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Oral squamous cell carcinoma (OSCC) remains a significant global challenge in the medical field, accounting for approximately 300,000 incidences and 145,000 mortalities annually. Studies suggest that early cancer detection is the most vital factor in improving OSCC patient outcomes. Effective clinical diagnosis methods for early OSCC are needed urgently. OSCC biomarkers are identified to be associated with cancer progression and biosensors are devices developed to detect the presence of OSCC biomarkers to allow early cancer diagnosis. Biosensor technology has significant potential in providing rapid and accurate detection of OSCC biomarkers with high sensitivity and specificity. Biosensors have various advantages compared to conventional diagnostic methods such as being non-invasive, low-cost, and convenient. Biosensors hold the potential to be adopted as point-of-care-testing (POCT) devices by bringing biosensor technology to the patients. This review aims to provide a comprehensive review by describing and comparing different categories of OSCC biosensors based on their advantages and drawbacks. The recent obstacles and opportunities for developing effective biosensors for cancer diagnosis are summarized. • Oral squamous cell carcinoma (OSCC) remains a significant global challenge. • Effective clinical diagnosis methods for early OSCC are needed urgently. • OSCC biomarkers are identified to be associated with cancer progression. • Biosensors are devices developed to detect the presence of OSCC biomarkers. • This review described and compared different categories of OSCC biosensors. [ABSTRACT FROM AUTHOR]

• Nanotechnology a new source of significant advancements for the agricultural industry. • Nano-based biosensors help to alleviate the impact of various stresses in plants. • Nano-based biosensors play a vital role in improving the performance of crop plants. With the confluence of various disciplines, advanced technologies have cropped up. Nanotechnology has developed various emerging devices such as nano-biosensors. A nano-biosensor is a small analytical system possessing multifaceted applications in the field of agriculture, health, environment and quality control. In agriculture, it has shown tremendous potential for simple and fast methods of plant disease detection and identification. In this review we discuss the applications of biosensors in modern agriculture and their role in diagnosing and managing biotic and abiotic stresses in plants. It has been a topic of keen interest among researchers to investigate the potentiality of biosensors in plant stress management. Nano-based biosensors in agricultural stress management encompass various biomasses like metals, electrodes, etc. The review also focuses on the extensive use of nano-based biosensors in plant disease detection and elucidation of metabolic factors involved at the cellular level. There seems to be a significant untapped potential in using biosensors of nano origin for use in plant sciences. The literature suggests that nano-based biosensors will be the future forerunners in plant stress diagnosis. Comprehensively, this review elucidates various high throughput methodologies to mitigate various plant stresses and the various achievements in developing nano-inspired biosensors in plant stress biology. [ABSTRACT FROM AUTHOR]

Confronted with the substantial environmental threat posed by organophosphorus pesticides, the urgency to develop reliable and efficient mitigation strategies is paramount. Photocatalytic technology, which catalyzes the generation of potent oxidizing radicals, emerges as a promising solution. In this study, we have successfully synthesized In 2 O 3 /WO 3 (IO/WO) nanocomposites, endowed with oxygen defects and S-scheme heterojunctions, exhibiting exceptional photocatalytic degradation activity and mineralization efficiency. Notably, the WO material synthesized in this study is blue in color, unlike the traditional yellow color of WO, indicating a rich presence of oxygen defects. The 60-IO/WO nanocomposite, containing 60 % IO, achieved superior photocatalytic degradation, reducing triazophos pesticide from 100 % to 21.29 % within 60 min, outperforming the individual materials IO (56.97 %) and WO (48.02 %). This nanocomposite also exhibited remarkable corrosion resistance across multiple cycles, showcasing significantly enhanced stability compared to the individual IO and WO materials. Electron paramagnetic resonance (EPR) spectroscopy confirmed the presence of oxygen defects in the blue WO, while both EPR and theoretical calculations substantiated the formation of the S-scheme heterojunction in the 60-IO/WO nanocomposite. The new nanocomposite's excellent photocatalytic degradation activity is influenced by various factors such as differing surface areas, composite amounts, photocurrent responses, and resistances, all of which impact the degradation performance of triazophos. Compared to traditional photocatalytic materials, the IO/WO nanocomposite demonstrates a significant edge in photocatalytic efficiency and chemical stability, offering considerable potential for environmental remediation, especially in the degradation of organophosphorus pesticides. [Display omitted] • The 60-In 2 O 3 /WO 3 nanocomposite with oxygen vacancies shows enhanced photocatalytic degradation of triazophos. • Tests confirm oxygen vacancies and an S-scheme heterojunction in the In 2 O 3 /WO 3 nanocomposite. • Oxygen defects and S-scheme heterojunctions increase photocatalytic efficiency by enhancing charge dynamics. [ABSTRACT FROM AUTHOR]

Since ancient times, Tuberculosis (TB) has been a severe invasive illness that has been prevalent for thousands of years and is also known as "consumption" or phthisis. TB is the most common chronic lung bacterial illness in the world, killing over 2 million people each year, caused by Mycobacterium tuberculosis (MTB). As per the reports of WHO, in spite of technology advancements, the average rate of decline in global TB infections from 2000-2018 was only 1.6% per year, and the worldwide reduction in TB deaths was only 11%. In addition, COVID-19 pandemic has reversed years of global progress in tackling TB with fewer diagnosed cases. The majority of undiagnosed patients of TB are found in low- and middle-income countries where the GeneXpert MTB/RIF assay and sputum smear microscopy have been approved by the WHO as reference procedures for quickly detecting TB. Biosensors, like other cutting-edge technologies, have piqued researchers' interest since they offer a quick and accurate way to identify MTB. Modern integrated technologies allow for the rapid, low-cost, and highly precise detection of analytes in extremely little amounts of sample by biosensors. Here in this review, we outlined the severity of tuberculosis (TB) and the most recent developments in the biosensors sector, as well as their various kinds and benefits for TB detection. The review also emphasizes how widespread TB is and how it needs accurate diagnosis and effective treatment. [ABSTRACT FROM AUTHOR]

• Heterogeneous kinetics of fenthion and parathion toward OH radicals was studied. • OH radicals play an important role in their atmospheric degradation. • A negative RH and a positive temperature dependences of kinetics were observed. • Heterogeneous rate constants and atmospheric lifetimes were obtained. Fenthion and parathion are two representative kinds of organophosphorus pesticides and widely used in agriculture. They are directly or indirectly released into the atmosphere by spraying or volatilization processes. However, their heterogeneous reactivity toward OH radicals has not yet been well understood. Therefore, this work investigated the heterogeneous kinetics of the OH-initiated degradation of surface-bound fenthion and parathion using a flow reactor. The results showed that OH radicals played an important role in the atmospheric degradation of fenthion and parathion. Their average rate constants were (7.20 ± 0.77) × 10−12 and (10.40 ± 0.60) × 10−12 cm3/(mol· sec) at a relative humidity (RH) and temperature of 35% and 20 °C, respectively, suggesting that they have relatively short lifetimes in the atmosphere. In addition, a negative RH dependence and a positive temperature dependence of the rate constants were observed. The Arrhenius expressions of fenthion and parathion were k 2 = (1.34 ± 0.48) × 10−9exp[−(1432.59 ± 105.29)/T] and k 2 = (1.96 ± 1.38) × 10−9exp[−(1619.98 ± 222.02)/T], respectively, and their overall activation energy was estimated to be (11.88 ± 0.87) and (13.48 ± 1.83) kJ/mol. The experimental results will update the kinetic data of fenthion and parathion in the atmosphere and be helpful to further understand their atmospheric transportation processes. [Display omitted] [ABSTRACT FROM AUTHOR]

In this study, a biosensor based on a central microring comprising miniature gold rings is reported for the detection of influenza avian viruses. The label-free microring resonator's design performance attributes as a function of the host analytes (viral samples) enable great sensitivity for detecting various viruses, such as H1N1 and H9N2. The microring resonator's optimised characteristics make the suggested biosensor sensitive to these viruses. The simulations show a sensitivity of 880 nm/RIU for H1N1 and around 2025 nm/RIU for H9N2. The use of two-dimensional black phosphorus materials with higher field enhancement, biocompatibility, and a greater surface-to-volume ratio resulted in a significant increase in sensitivity of 1425 nm/RIU for detecting H9N2. The sensor is proven to be more sensitive to H9N2 than H1N1. Furthermore, the biosensor based on 2D material has a compact footprint and a larger wavelength shift for H9N2, which can accelerate the development of nano optic biosensors for rapid, sensitive, and early detection of viruses. [ABSTRACT FROM AUTHOR]

Late 2019 witnessed the outbreak and widespread transmission of coronavirus disease 2019 (COVID-19), a new, highly contagious disease caused by novel severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2). Consequently, considerable attention has been paid to the development of new diagnostic tools for the early detection of SARS-CoV-2. In this study, a new poly-N-isopropylacrylamide microgel-based electrochemical sensor was explored to detect the SARS-CoV-2 spike protein (S protein) in human saliva. The microgel was composed of a copolymer of N-isopropylacrylamide and acrylic acid, and gold nanoparticles were encapsulated within the microgel through facile and economical fabrication. The electrochemical performance of the sensor was evaluated through differential pulse voltammetry. Under optimal experimental conditions, the linear range of the sensor was 10−13–10−9 mg/mL, whereas the detection limit was 9.55 fg/mL. Furthermore, the S protein was instilled in artificial saliva as the infected human saliva model, and the sensing platform showed satisfactory detection capability. The sensing platform exhibited excellent specificity and sensitivity in detecting spike protein, indicating its potential application for the time-saving and inexpensive detection of SARS-CoV-2. [ABSTRACT FROM AUTHOR]

