found that the MPs used in the present study hardly adsorbed Cu, but these MPs accumulated on the coats of rice seeds and significantly reduced Cu accumulation in rice seedlings. When Cu concentration was 10 mg/L, the presence of MPs reduced the accumulation of Cu in rice seedlings by 34%. We also found that, compared with only Cu present, the addition of MPs resulted in lower reactive oxygen species accumulation and higher catalase activity and glutathione levels in rice seedlings, which also contributed to Cu toxicity reduction. Collectively, the present study shows that polystyrene MPs have the potential to form associations with plant structures which can ultimately impact heavy metal bioaccessibility and therefore toxicity. Environ Toxicol Chem 2024;43:1870–1879. © 2024 SETAC [ABSTRACT FROM AUTHOR]

Sensors play a critical role in the detection and monitoring of various substances present in our environment, providing us with valuable information about the world around us. Within the field of sensor development, one area that holds particular importance is the detection of small molecules. Small molecules encompass a wide range of organic or inorganic compounds with low molecular weight, typically below 900 Daltons including gases, volatile organic compounds, solvents, pesticides, drugs, biomarkers, toxins, and pollutants. The accurate and efficient detection of these small molecules has attracted significant interest from the scientific community due to its relevance in diverse fields such as environmental pollutants monitoring, medical diagnostics, industrial optimization, healthcare remedies, food safety, ecosystems, and aquatic and terrestrial life preservation. To meet the demand for precise and efficient monitoring of small molecules, this summary aims to provide an overview of recent advancements in sensing and quantification strategies for various organic small molecules including Hydrazine, Glucose, Morpholine, Ethanol amine, Nitrosamine, Oxygen, Nitro-aromatics, Phospholipids, Carbohydrates, Antibiotics, Pesticides, Drugs, Adenosine Triphosphate, Aromatic Amine, Glutathione, Hydrogen Peroxide, Acetone, Methyl Parathion, and Thiophenol. The focus is on understanding the receptor sensing mechanism, along with the electrical, optical, and electrochemical response. Additionally, the variations in UV–visible spectral properties of the ligands upon treatment with the receptor, fluorescence and absorption titration analysis for limit of detection (LOD) determination, and bioimaging analysis are discussed wherever applicable. It is anticipated that the information gathered from this literature survey will be helpful for the perusal of innovation regarding sensing strategies. [ABSTRACT FROM AUTHOR]

One of the most pressing global environmental issues is the widespread abundance and distribution of microplastics (MPs). MPs can act as vectors for other contaminants in the environment making these small plastic particles hazardous for ecosystems. The presence of MPs in aquatic environments may pose threats to aquatic organisms that ingest them. This study examined effects of abamectin (ABM) and polyethylene terephthalate (PET) MP fragments on histopathological and enzymatic biomarkers in zebrafish (Danio rerio). Zebrafish were exposed for 96 h to pristine PET-MPs at concentrations of 5 mg/L and 10 mg/L, ABM alone at 0.006 mg/L, and the same concentration of ABM in the presence of PET-MPs in aquaria. Histopathological analysis revealed tissue content changes in liver and kidney in the presence of ABM individually and in combination with MPs. Results of enzymatic analysis showed that MPs increased the bioavailability and toxicity of pesticides due to inhibition of catalase (CAT) and acid phosphatase (ACP) enzymes. However, MPs did not affect the toxicity of ABM for glutathione s-transferase (GST) enzyme. Despite the inhibition of acetylcholinesterase (AChE) in MPs or ABM treatments, and some neurotoxicity, no change in activity of this enzyme and neurotoxicity was observed in the combined MPs and ABM treatments, although toxicity effects of MPs and ABM on zebrafish require more detailed studies. [ABSTRACT FROM AUTHOR]

Purpose: The aim of this study was to explore the effects of the variations in biodegradable and nonbiodegradable microplastic particles (MPs) on the absorption of lead (Pb) in maize. Materials and methods: Pot experiments were conducted using maize and two types of MPs, nonbiodegradable polyethylene (PE) and biodegradable polybutylene adipate/terephthalate (PBAT), at four different MP concentrations (0, 0.1, 1, and 10%). After one month of growth, the Pb content in aboveground and belowground parts of the maize seedlings, CaCl2-extracted Pb content, the proportion of different speciation of Pb within the soil, and soil properties were determined. We determined Pb uptake by maize seedlings, soil physicochemical properties, and Pb speciation in soil. Results: The addition of PE and PBAT particles led to the decrease in Pb content in maize root with the increase in concentration. The addition of 0.1% PBAT particles significantly increased the Pb content in the shoot of maize plants by 37.60% and Pb content in the root by 65.06% compared with 0.1% PE. The addition of PE and PBAT particles increased the proportion of residual Pb to 36.0% and 38.0%, respectively. The correlation analysis showed that the addition of MPs mainly affected the absorption of Pb by maize plants by affecting soil pH, dissolved organic carbon (DOC), cation exchange capacity (CEC), free crystalline Mn (MnDCB), and amorphous Fe (FeTamm). Conclusions: This study demonstrates that biodegradable and nonbiodegradable MPs in soil inhibited Pb accumulation in maize seedling roots. FeDCB, MnDCB, and FeTamm may be the main control factors affecting the inhibition of lead uptake by PE in maize seedling roots. Additionally, FeTamm may be the main controlling factor influencing PBAT to reduce lead accumulation in maize seedling roots. The results of the present study could provide novel insights into the toxicity and bioavailability effects of MPs and Pb on maize, as well as a valuable reference for ongoing research on the ecological risk assessment of MPs and other pollutants in the soil environment. [ABSTRACT FROM AUTHOR]