Diazinon (DZN) is a refractory organophosphorus pesticide (OP) in the surrounding environment due to its overuse in agriculture. The antioxidant activity of Epigallocatechin gallate (EGCG) from green tea is at least 100 times greater than that of vitamin C. This study aimed to study the effects of DZN on the meiotic maturation of porcine oocytes, as well as the protective roles of EGCG. Firstly, the effects of DZN and EGCG on meiotic nuclear maturation of porcine oocytes were detected, and then embryonic development was investigated by chemical parthenogenetic activation. Next, the spindle assembly, mitochondrial membrane potential (MMP), reactive oxygen species (ROS), DNA damage, and finally the early apoptosis of oocytes were examined by immunofluorescence staining. The results revealed that DZN exposure significantly reduced the quality of porcine oocytes, such as failure of nuclear and cytoplasmic maturation, evidenced by abnormal spindle assembly, disordered chromosome alignment, low MMP, observably increased ROS, severe DNA damage, and early apoptosis. Appropriate EGCG could significantly reduce all these defects caused by DZN. In conclusion, EGCG can help prevent the harm that DZN exposure can do. These findings offer convincing support for enhancing the oocyte quality from EGCG through daily ordinary beverages. • Effects of DZN and EGCG on the meiotic maturation of porcine oocytes. • EGCG protects the mitochondrial function of DZN-exposed oocytes. • EGCG reduces DNA damage and inhibits early apoptosis of DZN-exposed oocytes. [ABSTRACT FROM AUTHOR]

The possible role of voltage-sensitive calcium channels (VSCC) activation in the glufosinate ammonium (GLA)-induced dopamine release was investigated using selective VSCC blockers and the dopamine levels were measured by HPLC from samples obtained by in vivo cerebral microdialysis. While pretreatment with 10 μM flunarizine (T-type VSCC antagonist) or nicardipine (L -type VSCC antagonist) had no statistically significant effect on dopamine release induced by 10 mM GLA, pretreatment with 100 μM of both antagonists, or 20 μM ω-conotoxin MVIIC (non-selective P/Q-type VSCC antagonist) significantly decreased the GLA-induced dopamine release over 72.2%, 73%, and 70.2%, respectively. Administration of the specific antagonist of neuronal N-type VSCCs, the ω-conotoxin GVIA (20 μM), produced an almost complete blockade of in vivo dopamine release induced by GLA. These results show that GLA-induced dopamine release could be produced by the activation of a wide range of striatal VSCC located at the synaptic terminals and axons of striatal dopaminergic neurons, especially N-type VSCC. [Display omitted] • GLA increased the in vivo dopamine release from rat striatum. • Blockade of T-type VSCC significantly decreased the GLA-induced dopamine release. • Blockade of L -type VSCC significantly decreased the GLA-induced dopamine release. • Blockade of P/Q-type Ca2+ channels also reduced GLA-induced dopamine release. • Blockade of N-type Ca2+ channels totally abolished GLA-induced dopamine release. [ABSTRACT FROM AUTHOR]

The improper use of organophosphate pesticides (OPs) can lead to residue posing a serious threat to human health and environment. Therefore, the development of a simple, portable, and sensitive detection method is crucial. Herein, a bioenzyme-nanozyme-chromogen all-in-one paper-based sensor was synthesized. Initially, the Ce/Zr-MOF with peroxidase-like activity was grown on filter paper (FP) using in-situ solvent thermal method, resulting in Ce/Zr-MOF@FP. Subsequently, the AChE-ChO-TMB system was immobilized onto Ce/Zr-MOF@FP using biocompatible gelatin, which enhanced cascade catalysis efficiency through the proximity effect. Based on the inhibition principle of OPs on AChE, we integrated this sensor with Python-based image recognition algorithm to achieve detection of OPs. Using 2,2-dichlorovinyl dimethyl phosphate (DDVP) as a model of OPs, it has good detection performance with a detection limit of 0.32 ng mL−1 and a recovery rate range of 95–107%. The potential for on-site detection of DDVP residues in vegetables and fruit samples is highly promising. • A bioenzyme-nanozyme-chromogen all-in-one paper-based sensor was created. • The bimetal synergy significantly enhanced the catalytic activity of Ce/ Zr-MOF. • Circular microtest areas were created using wax-printing and cold-mounting technique. • Image recognition algorithm established based on Python intelligently detects DDVP. • The sensor is sensitive, easy to operate, and suitable for field testing. [ABSTRACT FROM AUTHOR]

In this study, a hydrophobic covalent organic framework-functionalized magnetic composite (CoFe 2 O 4 @Ti 3 C 2 @TAPB−TFTA) with a high specific area with 1,3,5-tris(4-aminophenyl)benzene (TAPB) and 2,3,5,6-tetrafluoroterephthalaldehyde (TFTA) was designed and synthesized through Schiff base reaction. An efficient magnetic solid-phase extraction method was established and combined with gas chromatography–triple quadrupole mass spectrometry to sensitively determine 10 organochlorine and organophosphorus pesticides in tea samples. The established method exhibited good linearity in the range of 0.05–120 μg/L and had low limits of detection (0.013–0.018 μg/L). The method was evaluated with tea samples, and the spiked recoveries of pesticides in different tea samples reached satisfactory values of 85.7–96.8%. Moreover, the adsorption of pesticides was spontaneous and followed Redlich–Peterson isotherm and pseudo-second-order kinetic models. These results demonstrate the sensitivity, effectiveness, and reliability of the proposed method for monitoring organochlorine and organophosphorus pesticides in tea samples, providing a preliminary basis for researchers to reasonably design adsorbents for the efficient extraction of pesticides. • Covalent organic framework functionalized magnetic MXene nanocomposites were synthesized. • The synthesized functional material exhibited excellent adsorption for OPP and OCP pesticides. • The adsorption of OPPs and OCPs abided by pseudo-second-order kinetic and Redlich-Peterson isotherm models. • The established method provided high sensitivity for OPP and OCP pesticides. [ABSTRACT FROM AUTHOR]

Enzyme-inhibited electrochemical sensor is a promising strategy for detecting organophosphorus pesticides (OPs). However, the poor stability of enzymes and the high oxidation potential of thiocholine signal probe limit their potential applications. To address this issue, an indirect strategy was proposed for highly sensitive and reliable detection of chlorpyrifos by integrating homogeneous reaction and heterogeneous catalysis. In the homogeneous reaction, Hg2+ with low oxidation potential was employed as signal probe for chlorpyrifos detection since its electroactivity can be inhibited by thiocholine, which was the hydrolysate of acetylthiocholine catalyzed by acetylcholinesterase. Additionally, Co,N-doped hollow porous carbon nanocage@carbon nanotubes (Co,N-HPNC@CNT) derived from ZIF-8@ZIF-67 was utilized as high-performance electrode material to amplify the stripping voltammetry signal of Hg2+. Thanks to their synergistic effect, the sensor exhibited outstanding sensing performance, excellent stability and good anti-interference ability. This strategy paves the way for the development of high-performance OP sensors and their application in food safety. • A novel turn-on indirect electrochemical chlorpyrifos sensor was proposed; • Integration of homogeneous reaction and heterogeneous catalytic signal amplification; • Hg2+ with low oxidation potential and high peak current was used as signal probe; • Hollow Co,N-HPNC@CNT was employed to catalyze signal amplification of Hg2+; • The sensor showed excellent performance in pesticide detection in real samples. [ABSTRACT FROM AUTHOR]

Profenofos (PFF) is a commonly used organophosphorus insecticide that requires strict monitoring due to its potential environmental, ecological, and human health risks originating from residues in soil and water systems, as well as accumulation in crops. In this study, a novel monoclonal antibody (mAb) specific to PFF was prepared for the first time and the recognition mechanism was investigated through molecular simulation. Subsequently, a mAb-based colloidal gold immunochromatographic assay (GICA) was developed for the rapid screening of PFF in fruit and vegetable samples. The mAb exhibited an IC 50 value of 12.9 ng/mL, and limit of detection (LOD) of 4.6 ng/mL, respectively in indirect competitive immunosorbent enzyme-linked immunosorbent assay (ic-ELISA). After optimization, the developed GICA exhibited a visual limit of detection (vLOD) of 20 ng/mL and a quantitative of detection (qLOD) of 5.2 ng/mL, with a linear range from 10.0 to 83.8 ng/mL. Good correlation was observed between the results of GICA and standard Gas Chromatography-Tandem Mass Spectrometry (GC-MS/MS) in matrix and recovery test. The developed GICA can be used for rapid sample detection within 15 min, which is an excellent tool for screening PFF in foods and environmental samples. [Display omitted] • Monoclonal antibody with good sensitivity and specificity to profenofos was produced. • Computer simulation was performed to study the interaction between antibody and profenofos. • Rapid and simple colloidal gold immunochromatographic assay was developed for visual detection of profenofos. [ABSTRACT FROM AUTHOR]

The coexistence of pesticides and plastic film residues in agricultural soils poses a significant threat to soil organisms due to their potential long-term contamination and combined toxic effects. Specifically, earthworms are at risk of simultaneously ingesting residual pesticides and microplastics, yet the impact of this combined exposure on their intestinal health and function remains poorly understood. In this study, earthworm (Eisenia fetida) were single and combined exposed to three particle sizes (10 μm, 500 μm, and 2 mm) of polyethylene microplastics (PE MPs) and imidacloprid (IMI) for 28 days, respectively. Our findings underscore that compared to single exposures, the combined exposure inflicted more profound injuries on intestinal tissues and elicited a heightened activation of intestinal digestive enzymes. Furthermore, the combined exposure significantly perturbed the relative abundance of several pivotal metabolic-associated gut microbiota, fostering an enrichment of pathogenic species. Metabolomics analysis showed combined exposure increased differential metabolites, disrupting amino acid, fatty acid, and carbohydrate metabolism in earthworm intestines, potentially hindering nutrient absorption and causing toxic metabolite accumulation. An integrated omics analysis implies that combined exposures have the potential to disrupt the relative abundance of crucial gut microbiota in earthworms, thereby altering their intestinal metabolism and subsequently impacting intestinal health and functionality. Overall, the results reveal that combined exposure of IMI and PE MPs exacerbate the negative effects on earthworm gut health, and this study holds significant implications for the holistic understanding of the combined toxic effects of microplastics and pesticide on soil ecosystems. [Display omitted] • Microplastics and imidacloprid co-exposure exacerbate negative effects on earthworm gut health. • Co-exposure significantly altered gut bacterial communities, increasing pathogenic species. • Co-exposure interfered with the amino acids, fatty acids and carbohydrates metabolic pathways. • The disruption of intestinal microbia and metabolites might be the mechanism of intestinal damage. [ABSTRACT FROM AUTHOR]

[Display omitted] • An extraction bar was fabricated by UIO-66-Py via facile method. • UIO-66-Py interpenetrated into PDMS uniformly to form functional film. • Detection of multiple pesticides was achieved by the optimized method. • Satisfactory linearity, accuracy, RSDs and LODs were obtained. • This method affords a great potential in clinical point-of-care testing. Acute pesticide poisoning can cause several symptoms that threaten life safety, and the development of a rapid detection method is conducive to identifying toxicants early. In this work, we proposed a facile post-modification method to fabricate functional metal-organic frameworks (UIO-66-Py) with high specific surface area, stability and target recognition sites. UIO-66-Py-coated extraction bar could be fabricated by using PDMS as a "solid glue" to immobilize UIO-66-Py, where UIO-66-Py interpenetrated into PDMS uniformly to form functional film. The UIO-66-Py-coated extraction bar could work as an efficient solid-phase microextraction device for extraction of toxicants (pesticides) in the fetal bovine serum, which ascribed to great binding energy between UIO-66-Py and pesticides. Moreover, the immobilized membrane fabricated by PDMS would increase penetration of pesticides and diffusion path, thus promoting the retention of pesticides to afford more affinity sites for capturing pesticides. In addition, rotation speed, extraction time, elution solvent, and desorption time were investigated to achieve excellent recovery, and the corresponding optimal conditions were 200 rpm, 10 min, methanol, and 3 min, respectively. Through the established quantitative method, low limit of detections (LODs) of 0.15 − 0.37 ng/mL with relative standard deviations (RSDs) of less than 4.5 %, and linear correlation coefficients (R2) of 0.99 for these pesticides were achieved. The proposed on-site detection method exhibited an excellent performance with great sensitivity, anti-interference, and reusability, which demonstrated that synergistic effect from UIO-66-Py and PDMS facilitated highly sensitive detection and selective extraction. The findings in this work develop efficient detection methods for toxicants in biological sample and provide deep insights to further improve treatment efficiency of pesticide poisoning and afford a great potential in clinical point-of-care testing (POCT). [ABSTRACT FROM AUTHOR]

The synthesis method of CoNi(OH) x /CeO 2 /MoS 2 -MWCNTs/GCE with the method to detect methyl parathion. The study introduces a novel composite electrode, CoNi(OH) x /CeO 2 /MoS 2 -MWCNTs, made using a two-step process with ZIF-67. It offers ultrasensitive detection of the pesticide methyl parathion, with high electrocatalytic activity and conductivity for rapid, accurate residue analysis in environmental and agricultural samples. The sensor provides a broad linear response, high sensitivity, and a detection limit of 0.1 nM, surpassing other methods. Validated with real samples, it shows accuracy and reliability with 98.4–108% recovery rates, enhancing the application of nanocomposites in electrochemical sensing. [Display omitted] • An electrochemical CoNi(OH) x /CeO 2 /MoS 2 -MWCNTs/GCE sensor is presented for methyl parathion determination. • High selectivity, repeatability and reproducibility of the sensor are obtained. • Good linear concentration ranges of 1.0 to 10.0 µM with low LOD (0.1 nM) are observed. • The developed sensor could be applied in methyl parathion detection in actual samples. This research presents the development of a novel composite electrode material, CoNi(OH) x /CeO 2 /MoS 2 -MWCNTs, synthesised via a two steps reflux process with ZIF-67 as precursor for the ultrasensitive detection of methyl parathion, a widely used organophosphorus pesticide. This electrode material demonstrates superior electrocatalytic activity and conductivity, enabling the rapid and accurate detection of methyl parathion residues in environmental and agricultural samples. The study extensively characterises the synthesised material using SEM, XRD, EDS, and EIS, confirming its unique nanostructure and elemental composition. The sensor exhibits a wide linear response range, high sensitivity, and a low detection limit of 0.1 nM, outperforming many existing methods. The practical application of the sensor is validated through objective sample analysis, showing high accuracy and reliability with recoveries between 98.4 % and 108 %. This work introduces a highly efficient sensor for methyl parathion detection and contributes to the broader application of nanocomposite materials in electrochemical sensing. [ABSTRACT FROM AUTHOR]

Phorate, an organophosphorus compound is known to have applications against pests. However, its hazardous nature is a matter of concern. Microbial biodegradation is a potent method that can eliminate pesticides from the environment by enzymatic reactions. As toxicity and binding specificity are inherently correlated to each other, this study was focussed on finding out binding sites for ensuing biodegradation. Brevibacterium frigoritolerans GD44 and Enterobacter cloacae subsp. cloacae ATCC 13047 were included in the study for genomic and structural analyses as alkaline phosphatase from Brevibacterium frigoritolerans GD44 and endonuclease/exonuclease/phosphatase from Enterobacter cloacae subsp. cloacae ATCC 13047 were found to degrade phorate. It was apparent from the present findings that alkaline phosphatase containing homologous bacterial species are AT-rich, while the phosphatase containing bacteria are GC-rich. Bacterial species having phosphatase enzyme contain more aromatic amino acids that stabilize the protein structure than alkaline phosphatase containing bacteria. Variation of relative synonymous codon usage (RSCU) value was found to be very little and natural selection pressure was preferred over mutational pressure in determining codon usage pattern. High level of codon adaptation index (CAI) found in both the bacterial species indicates higher level of codon usage bias and gene expression in them. Furthermore, docking results suggest that alkaline phosphatase has higher binding affinity to phorate than phosphatase that might be considered effective in bioremediation. The results obtained are considered to shed further light in the experimental biodegradation of organophosphorus pesticides by the bacteria. In silico structure –function analysis of enzyme involved in phorate biodegradation. [Display omitted] • Phylogenetic/MSA analyses show relatedness of bacterial phorate-degrading enzymes. • Enc plot/COA predict mutational pressure influence on codon usage pattern. • CAI values delineate the adaptability of protein/gene. • Molecular docking studies reveal specificity of degrading enzymes with phorate. [ABSTRACT FROM AUTHOR]

In this paper, an ultra-small-sized CuO x /GDYO nanozyme in situ grown on ITO glass was rationally synthesized from mixed precursors of graphdiyne oxide (GDYO) and copper based infinite coordination polymer (Cu-ICP, consisting of Cu ions and two organic ligands 3,5-di-tert-butylcatechol and 1,4-bis(imidazole-1-ylmethyl)benzene) via mild and simple electrochemical strategy. On one hand, the preferential electro-reduction of Cu-ICP enabled the formation of ultra-small CuO x with Cu(I) as the main component and avoided the loss of oxygen-containing functional groups and defects on the surface of GDYO; on the other hand, GDYO can also serve as electroless reductive species to facilitate the electrochemical deposition of CuO x and turn itself to a higher oxidation state with more exposed functional groups and defects. This one-stone-two-birds electrochemical strategy empowered CuO x /GDYO nanozyme with superior peroxidase-mimicking activity and robust anchoring stability on ITO glass, thus enabled further exploration of the portable device with availability for point-of-use applications. Based on the organophosphorus pesticides (OPs) blocked acetylcholinesterase (AChE) activity, the competitive redox reaction was regulated to initiate the chromogenic reaction of 3,3′,5,5′-tetramethylbenzidine (TMB) catalyzed by CuO x /GDYO peroxidase-like nanozyme, which laid out a foundation for the detection of OPs (with chlorpyrifos as an example). With a detection of limit low to 0.57 nM, the OPs residues during agricultural production can be directly monitored by the portable device we developed. [Display omitted] • Ultra-small CuO x /GDYO formed via one-stone-two-birds electrochemical strategy. • Synergistic effect between CuO x and GDYO boosts their peroxidase-like activity. • CuO x /GDYO nanozyme in-situ growth on ITO glass is endowed with robust stability. • Nanozymes involved competitive redox reaction is modulated for OPs detection. • Portable device is exploited for colorimetric sensing of OPs in farmland samples. [ABSTRACT FROM AUTHOR]

In this study, a nanozyme (ZIF-Co-Cys) with high oxidase-like catalytic activity was prepared, and a ratiometric fluorescent/photothermal dual-mode probe was constructed for organophosphorus pesticides (OPs) detection based on the competitive effect of ZIF-Co-Cys and the enzymatic reaction product of acid phosphatase (ACP) on o -phenylenediamine and the inhibition effect of OPs on ACP activity. Using dimethyl dichloroviny phosphate (DDVP) as the model, both the fluorescence intensity ratio and the temperature change of the probe solution exhibited an excellent correlation with OPs concentration. The detection limits were 1.64 ng/mL and 0.084 ng/mL, respectively. Additionally, the detection of DDVP residues in real samples verified the outstanding anti-interference and accuracy of the probe. This work not only provided a complementary dual-mode method for the accurate and rapid detection of OPs residues in complex samples, but also supplied a new insight into the design of a multi-mode sensing platform based on the cascade reaction of nanozyme. [Display omitted] • A dual-mode probe was constructed based on cascade reactions regulated by nanozyme. • It realized ratiometric fluorescent and photothermal detection for OPs. • It exhibited high sensitivity, low detection limit, and excellent selectivity. • The reliability was improved by mutual verification of the results of two modes. [ABSTRACT FROM AUTHOR]