The rapid and efficient identification and quantification of neurotoxic organophosphorus pesticides (OPs) are crucial for ensuring environmental safety and human health. However, the current acetylcholinesterase OP sensors are largely limited by the stability and cost of bio-enzymes, as well as the occurrence of false negatives in "signal-off" strategies. In this study, we present a pioneering approach that utilizes high-performance electrochemiluminescence (ECL) of tungsten disulfide quantum dots (WS2 QDs) to develop an alternative sustainable non-enzymatic ECL sensor for "signal-on" OP detection. The presence of phosphate esters in OPs efficiently mediates ECL enhancement of WS2 QDs using K2S2O8 as a coreactant. With this new strategy, we achieved highly sensitive and selective detection of common OPs, including methyl parathion, naled, dimethoate, and malathion, with detection limits of 1.48 pg mL−1, 4.30 pg mL−1, 0.35 pg mL−1, and 5.58 pg mL−1, respectively. When applied to river water and spinach samples, the sensor also demonstrated high reproducibility and good recovery. The electrochemical hydrolysis decomposition of OPs during the detection process in this study provides a "two birds with one stone" strategy, serving the dual objective of identifying and degrading OPs. This work paves a new avenue for direct ECL sensing in environmental and food screening, eliminating the reliance on common indirect biological identification elements. [ABSTRACT FROM AUTHOR]

A new catalyst, Sm2NdSbO7, was synthesized for the first time by solid-phase sintering. The study utilized X-ray diffraction, transmission electron microscope energy dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy to examine the structural characteristics of monocrystal BiDyO3, monocrystal Sm2NdSbO7 and Sm2NdSbO7/BiDyO3 heterojunction photocatalysts (SBHP) prepared by solid-phase sintering. The Sm2NdSbO7 photocatalyst owned a pyrochlorite structure, belonged to the face-centered cubic crystal system, possessed a space group of Fd3m and a bandgap width of 2.750 eV. After 145 min of visible light irradiation (145-VLIRD), the removal rate (RMR) of methyl parathion (MP) or total organic carbon of SBHP was 100% or 97.58%, respectively. After 145-VLIRD, the photocatalytic degradation rates of SBHP to MP were 1.13 times, 1.20 times, and 2.43 times higher than those of the Sm2NdSbO7 photocatalyst, the BiDyO3 photocatalyst, and the nitrogen-doped TiO2 catalyst, respectively. The experimental results showed that SBHP had good photocatalytic activity. After four cycles of cyclic degradation experiments with SBHP, the elimination rates of MP were 98.76%, 97.44%, 96.32%, and 95.72%, respectively. The results showed that SBHP had good stability. Finally, the possible degradation pathways and degradation mechanisms of MP were speculated. In this study, we successfully developed a high-efficiency heterojunction catalyst which responded to visible light and possessed significant photocatalytic activity. The catalyst could be used in photocatalytic reaction system for eliminating the harmful organic pollutants from wastewater. [ABSTRACT FROM AUTHOR]

In the ratiometric fluorescent (RF) strategy, the selection of fluorophores and their respective ratios helps to create visual quantitative detection of target analytes. This study presents a framework for optimizing ratiometric probes, employing both two-component and three-component RF designs. For this purpose, in a two-component ratiometric nanoprobe designed for detecting methyl parathion (MP), an organophosphate pesticide, yellow-emissive thioglycolic acid-capped CdTe quantum dots (Y-QDs) (analyte-responsive), and blue-emissive carbon dots (CDs) (internal reference) were utilized. Mathematical polynomial equations modeled the emission profiles of CDs and Y-QDs in the absence of MP, as well as the emission colors of Y-QDs in the presence of MP separately. In other two-/three-component examples, the detection of dopamine hydrochloride (DA) was investigated using an RF design based on blue-emissive carbon dots (B-CDs) (internal reference) and N-acetyl L-cysteine functionalized CdTe quantum dots with red/green emission colors (R-QDs/G-QDs) (analyte-responsive). The colors of binary/ternary mixtures in the absence and presence of MP/DA were predicted using fitted equations and additive color theory. Finally, the Euclidean distance method in the normalized CIE XYZ color space calculated the distance between predicted colors, with the maximum distance defining the real-optimal concentration of fluorophores. This strategy offers a more efficient and precise method for determining optimal probe concentrations compared to a trial-and-error approach. The model's effectiveness was confirmed through experimental validation, affirming its efficacy. [ABSTRACT FROM AUTHOR]