The toxicity of organophosphorus pesticides (OPs) can catastrophically cause liver cell damage and inhibit the catalytic activity of cholinesterase. We designed and synthesized a near-infrared fluorescent probe HP-LZB with large Stokes shift which can specifically identify and detect butyrylcholinesterase (BChE) and visually explore the interaction between OPs and endogenous BChE in living cells. Fluorescence was turned on when HP-LZB was hydrolyzed into HP-LZ in the presence of BChE, and OPs could inhibit BChE's activity resulting in a decrease of fluorescence. Six OPs including three oxon pesticides (paraoxon, chlorpyrifos oxon and diazoxon) and their corresponding thion pesticides (parathion, chlorpyrifos and diazinon) were investigated. Both in vitro and cell experiments indicated that only oxon pesticides could inhibit BChE's activity. The limits of detection (LODs) of paraoxon, chlorpyrifos oxon and diazoxon were as low as 0.295, 0.007 and 0.011 ng mL−1 respectively and the recovery of OPs residue in vegetable samples was satisfactory. Thion pesticides themselves could hardly inhibit the activity of BChE and are only toxic when they are converted to their corresponding oxon form in the metabolic process. However, in this work, thion pesticides were found not be oxidized into their oxon forms in living HepG2 cells due to the lack of cytochrome P450 in hepatoma HepG2 cell lines. Therefore, this probe has great application potential in effectively monitoring OPs in real plant samples and visually exploring the interaction between OPs and BChE in living cells. [Display omitted] • HP-LZB is a near-infrared probe that can specifically recognize and detect BChE. • HP-LZB was used to detect OPs in vitro and in living cells. • Oxon OPs inhibit BChE's activity, resulting in a decrease of cell fluorescence. • Thion pesticides were found not be oxidized into their oxon forms in HepG2 cells. • The LODs of chlorpyrifos oxon and diazoxon were as low as 0.007 and 0.011 ng mL−1. [ABSTRACT FROM AUTHOR]

For the first time, a magnetic carbon nanocomposite was synthesized using one-step hydrothermal procedure, employing bovine serum albumin, curcumin, and ferric ammonium citrate. Additionally, the application of this novel composite as an adsorbent for magnetic dispersive solid phase extraction of fungicides and pesticides from water and food samples is a unique aspect of this study. Under optimum conditions (salt concentration: 5.0% w / v , pH: 7.0, desorption solvent: ethanol, sorbent amount: 20 mg, extraction time: 20 min, desorption time: 3 min, stirring rate: 500 rpm, sample volume: 30 mL, extraction temperature: room temperature, and desorption solvent volume: 150 μL) linearity (2.5 to 1400 ng mL−1), coefficients of determination (R2 ≥ 0.997), limits of detection (0.75 to 1.5 ng mL−1), and limits of quantification (2.5 to 5.0 ng mL−1) were achieved. The method validation results showed extraction recovery ranging from 71.2% to 93.4%, and preconcentration factors ranging from 142.5 to 186.1. [Display omitted] • A green sorbent was synthetized from bovine serum albumin and curcumin • The nanocomposite was applied as an adsorbent in MSPE procedure • This procedure was used for the extraction of OPPs and TFs from food samples • The proposed sorbent could be regenerated and reused at least five cycles • The proposed method provided a very good analytical performance [ABSTRACT FROM AUTHOR]

As one of Maillard's hazards, acrylamide (AAm) can induce neurotoxicity, mutagenicity, and genotoxicity, and it's urgent to construct a detection method for sensitive and specific monitoring of AAm. Herein, an aptamer-gated colorimetric sensor was developed to detect AAm in food. UiO-66-NH 2 was selected to combine acetylcholinesterase (AChE) and the aptamer of AAm to construct the aptamer-gated probe UAzyme-Apt. The addition of AAm would detach Apt and expose the active sites of UAzyme, resulting in the transformation of acetylthiocholine (ATCh) into thiocholine (TCh) that could inhibit the oxidase mimic activity of MIL-53 (Fe/Mn). Consequently, the concentration of AAm was inversely proportional to the absorbance at 652 nm, thus providing a qualitative and quantitative detection of AAm. The aptamer-gated probe can recognize AAm to improve specificity and stability and regulate the enzyme activity of UAzyme. This aptasensor enhances the detection methods of AAm and broadens the scope of applications for AChE inhibition detection, and targets are not limited to the substrate or organophosphorus pesticides. The linear range and limit of detection were 0.05–100 μM (R2 = 0.992) and 9.94 nM, and spiked analysis revealed the efficiency and robustness of the developed assembly. The colorimetric aptasensor can specifically detect AAm at low concentrations, and will be a promising tool to ensure food safety in the coming future. [Display omitted] • UAzyme enhanced the stability and substrate affinity of AChE. • The catalytic product of UAzyme inhibited the oxidative capacity of MIL-53 (Fe/Mn). • Aptamer could identify AAm and regulate the catalytic ability of UAzyme. • The method could be applied to real samples with excellent performance. [ABSTRACT FROM AUTHOR]

A Mn-based nanozyme, Mn-uNF/Si, with excellent alkali phosphatase-like activity was designed by in-situ growth of ultrathin Mn-MOF on the surface of silicon spheres, and implemented as an effective solid Lewis-Brønsted acid catalyst for broad-spectrum dephosphorylation. H 2 18O-mediated GC-MS studies confirmed the cleavage sites and the involvement of H 2 O in the new bonds. DRIFT NH 3 -IR and in-situ ATR-FTIR confirmed the coexistence of Lewis-Brønsted acid sites and the adjustment of adsorption configurations at the interfacial sites. In addition, a green transformation route of "turning waste into treasure" was proposed for the first time ("OPs→PO 4 3−→P food additive") using edible C. reinhardtii as a transfer station. By alkali etching of Mn-uNF/Si, a nanozyme Mn-uNF with laccase-like activity was obtained. Intriguingly, glyphosate exhibits a laccase-like fingerprint-like response (+,−) of Mn-uNF, and a non-enzyme amplified sensor was thus designed, which shows a good linear relationship with Glyp in a wide range of 0.49–750 μM, with a low LOD of 0.61 μM, as well as high selectivity and anti-interference ability under the co-application of phosphate fertilizers and multiple pesticides. This work provides a controllable methodology for the design of bifunctional nanozymes, which sheds light on the highly efficient green transformation of OPs, and paves the way for the selective recognition and quantification of glyphosate. Mechanistically, we also provided deeper insights into the structure-activity relationship at the atomic scale. [ABSTRACT FROM AUTHOR]

[Display omitted] • Linker functionalized metal organic frameworks are fabricated by post-modification. • The defects and active sites favor tailoring their adsorption behavior. • The synergistic interaction boosts binding energy and adsorption capacity. • The UiO-66-PA exhibited excellent performance in analysis of environmental water. Water pollution caused by organophosphorus pesticides (OPPs) from agricultural production causes vital great threat to mankind lives and thus developing a method for rapid removal and detection of OPPs is urgent. In this work, we proposed the linker functionalization of metal organic frameworks (UiO-66) by post-modification to generate defects and active sites for tailoring their adsorption behavior. The metal organic frameworks (MOFs) modified by functional groups (amino and pyridine) exhibited similar physicochemical property and pore structure. The UiO-66-PA exhibited an excellent performance of rapid adsorption of OPPs in water with average capacity of 246.55 mg/g. Experimental characterizations and theoretical simulations revealed that the enhanced binding energy between UiO-66-PA and OPPs resulted from synergistic interaction between pyridine and OPPs via nucleophilic effect, π-π interaction, and metal electronic interaction, boosting the adsorption capacity and removal efficiency, which suggested that functional group plays important role in improving performance. When used it as adsorbent for analysis of OPPs in water coupled with ambient ionization source, UiO-66-PA exhibited an excellent performance of the quantitative detection of OPPs in water with limit of detections (LODs) of 0.076–––0.251 ng/mL and relative standard deviations (RSDs) of 1.13 % − 5.84 %. In addition, the proposed analytical method could be applied in analysis of three environmental water samples with great sensitivity, anti-interference and reusability, which demonstrated that UiO-66-PA afforded outstanding selectivity for OPPs and could be appropriate for high-throughput screening and on-site analysis. This work could provide a novel method to design MOFs-based adsorbents with functions of removal and purification via post-modification and exhibit a great potential to rapid analysis of OPPs in environmental water. [ABSTRACT FROM AUTHOR]

• A new method for the analysis of pesticides in soil using direct-immersion solid-phase microextraction (DI-SPME) is presented. • Extraction is performed by making an aqueous slurry and then extracting with constant stirring. • A plackett-burman screening was performed for ten variables. Extraction time and percentage of organic modifier on the slurry were the most crucial variables to optimize separately. • The method appears fit-for-purpose, with detection limits between 0.01–10 µ g/kg and adequate repeatability when using an isotopically labelled internal standard. A new method was evaluated and developed for the analysis of pesticides in sandy-loam soil by direct-immersion solid phase microextraction (DI-SPME) followed by gas chromatography tandem-mass spectrometry (GC–MS/MS) determination. Ten pesticides were selected based on a literature survey of the compounds reported to be present in EU soils. The extraction was performed using SPME LC-Tips, a new SPME configuration with the coated fibers attached to a disposable and easy-to-handle micropipette tip, which was immersed into a soil slurry made by the addition of an aqueous solution to the soil sample. Ten experimental parameters were evaluated with a Plackett-Burman design, after which the extraction time and percentage of organic solvent in the aqueous extraction were optimized separately. The two fiber chemistries available (PDMS/DVB and C 18) were evaluated in parallel for the entire work. In the final method, slurry samples were made by adding an aqueous solution (6 % methanol v/v) to 2 g of soil. The fiber was conditioned and then inserted, for extraction, into the samples, stirred by a magnetic bar. Afterwards, the analytes were desorbed onto 100 µ L of methanol. After the addition of analyte protectants (ethylglycerol, gulonolactone, and sorbitol) the extract was injected into the GC–MS/MS system. Isotopically labelled penconazole was used as internal standard. A calibration was performed by extracting spiked soil with analyte concentrations of 0.1–50 µg/kg. Coefficients of determination of the linear calibration were between 0.94–0.98 for the PDMS/DVB and 0.92–0.99 for the C 18. Limits of detection range between 0.01–10 µg/kg for the PDMS/DVB and 0.1–10 µg/kg for the C 18. Overall, the C 18 analytically outperformed the PDMS/DVB but required a longer extraction time (120 min vs 75 min for the PDMS/DVB). This method allows automation and generates low residual toxic waste, having the potential to be introduced as a greener and simpler alternative to currently used sample preparation methodologies. [ABSTRACT FROM AUTHOR]