Vanadium metal–organic frameworks (V-MOF) has a great potential to remove contaminants from water that come from agriculture wastewater methyl parathion (MP) pesticides with high effectiveness. Using a variety of methods, such as SEM, FT-IR, XPS), XRD, and BET analysis, the adsorbent was successfully synthesized and characterized. The dimensions of the pores measured at 1.33 nm correspond to the classification of micropores under the IUPAC system. Before the adsorption process, the material had a surface area of 1489.42 m2/g and a pore volume of 0.98 cc/g. After MP adsorption, the surface area, pore size, and pore volume decreased to 1268.42 m2/g, 1.12 nm, and 0.64 cc/g, respectively. Changes in the material’s physical properties indicate that the adsorption process had an effect. 7.2 was the result of controlling the point of zero charge through surface characterization. This information suggests that the surface of the adsorbent has a positive charge at pH below 7.2 and at the pH higher than this value the surface will have a negative charge. It was also looked into how pH affected the adsorption equilibrium. Although fitting to Langmuir isothermally, the kinetics of MP adsorption onto V-MOF are pseudo-second-order fitting. It is very probable that chemisorption was the mode of adsorption because the adsorption energy was 23.62 kJ.mol−1. The enthalpy (ΔHo) values obtained as a result of studying the thermodynamic parameters are positive, demonstrating that, within this temperature range, the pesticide adsorption process was endothermic., measuring 32.79 kJ.mol−1. Entropy (ΔSo) readings that are positive indicate that the system’s randomness increased during the adsorption process, reaching 119 J.mol−1K−1, and with rising temperatures, the negative of ΔGo rise. The effectiveness of the recommended adsorbent was evaluated by filtering wastewater samples in a laboratory environment. It is hypothesized that V-MOF and MP will interact by pore filling, π-π interaction, H-bonding, electrostatic contact, and other possible methods. Considering the specifics of this interaction in great detail is essential to comprehending the nature of adsorption and effectively constructing the adsorbent for use in real-world applications. Water filtering and the treatment of industrial effluents were made simple and effective by the use of V-MOF adsorbent technology. The results indicated that 383.6 mg/g was the maximal adsorption capacity at pH = 6. To evaluate the renewal of the adsorbent, more tests were carried out, and the outcomes showed that the renewal continued even after more than six cycles. The stability of the adsorbent during regeneration was confirmed by using XRD and FT-IR. The Box Behnken design (BBD) was then employed to optimize the adsorption outcomes.

Low-power and smart sensing systems for iron detection are necessary for in situ monitoring of water quality. Here, a potentiometric Fe2+-selective electrode (ISE) was fabricated based on cyanomethyl N-methyl-N-phenyl dithiocarbamate for the first time as an ionophore. Under optimal conditions, the ISE showed a Nernstian slope of 29.76 ± 0.6 mV per decade for Fe2+ ions over a wide concentration range from 1.0 × 10−1 to 1.0 × 10−5 M with a lower detection limit (LOD) of 1.0 × 10−6 M. The ISE interference of various cations on the potentiometric response was also investigated. The ISE had a response time less than 3 s and the lifetime was two months. Also, an automated, long-range (LoRa), wireless enabled sampling microfluidic device powered with a solar panel as an autonomous power source was developed for a continuous sampling and sensing process. The sensing platform was employed in the determination of Fe2+ in acid mine drainage and spiked water samples with an average recovery of 100.7%. This simple, inexpensive (below $350), portable sensing platform will allow for rapid real-time monitoring of ground-, drinking-, and industrial waters contaminated with iron. [ABSTRACT FROM AUTHOR]

Introduction: A new analytical method based on the coupling of microextraction and microfluidics was developed and investigated for the pre-concentration, separation, and electrochemical detection of fenitrothion (FT) and parathion (PA) at the sub-ppm concentrations. Methods: In the first step, the microchip capillary electrophoresis technique was used to serve as a separation and detection system. Analytes were injected in the 40 mm long microchannel with 10 mm sidearms. Then, they were separated by applying a direct electrical field (+1800 V) between the buffer and detection reservoirs. 2-(n-morpholino)ethanesulfonic acid (MES) buffer (20 mM, pH 5) was used as a running buffer. The electrochemical detection was performed using three Pt microelectrodes with the width of working, counter, and reference electrodes (50, 250, and 250 µm, respectively) in the out-channel approach. Results: The system was devised to have the optimum detection potential equal to -1.2 V vs. pseudo-reference electrode. The dimensions of the SU-8 channel have 20 µm depth and 50 µm width. In the second step, an air-assisted liquid-liquid microextraction technique was used to extract and preconcentration of analytes from human blood plasma. Then, 1, 2 di-bromoethan was used as extractant solvent, the analytes were preconcentrated, and the sedimented solvent (50 µL) was evaporated in a 60 °C water bath followed by substitution of running buffer containing 10% ethanol. The optimal extraction cycles were found to be 8 with adding 1% NaCl to the aqueous phase. Analyzing time of the mentioned analytes was less than 100s, the precision range was 3.3 - 8.2 with a linear range of 0.8-100 ppm and 1.2-100 ppm for FT and PA, respectively. The extraction recoveries were about 91% and 87% for FT and PA, respectively. The detection limits for FT and PA were 240 and 360 ppb, respectively. Finally, the reliability of the method was investigated by GC-FID. Conclusion: The proposed method and device were validated and can be used as in situ and portable detection systems for detecting fenitrothion and parathion insecticides. [ABSTRACT FROM AUTHOR]