[Display omitted] • TEMPO-MWCNT, as a metal-free electrocatalyst, was prepared to enhance luminol ECL for the first time. • TEMPO-MWCNTs enable the generation of three ECL peaks in luminol/O 2 system and two ECL peaks in luminol/H 2 O 2 system. • The natures of these ECL peaks was revealed by the spooling ECL spectra. • Sensitive detection of malathion was achieved through ECL of luminol/H 2 O 2 system enhanced by TEMPO-MWCNTs. The utilization of an elaborate nanomaterial is still a prevalent method to generate luminol electrochemiluminescence (ECL). Herein, we report on the multimodal generation of anodic and cathodic luminol ECL through a metal-free nanomaterial. This nanomaterial was prepared by covalently grafting 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) on the surface of multi-walled carbon nanotube (MWCNT). TEMPO-MWCNTs modified electrode exhibit high electrocatalytic activities toward H 2 O, luminol, H 2 O 2 and O 2 during the oxidation/reduction processes. Such electrocatalysis has not only resulted in significant enhancement of luminol ECL, but also enabled the generation of three ECL peaks in luminol/O 2 system and two ECL peaks in luminol/H 2 O 2 system on the electrode via different pathways. The natures of these ECL peaks are also revealed through the spooling ECL spectra. Furthermore, an ECL sensor has been designed for sensitive detection of an organophosphorus pesticide (OP) based on the enhanced ECL of luminol/H 2 O 2 system. Therefore, this work suggests that nitroxyl radical functionalized carbon nanomaterial can be used as a new electrocatalyst for studying luminol ECL in the presence of either an endogenous or exogenous co-reactant. [ABSTRACT FROM AUTHOR]

Construction of highly-active artificial nanozymes for pesticides detection has great significance of human health and ecological systems. Herein, we have successfully designed a two-step approach to synthesize the TAPB-DMTP-COF (hereafter denoted as COF-OMe, TAPB, 1,3,5-tris(4-aminophenyl)benzene; DMTP, 2,5-dimethoxyterephaldehyde; COF, covalent organic framework)@Valine integrated cerium oxide nanozymes (COF-OMe@Valine-CeO 2) with phosphatase-like activities, which can cleave phosphate bonds (P O) of organophosphorus pesticides (OPs) for the formation of electroactive p-nitrophenol (p-NP). In detail, the Ce (IV)/Ce (III) species serve as the active sites to polarize and hydrolyze P O bond in OPs, and the excellent adsorption performance of porous COF-OMe toward OPs could promote the hydrolysis process of P O. Moreover, the efficient charge transfer at the covalent interface of COF-OMe@Valine-CeO 2 also contributed to this excellent catalytic process. By virtue of those advantages, the COF-OMe@Valine-CeO 2 electrochemical platform was successfully applied in methyl-paraoxon (MP) detection. The resulting electrochemical sensors displayed high sensitivity, a wide linear response range of 0.034–76 μmol/L, and low detection limits of 0.011 μmol/L for MP. The research not only provides a preparation method for COF with excellent nanozyme activity, but broadens some new insights for the design of highly efficient nanozymes for on-time detection for OPs. • The COF-OMe@Valine-CeO 2 nanocomposites were constructed through a two-step approach. • The mesopores of COF-OMe@Valine-CeO 2 enabling efficient diffusion and capture of the MP. • The resulting COF-OMe@Valine-CeO 2 showed sensitive detection of MP. • The proposed sensor presented a good sensitivity in real samples detection. [ABSTRACT FROM AUTHOR]

[Display omitted] • A fluorescence sensing system, employing low-toxicity quantum dots, was developed independent of enzymes and antibodies. • The quantum dot sensor achieves a remarkable detection limit of 10 ppb for chlorpyrifos, demonstrating notable resistance to interference from other pesticides. • The quantum dot sensor enables rapid and precise detection of organophosphorus thiophosphate pesticides in agricultural products, aligning with the capabilities of high-performance liquid chromatography detection. Organophosphorus pesticides (OPPs) constitute the most widely employed class of pesticides. However, the prevalent use of OPPs, while advantageous, raises concerns due to their toxicity, posing serious threats to food safety. Chemical sensors utilizing quantum dots (QDs) demonstrate promising applications in rapidly detecting OPPs residues, thereby facilitating efficient inspection of agricultural products. In this study, we employ an aqueous synthesis approach to prepare low toxic CdTe@ZnS QDs with stable fluorescence properties. To mitigate the risk of imprecise measurements stemming from the inherent susceptibility of fluorescence to quenching, we have adopted the principle of fluorescence resonance energy transfer (FRET) for the construction of the turn-on quantum dot sensor. With a detection limit for chlorpyrifos as low as 10 ppb (10 μg/L), the QDs sensor exhibits notable resistance to interference from various pesticides. Application of this system to detect organophosphorothioate pesticides in apples produced results consistent with those obtained from high-performance liquid chromatography (HPLC) detection, affirming the promising application prospects of this sensing system for the rapid detection of OPPs residues. [ABSTRACT FROM AUTHOR]

[Display omitted] • A novel oxidation-adsorption bifunctional material was successfully synthesized. • The introduction of Ce facilitated the capture of H 2 O 2 into the Fe-based catalysts. • Doped Ce promoted H 2 O 2 activation to produce more •OH and O 2 •-. • Inner-sphere complexation dominated adsorption of the generated phosphate. • The treated glyphosate solution enhanced germination and growth of Solanum nigrum L. Organophosphorus pesticides, widespread and hazardous to ecosystems and human health, were mainly decomposed thoroughly by advanced oxidation processes (AOPs). However, the generated inorganic phosphate (IP) was prone to accumulation and led to eutrophication of water bodies. Herein, a Fe/Ce bimetallic-loaded biochar (FeCe@BC-400–5) with excellent H 2 O 2 activation and IP adsorption properties was designed and used to treat glyphosate (GLY)-contaminated water. Results showed that ∼ 92 % of GLY (20 mg P/L) was removed in the FeCe@BC-400–5/H 2 O 2 system within 120 min, and the converted IP was almost completely adsorbed onto FeCe@BC-400. Experiment and theoretical calculations revealed that Ce doping facilitated the capture of H 2 O 2 by the iron-based catalysts and promoted the activation of H 2 O 2 to produce more reactive oxygen species (•OH and O 2 •-). Meanwhile, the released IP was adsorbed onto FeCe@BC-400–5 via inner-sphere complexation to avoid secondary contamination. Intriguingly, toxicity tests showed that the degraded GLY solution in FeCe@BC-400–5/H 2 O 2 system promoted germination rate, root and stem growth of Solanum nigrum L (herbaceous plant). This study provided a new idea on constructing oxidation-adsorption bifunctional materials for the comprehensive removal of organophosphorus in the Fenton-like field. [ABSTRACT FROM AUTHOR]

Organophosphorus pesticides (OPs) are the most widely used pesticides in agriculture, while their residues pose a potential threat to food safety and human health. The monitoring of OPs levels in food is of utmost importance. Meanwhile, the phenomenon of mixed-use multiple types of pesticides in agricultural production leads to the rise in analytical error. Identifying and discriminating multiple species of OPs with similar chemical structures is still challenging. Given the superior characteristics of colorimetry, in this review, colorimetric sensing strategies of OPs detection are first classified and summarized with specific recognition elements (biotic or abiotic) as the breakthrough point. Secondly, the colorimetric sensor arrays (CSAs) for OPs monitoring are reviewed, highlighting the design principles and analytical performances of chemometrics integrated CSAs for achieving simultaneous identification and discrimination of OPs in food. Finally, the current challenges and future perspectives in this hot topic are also discussed. Emerging colorimetric sensors have showed great potential for the detection of OPs in food. Chemometrics integrated CSAs can efficiently conquer the deficiency of conventional "lock-and-key" sensing mode and inject new vitality for the identification and discrimination of multi-OPs. • Colorimetric sensing strategies of OPs detection in food are summarized. • Applications of chemometrics integrated CSAs for OPs discrimination are discussed. • Current challenges and directions for OPs colorimetric detection are proposed. [ABSTRACT FROM AUTHOR]

• Using electrochemical biosensors for rapid detection of SARS-CoV-2 gene fragments. • Electrode material selection is Bi2Se3 single crystal obtained by mechanical peeling. • The peak current has a linear relationship with the logarithm of DNA concentration. • There is excellent specificity in identifying DNA, RNA, and viruses. • Sensors can clearly distinguish between positive and negative results. In this study, we have designed an electrochemical biosensor based on topological material Bi 2 Se 3 for the sensitive detection of SARS-CoV-2 in the COVID-19 pandemic. Flake-shaped Bi 2 Se 3 was obtained directly from high-quality single crystals using mechanical exfoliation, and the single-stranded DNA was immobilized onto it. Under optimal conditions, the peak current of the differential pulse voltammetry method exhibited a linear relationship with the logarithm of the concentration of target-complementary-stranded DNA, ranging from 1.0 × 10-15 to 1.0 × 10-11 M, with a detection limit of 3.46 × 10-16 M. The topological material Bi 2 Se 3 , with Dirac surface states, enhanced the signal-to-interference plus noise ratio of the electrochemical measurements, thereby improving the sensitivity of the sensor. Furthermore, the electrochemical sensor demonstrated excellent specificity in recognizing RNA. It can detect complementary RNA by amplifying and transcribing the initial DNA template, with an initial DNA template concentration ranging from 1.0 × 10-18 to 1.0 × 10-15 M. Furthermore, the sensor also effectively distinguished negative and positive results by detecting splitting-synthetic SARS-CoV-2 pseudovirus with a concentration of 1 copy/μL input. Our work underscores the immense potential of the electrochemical sensing platform based on the topological material Bi 2 Se 3 in the detection of pathogens during the rapid spread of acute infectious diseases. [ABSTRACT FROM AUTHOR]