Pesticides containing chlorine, which are released during agricultural activities, are chemical substances that mix with surface and underground waters and have toxic, carcinogenic, and mutagenic effects on the entire living ecosystem. Due to their chemically stable structure, conventional water and wastewater treatment techniques such as coagulation, flocculation, and biological oxidation do not entirely remove these chemical substances. Therefore, before releasing them into the environmental receptor, these chemical substances must be transformed into harmless products or mineralized through advanced oxidation processes. When we look at the literature, there are not many studies on methods of removing diclofop methyl from aquatic media. Our study on the removal of diclofop methyl herbicide from aquatic media using the peroxy electrocoagulation method will provide the first information on this subject in the literature. In addition, this treatment method will contribute significantly to filling an important gap in the literature as an innovative approach for diclofop methyl removal. Moreover, peroxy electrocoagulation, which produces less sludge, provides treatment in a short time, and is economical, has been determined to be an advantageous process. The effects of conductivity, pH, H2O2 concentration, current, and time parameters on the removal of diclofop methyl were investigated using a GC–MS instrument. Kinetics, energy consumption, and cost calculations were also made. Under the optimum conditions determined (pH = 5, H2O2 = 500 mg/L, NaCl = 0.75 g/L, current density = 2.66 mA/cm2), the peroxydic electrocoagulation process resulted in a diclofop methyl removal efficiency of 79.2% after a 25-min reaction. When the experimental results were analyzed, it was found that the results fitted the pseudo-second-order kinetic model. [ABSTRACT FROM AUTHOR]

Reformatsky reagent obtained from methyl 1-bromocyclopentanecarboxylate and zinc selectively added to the carbon–carbon double bond of the heterocyclic fragment of 3-(3-arylacryloyl)-2H-chromen-2-ones to give the corresponding addition products after hydrolysis of the reaction mixture. According to the X-ray diffraction data, the products exist in the enol form. Despite the use of excess Reformatsky reagent, elevated temperature, and prolonged reaction time, neither addition to the acryloyl fragment nor intramolecular cycliza-tion of the addition products was observed. [ABSTRACT FROM AUTHOR]

Herein, an efficient and sensitive methyl parathion (MP) electrochemical sensor was fabricated by using β-cyclodextrin (β-CD) decorated single-wall carbon nanotubes (SCN), which were used to modify the glassy carbon electrode (GCE). The β-CD@SCN/GCE sensor achieved the sensitive MP detection. For the obtained β-CD@SCN nanocomposite, SCN could form three-dimensional reinforced carbon conductive network with good conductivity property and efficient charge transport channels; β-CD could promote the dispersion of carbon materials and boost the accumulation capability of MP on the surface of β-CD@SCN/GCE. The combination of β-CD and SCN significantly optimized the electrochemical property of β-CD@SCN/GCE sensor for the detection of MP. The β-CD@SCN/GCE sensor exhibited good MP electrochemical detection performance with low limit of detection of 7.23 nM. When used for the detection of MP in grape juice, the β-CD@SCN/GCE sensor exhibited good MP electrochemical sensing analysis performance with satisfactory recovery rates (96.54–98.18%) and relative standard deviation values (1.60–2.07%). [ABSTRACT FROM AUTHOR]

Herein, a novel electrochemical sensor was designed for the sensitive determination of methyl parathion (MP) using the Super P Li carbon black@β-cyclodextrin (SPLCB@β-CD) decorated glassy carbon electrode (GCE). SPLCB with high electroactive area exhibited exceptional conductivity and good dispersive property, which is beneficial for forming the interlinked conductive network structure. β-CD could not only promote the uniform dispersion of SPLCB but also effectively realise the enrichment of MP molecules. Moreover, the existence of SPLCB could make up for the defect of poor conductivity of β-CD. Under the optimal experimental condition (pH = 7.0, enrichment time: 60 s). The collaborative cooperation of SPLCB and β-CD achieved the excellent MP detection property (LOD: 8.6 nM; concentration range: 0.01–10 μM). The SPLCB@β-CD/GCE sensor exhibited acceptable repeatability and reproducibility. In addition, the proposed sensor was successfully employed to detect MP in apple juice (Recoveries: 98.0–98.6%, RSD values: 3.68–4.63%). [ABSTRACT FROM AUTHOR]

The samples of greenhouse cucumbers were collected from the Central Fruit and Vegetable Market of Tabriz between June and December 2017. In the twenty-four cucumber samples (unwashed, washed, peeled), the residue of 18 organophosphates pesticides (OPPs) was analyzed using gas chromatography-mass spectrometry (GC-MS) following the modified QuEChERS method (quick, easy, cheap, effective, rugged and safe). Chronic non-carcinogenic risk assessment from pesticide residues in the samples was also performed for age groups of adults (women and men) and children using the Monte Carlo Simulation (MCS). Amongst the eighteen studied pesticides, eight pesticides including dimethoate, diazinon, methyl parathion, fenitrothion, chlorpyrifos, profenofos, ethion, and azinphos-methyl were detected. Pesticide residues were detected in 100% of unwashed, washed and peeled samples in the range of 0.08 to 0.37 mg.kg-1, 0.03 to 0.17 mg.kg-1 and 0.01 to 0.08 mg.kg-1, respectively. The maximum and minimum values were found for diazinon pesticides with 0.37 mg.kg-1 and profenofos and fenitrothion with 0.01 mg.kg-1. 100 % of samples contained at least three pesticide residues (dimethoate, diazinon, and methyl parathion), while 87.5% of the samples contained more pesticides residues. The residues of dimethoate, diazinon, and methyl parathion were above Maximum Residue Limits (MRL) in 100%, 83.33%, and 66.66% of samples, respectively. The identified residues were more than the EU MRLs and the IR MRLs in 100% and 95.83% samples, respectively. The mean reduction of pesticide residues in the washed and peeled samples was in the range of 37.74 to 56.52% and 66.66 to 92.30%, respectively. According to the performed risk assessment, there is no significant non-carcinogenic health risk due to the consumption of cucumber for the age group of adults. Hence, there is a considerable non-carcinogenic health risk to children due to the consumption of unwashed (HI = 2.22) and water-washed (HI = 1.36) greenhouse cucumbers. [ABSTRACT FROM AUTHOR]

Herein, a deep eutectic solvent (DES)‐based miniaturized pressurized liquid extraction in combination with DES‐based dispersive liquid–liquid microextraction (DLLME) was developed for the extraction of organophosphorus pesticides (parathion–methyl, triazophos, parathion, diazinon, and phoxim) from egg powder samples prior to their analysis by a high‐performance liquid chromatography‐diode array detector. In this work, first, the analytes' extraction was done by a pressurized liquid phase extraction for effective extraction of the analytes from the solid matrix, and then they were concentrated on a DLLME for more concentration of the analytes to reach low limits of detections. The use of DESs was done in both steps to omit the use of toxic organic solvents. Satisfactory results including high extraction recoveries (74–90%), great repeatability (relative standard deviations equal or less than 4.3% and 5.3% for intra‐ and inter‐day precisions), and low limits of detection (0.11–0.29 ng/g) and quantification (0.38–0.98 ng/g) were attained under the optimum conditions. Lastly, the suggested approach was utilized for the determination of the studied pesticides in various egg powder samples marketed in Tabriz, Iran. [ABSTRACT FROM AUTHOR]

Objective: In order to achieve rapid detection of methyl parathion. Methods: An acetylcholinesterase sensor was prepared based on gold nanoparticles and reduced graphene oxide for quantitative detection of Methyl parathion. Reduced graphene oxide, gold nanoparticles and acetylcholinesterase were successively modified on the surface of the screen printing electrode by layer-by-layer assembly method. The catalytic activity and impedance characteristics of the sensor, the relationship between the sensor's inhibition rate and MP concentration, and the actual sample detection were evaluated. Results: The prepared acetylcholinesterase biosensors showed excellent affinity for acetylthiocholine chloride with the Michaelis-Menten constant of 2.76 mmol/L. Under the optimal conditions, Methylparathion could be effectively detected with a linear range of 5 ng/mL to 500 ng/mL and a detection limit of 0.692 ng/mL. Conclusion: The method is simple, practical and stable. It provides a reliable method for rapid detection of organophosphorus pesticides.