[Display omitted] • A D-µSPE-GC procedure developed for Organophosphorus Pesticide determination in water samples. • Fe 3 O 4 NPs@SiO 2 @Bimetallic Ni, Zn-MOF identified as optimal sorbent for the OPP extraction. • Method shows wide linear ranges, low LODs, and high precision for accurate OPP detection. • The method was successfully applied for monitoring OPPs in several real water samples. A dispersive micro solid-phase extraction coupled with the GC-FID method was developed to determine three Organophosphorus pesticides: Fenitrothion, Chlorpyrifos, and Diazinon. Various sorbents, including Fe 3 O 4 NPs, Zn-MOF, Ni-MOF, Bimetallic Ni, Zn-MOF, and Fe 3 O 4 NPs@SiO 2 @ Bimetallic Ni, Zn-MOF, were synthesized and evaluated for their extraction efficiency of OPPs. Fe 3 O 4 NPs@SiO 2 @ Bimetallic Ni, Zn-MOF was identified as the optimal sorbent based on its performance. The affective factors in the procedure were optimized using one factor of the time and experimental design methods. The significant factors in this method included sorbent amount, extraction time, and desorption solvent volume with an optimum value of 37 mg, 8.3 min, and 231 µL, respectively. Under optimized conditions, the method exhibited distinct linear ranges for Fenitrothion, Chlorpyrifos, and Diazinon, ranging from 0.24 to 259, 0.17–234, and 0.25–247 ng mL−1, respectively, with high corresponding R2 values (0.9947, 0.9929, and 0.9943). The limits of detection (LOD) were determined based on three times the standard deviation of the blank sample divided by the slope of the calibration curve for each OPP to be 0.07, 0.05, and 0.07 ng mL−1 for Fenitrothion, Chlorpyrifos, and Diazinon, respectively, while the limits of quantification (LOQ) were 0.24, 0.17, and 0.25 ng mL−1. Precision was assessed by calculating intra-day and inter-day relative standard deviation (RSD%) values in one day and three consecutive days with three replicates of each analysis for three concentrations of 10, 25, and 50 ng mL−1, which were found to be below 4.27 %, 4.35 %, and 4.32 % for Fenitrothion, Chlorpyrifos, and Diazinon, respectively, for intra-day analysis, and below 5.43 %, 5.11 %, and 5.29 % for inter-day analysis, respectively. Additionally, the enrichment factor (EF) values for Fenitrothion, Chlorpyrifos, and Diazinon with a concentration of 20 ng mL−1 were determined to be 78.6, 82.4, and 75.7, respectively. Analysis of spiked real samples in two concentrations of 5.0 or 25.0 ng mL−1, such as tap water, river water, dam water, and well water, revealed recovery percentages in the range of 91.2 % to 97.7 %, with relative standard deviations ranging from 3.79 % to 4.98 %, further validating the method's reliability for practical applications. Overall, the method provides wide linearity, low LODs and LOQs, responsible RSDs, high EFs, and proper recovery percentages for determining OPPs. [ABSTRACT FROM AUTHOR]

The residues of organophosphorus pesticides (OPs) are increasing environmental pollution and public health concerns. Thus, the development of simple, convenient and sensitive method for detection of OPs is crucial. Herein, a multifunctional Fe-based MOF with fluorescence, catalytic and adsorption, is synthesized by a simple one-pot hydrothermal method. The ratiometric fluorescence sensor for detection of OPs is constructed by using only one multifunctional sensing material. The NH 2 -MIL-101(Fe) is able catalyze the o -phenylenediamine (OPD) into 2,3-diaminophenazine (DAP) in the presence of H 2 O 2. The generated DAP can significantly quench the intrinsic fluorescence of NH 2 -MIL-101(Fe) by the fluorescence resonance energy transfer (FRET) and internal filtration effect (IFE), while producing a new measurable fluorescence. Without immobilization or molecular imprinting, pyrophosphate ion (PPi) can inhibit the peroxidase-like activity of the NH 2 -MIL-101(Fe) by chelating with Fe3+/Fe2+ redox couple. Moreover, PPi can also be hydrolyzed by alkaline phosphatase (ALP), the presence of OPs inhibits the activity of ALP, resulting in the increase of extra PPi preservation and signal changes of ratiometric fluorescence, the interactions of ALP with different OPs are explored by molecular docking, the OPs (e.g., glyphosate) interact with crucial amino acid residues (Asp, Ser, Ala, Lys and Arg) are indicated. The proposed sensor exhibits excellent detection performance for OPs with the detection limit of 18.7 nM, which provides a promising strategy for detection of OPs. [Display omitted] • Three functions (fluorescence, catalytic and adsorption) were integrated in NH 2 -MIL-101(Fe). • Ratiometric fluorescence sensor was constructed for OPs detection. • The inhibitory differences of OPs against the ALP were explained by molecular simulations. • This proposed method can be applied in environment and food samples. [ABSTRACT FROM AUTHOR]

Accurate and rapid monitoring of organophosphorus pesticides (OPs) residues is crucial for regulating food safety. Herein, dual-emission carbon dots (de-CDs) were fabricated for the ratiometric detection of OPs and Hg2+. The de-CDs exhibited two emission peaks at 678 and 485 nm when excited with visible light. Interestingly, the fluorescence at 678 nm was significantly quenched by Hg2+ mainly because of the static quenching effect, whereas that at 485 nm exhibited a slight change. More significantly, the quenched fluorescence of the de-CDs recovered remarkably after introducing omethoate, diazinon and malathion. Accordingly, the ratiometric detection of the three OPs and Hg2+ was achieved with high selectivity and robust performance. In addition, the OPs residues assay in Brassica chinensis was successfully performed with satisfactory results. This study not only provides an attractive tool for the simple and rapid assay of OPs but also offers new insights into the fabrication of multi-functional carbon dots. [Display omitted] • The intrinsic dual-emission de-CDs are synthesised in this work. • The de-CDs show high fluorescence quantum yields under visible light excitation. • Ratiometric detection of three OPs and Hg2+ is achieved based on de-CDs. • The proposed probe is successfully used to monitor OPs residues in vegetables. [ABSTRACT FROM AUTHOR]

[Display omitted] • Bimetallic porous Ni-Pd nanocatalyst synthesis from wet chemical method. • GRR reaction and simultaneous Kirkendall effect to evolve hierarchical Ni-Pd catalyst. • Catalytic degradation of methyl parathion via hydrolysis with the bimetallic nanocatalyst. • Product of the pesticide degradation has been transformed to a value added product. In this work a wet-chemical recipe has been accounted for the synthesis of bimetallic Ni-Pd nanostructures at ambient condition involving pre-synthesized nickel nanoparticles and aqueous tetrachloropalladate, [PdCl 4 ]2- solution. The Galvanic replacement reaction (GRR) starts instantaneously between less noble Ni0 nanoparticle i.e., zero valent nickel (ZVN) and more noble [PdCl 4 ]2-. Thus ZVN is oxidatively etched out as soluble Ni2+ by more noble [PdCl 4 ]2- depositing Pd0 onto the residual ZVN. Concurrently the Ni2+ ions move outwardly into the bulk solution and the Pd0enters into the inwardly fashion owing to their different diffusivities and results in the formation of hollow bimetallic nanostructures following diffusion limited nanoscale Kirkendall effect. Finally, the bimetallic nanomaterial was shown to be a competent heterogeneous catalyst for facile hydrolytic degradation of an organothiophosphate pesticide, methyl parathion (MP). After the completion of the degradation, the degraded product, 4-nitrophenolate (4-NP) was subsequently reduced to 4-aminophenolate (4-AP) in the same reaction pot in presence of the same catalyst using borohydride. 4-AP is the principal ingredient for the production of the medicine paracetamol. Hence the bimetallic Ni-Pd nanoparticles turn out to be a promising heterogeneous catalyst for water pollution abatement through pesticide degradation vis-à-vis generation of value added product out of the degraded product of the pesticide. [ABSTRACT FROM AUTHOR]

[Display omitted] • Synthesis of magnetic Fe 3 O 4 @N-GO electrode via a simple one-step hydrothermal method. • Complete DIM degradation in 40 min achieved using Fe 3 O 4 @N-GO as Heter-EF catalyst. • DFT reveals reactive sites and bond-breaking patterns in DIM. • Toxicity prediction conducted for degradation products. The treatment of organic phosphorus pesticide (OPP) wastewater faces challenges such as incomplete degradation and low reaction efficiency. While heterogeneous electro-Fenton (Hetero-EF) has emerged as the preferred technology for addressing these issues due to its high treatment efficiency, further optimization is still necessary. This study used a one-pot hydrothermal method to prepare magnetic nitrogen-doped graphene oxide (Fe 3 O 4 @N-GO) composite electrodes to construct a novel Hetero-EF system. Dimethoate (DIM) was chosen as the representative pollutant to investigate the effects of parameters such as current density, pH, electrode spacing, and loading amount on degradation efficiency. The results demonstrated complete degradation of DIM within 40 min. Density functional theory (DFT) calculations and intermediate product analysis revealed that the reactive sites for DIM degradation were the P=S and P=S bonds, involving both hydrolysis and •OH pathways, with a decrease in toxicity of degradation products observed. Compared to graphite electrodes, Fe 3 O 4 @N-GO composite electrodes significantly increased H 2 O 2 production, achieving complete DIM degradation even after 5 cycles, with a phosphate conversion rate of 30–40 %. This study highlights the innovative strategy of the Hetero-EF system in its significant application value for OPP treatment. [ABSTRACT FROM AUTHOR]