Organophosphorous (OP) pesticides can cause many human diseases. In this study, the separation and determination of two organophosphorous pesticides (diazinon and methyl-parathion) in biological samples using solid-phase extraction method prior to their measurements by high‐performance liquid chromatography (HPLC) were investigated. Herein, a new functionalized cerium-based metal–organic framework (MOF) bearing oxime moiety, denoted here UiO-66(Ce)-MO, was synthesized through two-synthetic steps from the pristine UiO-66(Ce) and then applied as an efficient porous adsorbent for the extraction of pesticides from biological samples. Various techniques including Fourier-transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD) analysis, scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), and Brunauer–Emmett–Teller (BET) analysis were used for the description of adsorbent. The optimization of variables was performed by Box–Behnken design combined with response surface methodology. The factors' effects including pH, eluent volume (EV), sample flow rate (SF) and eluent flow rate (EF) were also examined. The optimum conditions for both compounds were pH 5.5, eluent volume 0.6 mL, SF 2 mL min−1, and EF 0.2 mL min−1, leading to 97.1% and 96.0% removal of diazinon and methyl-parathion, respectively. Under the optimum conditions, the maximum adsorption capacity was obtained 454.5 mg g−1 for methyl-parathion and 476.2 mg g−1 for diazinon. The limit of detection (LOD) was found to be 0.04 μgL−1 for diazinon and 0.06 μgL−1 for methyl-parathion. Sensitivity analysis showed that pH plays a significant role on the efficiency of both organic pollutants. Remarkably, the results showed that this adsorbent outperforms the other UiO-66(Ce) samples and is suitable for separation and determination of these organic materials from water and biological real samples (blood plasma and urine). A porous oxime-functionalized Ce-MOF, UiO-66(Ce)-MO, was synthesized and applied for efficient extraction and determination of trace amounts of methyl-parathion and diazinon from water and biological samples. [ABSTRACT FROM AUTHOR]

It is of great significance to develop an effective method for methyl parathion (MP) detection. Herein, a novel nitrogen‐doped titanium carbide quantum dots (N‐Ti3C2 QDs) was prepared and used to construct a simple and sensitive fluorescence sensing platform of MP by making use of inner filter effect (IFE). The prepared N‐Ti3C2 QDs can exhibit strong blue fluorescence at 434 nm. Meanwhile, MP could hydrolyze to produce p‐nitrophenol (p‐NP) under alkaline conditions, which showed a characteristic ultraviolet‐visible (UV‐visible) absorption peak at 405 nm, resulting in the fluorescence of N‐Ti3C2 QDs is effectively quenched by p‐NP. In addition, the investigation of time‐resolved fluorescence decays indicated that the corresponding quenching mechanism of p‐NP on N‐Ti3C2 QDs is due to the IFE. After optimizing the conditions, the as‐developed fluorescence sensing platform displayed wide detection range (0.1–30 μg mL−1) and low detection limit (0.036 μg mL−1) for MP, and it was also successfully applied for MP analysis in real water samples, thus it is expected that this simple, sensitive and enzyme‐free sensing platform shows great applications. [ABSTRACT FROM AUTHOR]

The hydrochloric acid (HCl 0.1 M) supporting electrolyte was used in the electrochemical estimation cyclic voltammetry for CaCl2 concentrations also using crystal violet dye or (hexamethyl pararosaniline) as ligand. For oxidation and reduction waves, the potential range is 0.5 V, -0.5 V. The interaction of calcium ions with crystal violet was examined using several analytical estimates, and kinetic and thermodynamic parameters. The analytical concentration for calcium ions in different samples especially in Nile River were estimated in the range from 1.6 to 14.3 mmol. The estimation of calcium ion concentrations was achieved up to 11.49 mmol in waste water in Mansoura University. Applications were made for calcium estimation of different water samples and molecular docking of the calcium-crystal violet complex against the Hepatitis C viral proteins (4i33, 4KTC), roving strong bonds of interaction were observed. And anti-bacterial effect on calcium complex with crystal violet and face mask N-95 tissue. [ABSTRACT FROM AUTHOR]

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An unprecedented photocatalyst, Sm2EuSbO7, was successfully fabricated in this paper, through a high-temperature solid-state calcination method, which represented its first ever synthesis. Additionally, using the solvothermal method, the Sm2EuSbO7/ZnBiSbO5 heterojunction photocatalyst (SZHP) was fabricated, marking its debut in this study. XRD analysis confirmed that both Sm2EuSbO7 and ZnBiSbO5 exhibited pyrochlore-type crystal structures with a cubic lattice, belonging to the Fd3m space group. The crystal cell parameter was determined to be 10.5682 Å or 10.2943 Å for Sm2EuSbO7 or ZnBiSbO5, respectively. The band gap width measured for Sm2EuSbO7 or ZnBiSbO5 was 2.73 eV or 2.61 eV, respectively. Under visible light irradiation for 150 min (VLTI-150 min), SZHP exhibited remarkable photocatalytic activity, achieving 100% removal of parathion methyl (PM) concentration and 99.45% removal of total organic carbon (TOC) concentration. The kinetic constant (k) for PM degradation and visible light illumination treatment was determined to be 0.0206 min−1, with a similar constant k of 0.0202 min−1 observed for TOC degradation. Remarkably, SZHP exhibited superior PM removal rates compared with Sm2EuSbO7, ZnBiSbO5, or N-doped TiO2 photocatalyst, accompanied by removal rates 1.09 times, 1.20 times, or 2.38 times higher, respectively. Furthermore, the study investigated the oxidizing capability of free radicals through the use of trapping agents. The results showed that hydroxyl radicals had the strongest oxidative capability, followed by superoxide anions and holes. These findings provide a solid scientific foundation for future research and development of efficient heterojunction compound catalysts. [ABSTRACT FROM AUTHOR]

Summary: The effect of complex organic acids (COA) treatment at different concentrations (0%, 1%, 5%, 10% and 15%) on the myofibrillar protein (MP) structure and meat quality of crayfish (Procambarus clarkii) was investigated. The results showed that with increasing concentrations of COA treatment, the sulfhydryl content of MP decreased and dityrosine content increased. The MP secondary structure has a reduced α‐helix content and an increased β‐fold content. The MP tertiary structure unfolded, exposing hydrophobic and other amino acids to a polar environment. MP aggregation was induced in the 1% and 5% COA treatment groups and MP degradation was induced in the 10% and 15% COA treatment groups. Crayfish meat in the 5% COA treatment group showed improved textural properties due to protein aggregation. It also enhanced the colour, aroma and micromorphology of the crayfish meat. [ABSTRACT FROM AUTHOR]

In this work, we proposed a template-free synthesis strategy for the preparation of morning glory-like porous carbon nanosheets (MGPCS) with three-dimensional (3D) interconnected porous carbon structure, which was applied to modify the glassy carbon electrode (GCE) for the fabrication of methyl parathion (MP) electrochemical sensor (MGPCS/GCE). MGPCS was successfully prepared by a template-free synthesis strategy with sodium citrate as carbon source. Benefitting from the high-temperature thermal decomposition and acid treatment process, the sodium citrate-derived MGPCS sample presented 3D interconnected morning glory-like porous carbon structure with good electrical conductivity, which provided more efficient charge transfer channels. In particular, the morning glory-like surface morphology significantly increased the specific surface area and adsorption capacity of sensing electrode. Under the optimal conditions, the fabricated MGPCS/GCE sensor showed highly sensitive MP detection property with low limit of detection of 10.7 nM (Linear MP concentration: 0.1–15 µM). Moreover, the fabricated sensor presented good reproducibility, repeatability, stability, and selectivity. The good practical performance of the MGPCS/GCE sensor was confirmed by detecting the MP amount in apple juice and peach juice samples. [ABSTRACT FROM AUTHOR]

Methyl parathion (MP), an organophosphorus insecticide, is commonly used in agricultural products for food preservation and pest control. Due to the severe threat it poses to food safety and the environment, monitoring MP residues has attracted much attention. Traditional spectroscopic and chromatographic methods have been used successfully to analyze MP in a wide range of samples; however, these approaches have several drawbacks, such as requiring specialized equipment, trained technicians, and extensive sample preparation time. Due to these restrictions, there is a growing demand for analysis methods that can reliably and quickly detect MP at trace quantities while also being quick, sensitive, and selective. Electrochemical sensors have emerged over the past few decades as a viable alternative to more time-consuming and laborious analysis methods for detecting MP. However, the performance of electrochemical sensors has been dramatically improved thanks to recent breakthroughs in nanoscience. This study offers an overview of the creation and operation of carbon nanomaterial-based electrochemical sensors (including carbon nanotubes (CNTs), graphene (Gr), and other carbon nanomaterials) to identify MP residues in waters, fruits, and vegetables. A brief discussion of the potential benefits, drawbacks, and future research prospects of MP electrochemical sensors based on carbon nanomaterials is also offered. [ABSTRACT FROM AUTHOR]

Pesticides are chemicals used to control a wide variety of animals and plants. Methyl parathion (MP) is an organic phosphorus insecticide used in agriculture against animal organisms that damage the crop. Pesticides can reach water resources in different ways. May affect non-target organisms such as fish to varying degrees. Since fish is a valuable nutrient in human nutrition, its sustainability is very important. For this reason, sublethal effects of MP on Alburnus tarichi, which is economically important for the Lake Van basin, were studied. This study was carried out to determine the pathological effects of MP on the gonad, gill and liver tissues of Alburnus tarichi. Fish weighing 3‒7 g were used in the study. The semistatic test method was applied. Fish were exposed to 4.28 mg L-1 MP. The bioassay was carried out at 17.9 °C for 30 days. At the end of the test, gonad, gill and liver tissues were removed from the dissected fish for pathological evaluations. In the examinations made, cells with eosinophilic and fat accumulation in the liver, local necrosis and enlarged vessels, and yellow colored structures were determined. Thickened primary lamella, folded secondary lamella and epithelial layer separations were observed in the gills. No pathology was found in ovarian cells. Degeneration in the germ cells in the mitotic phase, interstitial tissue containing eosinophilic cell groups, enlarged follicle lumen and bleeding were observed in the testes that were not in the mitotic phase. As a result, MP is a chronic toxic substance according to histological criteria for Alburnus tarichi. MP should be used in agriculture in a controlled and careful way. [ABSTRACT FROM AUTHOR]