Facing the increasingly severe issue of organophosphorus pesticide contamination globally, this study has developed a novel g-C 3 N 4 /WO 2.72 nanocomposite (abbreviated as CN/WO), featuring a specially designed S-scheme heterojunction and oxygen vacancies, to optimize the photocatalytic degradation of triazophos pesticides. Experiments demonstrate that the composite containing 30 % CN (termed 30-CN/WO) can efficiently degrade most of the triazophos within 100 minutes, and it exhibits exceptional stability across four successive cycles, significantly outperforming the individual CN and WO materials. Advanced analytical techniques such as X-ray photoelectron spectroscopy (XPS), electron paramagnetic resonance (EPR), and surface work function assessments have confirmed the pivotal role of the S-scheme heterojunction and oxygen vacancies in enhancing charge separation efficiency. This work not only advances the development of high-performance photocatalytic materials but also provides new strategies and practical scientific evidence for addressing organophosphorus pesticide pollution globally, showcasing its broad application prospects and scientific significance in environmental management. • g-C 3 N 4 /WO 2.72 enhances triazophos degradation via S-scheme heterojunction and oxygen vacancies. • Techniques confirm S-scheme heterojunction and oxygen vacancies improve charge separation efficiency. • Study shows g-C 3 N 4 /WO 2.72 's potential in managing global organophosphorus pesticide pollution. [ABSTRACT FROM AUTHOR]

Organophosphorus pesticides (OPs) are commonly employed in agriculture because they effectively control pests and increase crop output. However, most OPs are highly toxic. As a result, precise detection of OPs residues is critical for monitoring human disease and protecting the environment. In this work, we developed an aggregation-induced emission (AIE) probe of Sm-GSH-CuNCs for sensitive and visual detection of OPs by combining Sm3+ with glutathione-modified copper nanoclusters (GSH-CuNCs). Using glyphosate as the OPs model, the fluorescence of GSH-CuNCs was quenched due to the stronger affinity between Sm3+ and glyphosate than that between Sm3+ and GSH-CuNCs, as well as the formation of new P-O-Sm bonds between Sm3+ and glyphosate, resulting in the "on-off" response of the AIE probe. The Sm-GSH-CuNCs probe detected glyphosate throughout a linear range of 0.338–5.070 mg/L, with a detection limit of 0.013 mg/L. Furthermore, we have constructed an Sm-GSH-CuNCs agar slice detection platform that used smartphone assistance to detect glyphosate visually and quantitatively. A good linear relationship between R/B values and OPs concentrations(C i) was discovered: R/B =-0.316 C i +1.943 (R 2=0.9970). This work provided a simple, low-cost, and portable detection method for quantifying or visualizing OPs. • The AIE effects of GSH-CuNCs were amplified by Sm3+. • OPs were detected with high sensitivity using the AIE probe of Sm-GSH-CuNCs. • The agar slice with smartphone assistance could visually and quantitatively identify OPs on the spot. [ABSTRACT FROM AUTHOR]

Pesticide residues in agricultural products pose a significant threat to human health. Herein, a sensitive fluorescence method employing upconversion nanoparticles was developed for detecting organophosphorus pesticides (OPs) based on the principle of enzyme inhibition and copper-triggered o -phenylenediamine (OPD) oxidation. Copper ions (Cu2+) oxidized the colorless OPD to a yellow 2,3-diaminophenazine (oxOPD). The yellow solution oxOPD quenched the fluorescence of upconversion nanoparticles due to the fluorescence resonance energy transfer. The high affinity of Cu2+ for thiocholine reduced the level of oxOPD, resulting in almost no fluorescence quenching. The addition of dimethoate led to the inhibition of acetylcholinesterase activity and thus prevented the formation of thiocholine. Subsequently, Cu2+ oxidized OPD to form oxOPD, which attenuated the fluorescence signal of the system. The detection system has a good linear range of 0.01 ng/mL to 50 ng/mL with a detection limit of 0.008 ng/mL, providing promising applications for rapid detection of dimethoate. • An AChE-modulated UCNPs-oxOPD sensor for the detection of dimethoate was first proposed. • More than 80% quenching efficiency. • The proposed nanosensor has a low detection limit of 0.008 ng/mL. • A broader detection linear range with nearly 4 orders of magnitude. [ABSTRACT FROM AUTHOR]

• Graphene oxide decorated NiCo 2 (OH) 6 nanoflowers as a novel nanostructure was synthetized. • It was introduced for separation of the pesticides from food samples. • The main factors were inquired using matrixed match method. • High relative recoveries ascertained high potential of the presented method. Food safety is an important issue to protect humane health and improve the life quality. Hence, analysis of the possible contaminants in food samples is essential. A rapid and efficient vortexed-assisted dispersive µ-solid-phase extraction coupled with gas chromatography-mass spectrometry was proposed for simultaneous separation/preconcentration and determination of five commonly used organophosphorus pesticides. Reduced graphene oxide decorated NiCo 2 (OH) 6 nanoflowers as a novel nanostructure was synthetized and introduced for separation of the target pesticides from the wheat flour, rice flour, and baby food cereal samples. The characterization of the nanoflowers was accomplished by SEM-EDX, XRD, and FT-IR techniques. The main factors including pH, the amount of nanoflower, the volume of sample solution, salt concentration (ionic strength), desorption conditions (i.e. desorption solvent type and volume, and desorption time) on the pesticides extraction efficiencies were inquired using matrixed match method. Applying the optimum conditions, the linearity of 0.100–500.000 µg kg−1, LODs and LOQs in the range of 0.03–0.04 µg kg−1 and 0.1 µg kg−1 for the studied food samples were obtained. The repeatability (intra–day precision (n = 5)) of ≤ 2.0 % and reproducibility (inter–day precision, days = 5, n = 3) of ≤3.1 % and were appraise at three concentration levels (10, 50 and 100 μg kg−1 of each analyte). High relative recoveries of 90.0–99.3 % ascertained high potential of the presented method for complex matrix analysis. [ABSTRACT FROM AUTHOR]

• Organophosphorus pesticides degradation and in-situ phosphate recovery system was constructed. • The degradation efficiency of trichlorfon in this system surpassed 98% • Phosphorus from the degradation process was recovered in the form of vivianite with the overall recovery rate of 85.1%. • In this system, the toxicity of degradation byproduct was lower than trichlorfon, and iron in the photo-Fenton system is also recovered. • The recovered vivianite has great potential for water treatment. Efficient recovery and utilization of the generated phosphorus during the process of organophosphorus pesticides degradation is promising but still challenging. In this study, a photo-Fenton-crystallization sequential processes were developed to achieve the degradation of organophosphorus pesticides and simultaneous recovery/utilization of the generated phosphate. In this system, iron ions exhibited dual functionality: activator of the photo-Fenton reaction and crystallizing agent of the generated phosphate and the crystals obtained were proved to be vivianite by X-ray Diffraction and Scanning Electron Microscopy. The results showed that a trichlorfon degradation rate exceeding 90% and a vivianite yield of 85.1% was achieved. Parameters such as pH and the Fe-P ratio play pivotal roles in phosphorus recovery efficiency from wastewater. In addition, the toxicity of the degradation by-products was much less than that of trichlorfon by the Toxicity Estimation Software Tool. Additionally, the recovered vivianite exhibits advantageous catalytic properties to activate peroxymonosulfate for the degradation of different pollutants. This study provides a novel perspective for the treatment and utilization of organophosphorus pesticides. [ABSTRACT FROM AUTHOR]

• Fe 3 O 4 @Ag@COF based detection flow exhibits an excellent SERS performance. • COF endows Fe 3 O 4 @Ag@COF with a platform for enriching MTD molecules. • Fe 3 O 4 @Ag@COF with MTD molecules can be separated from complex matrix by magnetism. • The Raman peaks of COF can be employed as an internal standard for ratiometric SERS sensing. • The detection flow exhibited an ultra-low MTD detection of 8.3 × 10-5 mg/kg. As a typical organophosphorus pesticide widely utilized in agricultural production with its residue as enormous threat to human health and environment, methamidophos (MTD) has gained increasing attention in recent years, so, it is necessary to develop an effective strategy to detect MTD from complex matrix. Here, an efficient molecular enrichment and magnetic separation flow was constructed through Fe 3 O 4 @Ag@COF (covalent organic framework) for ratiometric SERS detection of MTD. Specifically, Fe 3 O 4 @Ag@COF is shown to have a high-density hot-spot region and optimal SERS performance by adjusting the particle size and addition volume of Fe 3 O 4 @Ag. COF endows Fe 3 O 4 @Ag@COF with a platform for enriching MTD molecules and isolating impurities, allowing the separation of Fe 3 O 4 @Ag@COF with MTD molecules from complex matrix by magnetism. More importantly, due to its natural core–shell structure, the Raman peaks of COF can be employed as an internal standard for ratiometric SERS sensing, thereby increasing its analysis accuracy and reliability. Under the optimal extraction method and solvent conditions, the developed detection flow exhibited a wide linear range from 10-4 M to 10-9 M and a low MTD detection limit of 8.3 × 10-5 mg/kg. Furthermore, the SERS sensor had excellent reproducibility and long-term stability with a low relative standard deviation (RSD). In practical application, this detection flow was tested for quantifying trace MTD in green tea samples, with recoveries of 89.54 % to 101.89 % and RSDs below 5 % (n = 5), comparable to the performance of gas chromatography mass spectrometry (GC–MS). [ABSTRACT FROM AUTHOR]