Highly sensitive and uniform three‐dimensional (3D) hybrid heterogeneous structures for use in surface‐enhanced Raman scattering (SERS) experiments were fabricated by sequentially decorating high‐quality, ultra‐clean, graphene quantum dots (GQDs) and Ag nanoparticles (Ag‐NPs) onto 3D‐graphene. Finite‐difference time‐domain calculations and scanning Kelvin probe microscopy were used to verify that the Ag‐NPs/GQDs/3D‐graphene system facilitates substantial electromagnetic enhancement (due to the occurrence of two kinds of "gaps" between the Ag‐NPs that form 3D "hot spots") and additional chemical enhancement (in detecting some π‐conjugated molecules). The SERS mechanism was explored in further detail via experimental analysis and confirmed by performing theoretical calculations. The large surface area of the 3D substrate (due to the large specific surface areas of the GQDs and 3D‐graphene) results in a better enrichment effect which helps produce lower detection limits. In particular, the detection limits obtained using the Ag‐NPs/GQDs/3D‐graphene platform can reach 10−11 M for rhodamine 6G, 10−10 M for methylene blue and dopamine, and 10−7 M for tetramethylthiuram disulfide and methyl parathion in apple juice (these are superior to most of the results reported using graphene‐based SERS substrates). In summary, the 3D‐platform Ag‐NPs/GQDs/3D‐graphene/Si shows outstanding SERS performance. It therefore has excellent application prospects in biochemical molecular detection and food safety monitoring. [ABSTRACT FROM AUTHOR]

The recovery of organophosphate pesticides (OPPs) from aqueous solutions is imperative considering their agricultural and environmental implications. Among various mitigation approaches used for OPPs' removal, adsorption offers many advantageous features for OPPs abatement owing to its benign nature, cost-effective processing, and non-requirement of excessive equipment. This research describes the adsorptive removal of three organophosphate pesticides (OPPs) namely chlorpyrifos (CPF), methyl parathion (MP), and malathion (MAL) by HKUST–1 (HKUST = Hong Kong University of Science and Technology) metal–organic framework (MOF). The synthesis of HKUST–1 MOFs was confirmed by various spectroscopic and microscopic techniques. The adsorption kinetics was systematically investigated by varying three parameters to include solution pH, contact time, and initial pesticide concentration. Among all the three pesticides, HKUST–1 showed enhanced removal of CPF in terms of pH, resulting in an adsorption capacity of 1.82 mg·g−1. However, under the effect of contact time at 60 min, the adsorption capacity of HKUST-1 for PM, MAL, and CPF were computed to be 1.83, 1.79, and 0.44 mg·g−1, respectively. Besides, HKUST–1 showed a remarkable performance towards adsorptive removal of MAL (14.01 mg·g−1 at 10 mg·L−1 concentration) with linear increase in adsorption capacity as the function of initial pesticide concentration. The MOFs were also able to retain ca. 50% of their adsorption efficiency over the course of five cycles of adsorptive removal of CP. In the future, a comprehensive data table showing the performance of various MOFs against various OPPs can be constructed on the basis of parameters used in this study. [ABSTRACT FROM AUTHOR]

In this contribution, we describe the kinetics associated with the rac-Me2Si[2-Me-4-Ph-Ind]2ZrCl2 (Cat-1)/borate/TIBA catalyzed copolymerization of E/dienes (isoprene (IP), butadiene (BD), 5-ethylidene-2-norbornene (ENB), 4-vinylcyclohexene (VCH) and vinyl norbornene (VNB)), and E/diene/1-hexene (1H) terpolymerization by using thiophenecarbonyl chloride (TPCC) that was used in Ziegler-Natta (Z-N) and metallocene-catalyzed polyethylene (PE) and polypropylene (PP) and E/P polymerizations. In both types of polymerizations, a higher amount of dienes was incorporated when VNB (2.70 mole %) and VCH (1.56 mole %) were added as comonomer, but IP and BD were incorporated with the moderated rate (0.6-1.1 mole %) with higher activities (3.45x106gm/mmolMt·h). The active center [Zr]/[C*] fraction is higher (61%) than previously reported PE polymerizations, especially in the case of E/IP, E/BD and E/IP/1H but lower than E/P (87%) copolymerization. Significantly, IP and BD activated the inactive catalytic sites that were dormant in the PE. The propagation rate constant (kpE) with IP was higher (kp564 Lmol-1s-1), while kpE with VNB (kp379 Lmol-1s-1) and VCH (kp304 Lmol-1s-1), which were lower than PE. This difference is built because of the diffusion barrier in the system. Compared to E/diene copolymers, kpE values in E/diene/1H terpolymerizations for IP, VCH, and VNB are higher and stable except ENB and determine that 1H prevents the insertion of dienes and reduces the crystalline properties resultant moderate kpE. Even though the E/BD copolymers decreased butadiene content of over 2 mol% resulted in better crystalline characteristics, lower diffusion barriers, and a higher kpE value. In concept, IP and BD are linear and readily available for coordination. While VCH, ENB and VNB are cyclic and bulky, metallocene in contact ion pairs cannot accept ENB, VNB, and VCH for coordination and subsequently act as dormant in the polymerization. [ABSTRACT FROM AUTHOR]