To address the potential hazards of organophosphorus pesticides (OPs) residues in tea, an electrochemiluminescence (ECL) aptasensor based on functionalized nanomaterials was constructed in this work. Firstly, gold nanoparticles (AuNPs) were attached on the surface of multi-walled carbon nanotubes (MWCNTs) by the constant potential electrodeposition to form a compound, and it was utilized to provide excellent immobilization sites for complementary DNA (cDNA). Subsequently, composite nanomaterials were synthesized by a one-pot method with aminated Luminol/silver nanoparticles@silica nanospheres (NH 2 -Luminol/Ag@SiO 2 NSs). Finally, NH 2 -Luminol/Ag@SiO 2 NSs was combined with a malathion aptamer (Apt) to obtain signal probes (SPs) for the construction of an aptasensor. The aptasensor had a wide linear range (1×10−3-1×103 ng/mL) and a low limit of detection (LOD) (0.3×10−3 ng/mL). It had the virtues of high sensitivity, wonderful stability and excellent specificity, which could be used for the detection of malathion residue in tea. The work provides a proven way for the construction of a rapid and ultrasensitive aptasensor with low-cost. [Display omitted] • NH 2 -Luminol/Ag@SiO 2 NSs was used to prepare the ECL aptasensors for the first time. • The ECL signal was amplified by a large number of loaded Luminol and AgNPs. • A signal-variable ECL aptasensor for detection of malathion in tea. [ABSTRACT FROM AUTHOR]

Designing efficient and rapid methods for the detection of organophosphorus pesticides (OPs) residue is a prerequisite to mitigate their negative health impacts. In this study, we propose the concept of an enzyme catalysis system-based hydrogel kit integrated with a smartphone detector for in-field screening of OPs. Here, we rapidly prepared phosphotriesterase hybrid nanoflowers (PTE-HNFs) using a self-assembly strategy by adding external energy and embedded the nanocomposite in sodium alginate (SA) hydrogel to construct a target-responsive hydrogel kit. The color response of the kit is induced by catalyzing methyl parathion (MP) to produce p-nitrophenol. For on-site quantification, the color variations of the portable kit are converted into digital information through a smartphone, which exhibits an applicable linear range towards OPs. The hydrogel sensing platform demonstrates a wide linear range (1–150 μM) and low detection limit (0.15 μM) for MP while maintaining high reliability, excellent long-term stability, and ease of operation. Overall, the PTE-HNFs-based SA hydrogel kit provides a useful strategy for simple and sensitive detection of MP and holds great potential for applications in detecting OPs in food and environmental water. [Display omitted] • A hydrogel test kit is fabricated for the monitoring of organophosphorus pesticides. • Hydrogel kit possess high anti-interference ability. • Smartphone combined with test kit for on-site monitoring of methyl parathion. • The test kit had been used in real samples with acceptable recovery. [ABSTRACT FROM AUTHOR]

—The development of sensitive analytical methods is of prime importance for the detection of pesticide residues on the surfaces of fruits and vegetables at extremely low concentrations. Here, we synthesized Ag-decorated three-dimensional ZnO nanoflowers (ZnO@Ag) composed of ultrathin nanosheets as surface-enhanced Raman spectroscopy (SERS) substrates. Combined with the finite-difference time-domain (FDTD) method, it is proven that the ultrathin nanosheets greatly improve the electromagnetic coupling between the two metal nanoparticles due to the high refractive index of ZnO and generate new "hot spots". The nanosheets also endow the incident light with multiple reflections to motivate the local electromagnetic field. The substrate presents high sensitivity and the enhancement factor was as high as 2.98 × 107 utilizing R6G as probe molecules. The detection concentration of thiram and malachite green (MG) solutions can reach 10−10 M and 10−9 M, respectively. For the real-life sample assays, the substrate can simultaneously detect the two pesticides on apple skin with high sensitivity. The research also reveals the importance of semiconductors toward the local electromagnetic field enhancement in noble metal-semiconductor substrates, benefiting the realization of highly sensitive SERS substrates and the wide application of the SERS technology in real-world scenarios. [Display omitted] • The ZnO nanosheets significantly enhance the electromagnetic coupling using FDTD. • The nanosheets endow incident light with multiply motivating the local field. • The enhancement factor of the SERS substrate is as high as 2.98 × 107. • The substrate can simultaneously detect thiram and MG with high sensitivity. [ABSTRACT FROM AUTHOR]

Diazinon is an organophosphorus pesticide widely used in agriculture and household pest control, and its use also poses several environmental and health hazards. In this study, we investigated the spatial and temporal distribution of diazinon in Baiyangdian, evaluated its potential ecological risk and toxicity to aquatic organisms based on RQ (Risk quotient) and TU (Toxic unit) analysis, and assessed the potential effects of diazinon accumulation on probiotics and pathogens based on statistical analysis of high-throughput sequencing data. The results showed that diazinon in Baiyangdian posed a low to moderate chronic risk to sediment-dwelling organisms and a low toxicity effect on aquatic invertebrates, which was mainly concentrated in October and human-intensive areas. Meanwhile, increases in sediment electrical conductivity (EC), amorphous iron oxides content and phenol oxidase activity favored diazinon accumulation in sediments, whereas the opposite was the case for sediment organic carbon, β-1,4-glucosidase, phosphatase, catalase and pH, suggesting that environmental indicators play a key role in the behavior and distribution of diazinon. In addition, diazinon in heavily contaminated areas seem to inhibit the rare probiotics (Bifidobacterium adolescentis and Serratia sp.), while promoted dominant pathogens (e.g., Burkholderia cenocepacia), which can lead to increased disease risk to humans and ecosystems, disruption of ecological balance and potential health problems. However, probiotic Streptomyces xiamenensis resist to diazinon would be a potential degrader for diazinon remove. In conclusion, this study unveiled the effects of diazinon pollution on wetland ecosystems, emphasizing ecological impacts and potential health concerns. In addition, the discovery of diazinon resistant probiotics provided new insights into wetland ecological restoration. [Display omitted] • Low to medium potential risk of diazinon (DIZ) in Baiyangdian sediments. • Absolute abundance of probiotic and pathogen was highest in DIZ contaminated areas. • DIZ may inhibit relative abundance of probiotics B.adolescentis and Serratia sp. • Probiotic S.xiamenensis resistant to DIZ maybe a potential degrader of DIZ. • DIZ may promote growth of dominant pathogens B.cenocepacia and others. [ABSTRACT FROM AUTHOR]

Designing an electrode that can generate abundant free radicals and 1O 2 , which can effectively degrade and detoxify organophosphorus pesticides (OPPs) through a co-oxidation pathway, is important. In this study, we prepared a electrode GO/MoS 2 @AS by supporting MoS 2 on alum sludge (AS) under graphene oxide (GO) nanoconfinement. The results show that the dominant role of 1O 2 at the cathode and •OH ads at the anode for degradation, in addition to the involvement of 1O 2 in the cathodic degradation mechanism, can be attributed to the abundant precursor •O 2 – and H 2 O 2. Furthermore, calculations using density functional theory and toxicity prediction of products show that the energy (∆ E) requirements of •OH free to break the C–O bond of the pyridine ring and phosphate group are higher than that required for 1O 2 , and this non-radical oxidation plays a key role in detoxification. In contrast, accelerating ring opening and oxidation processes are attributed to radical oxidation. Above all, the cathodic detoxification is more effective than anodic detoxification. Three prevalent OPPs, chlorpyrifos, glyphosate, and trichlorfon, were degraded in the GO/MoS 2 @AS system by over 90 %, with mineralization rates of 76.66 %, 85.46 %, and 82.18 %, respectively. This study provides insights into the co-oxidation degradation and detoxification mechanism mediated by 1O 2 and •OH free. [Display omitted] • Design an electrode to effectively degrade and detoxify organophosphorus pesticides. • Exceed 90 % removal efficiency and 73 % mineralization rate for three OPPs achieved. • The co-oxidation mechanism mediated by 1O 2 of cathode and •OH ads of anode. • The mineralization and detoxification are respectively due to radical and non-radical. [ABSTRACT FROM AUTHOR]

Organophosphorus pesticides (OPs), such as chlorpyrifos (CPF), are the most commonly used pesticides worldwide. Considering that OPs will eventually enter aquatic ecosystems due to runoff from agricultural lands, accidental leakage, and other unforeseen emergencies, monitoring water pollution of those substances is crucial for environmental protection and public health. In this study, Japanese medaka (Oryzias latipes) were exposed to CPF (0.03, 0.06, and 0.12 mg/L) for 6 h, and the time-series variations in their locomotor behavior and vocal traits were investigated. Compared with that measured before exposure, significantly changed locomotor behavior and vocal traits in Japanese medaka exposed to CPF could be observed at 4 h after exposure and thereafter, and the pattern of behavioral changes depends on the CPF concentrations. Exposure to CPF also changed the frequency-sound pressure level curve of Japanese medaka at 6 h after exposure, especially at 0.12 mg/L. Moreover, CPF exposure could significantly inhibit the acetylcholinesterase (AChE) activity in the brains and eyes of medaka, which exhibited significant correlations with the variation of locomotor behavioral and vocal traits. Considering that inhibiting the AChE activity is the primary mechanism underlying the neurobehavioral toxicity of all OPs, our finding suggested that simultaneously monitoring changes in the locomotor behavioral and vocal traits has a high potential to reflect the pollution of organophosphorus substances. [Display omitted] • CPF at 0.06 and 0.12 mg/L decreased motor activity and anxiety of Japanese medaka • CPF at 0.03 and 0.06 mg/L increased the pulse number of sound produced by medaka • CPF at 0.12 mg/L decreased pulse number and altered the acoustic spectrum of sound • CPF (0.03–0.12 mg/L) inhibited the AchE activity in fish brains and eyes within 6 h • Inhibited AchE activity associated with altered locomotor behavior and vocal traits [ABSTRACT FROM AUTHOR]

(a) Synthesis of Zr-BDC-MOF by solvothermal method, and (b) Electrochemical sensing of prepared Zr-BDC/GCE. [Display omitted] • Zr-BDC-MOF made by solvothermal method, resulting specific surface area (868 m2g−1) • Employed EIS to study non-electroactive OPPs' interaction with Zr-BDC-MOF/GCE. • LODs for malathion 3.6 nM, dimethoate 4.1 nM, chlorpyrifos 4.5 nM, monocrotophos 3.8 nM, and glyphosate 4.3 nM. • EIS showed Zr-BDC-MOF/GCE favors sulfur OPPs ((P = S), (P-S)) over P = O and other pesticides. Residues of pesticides found in fruits and vegetables pose a grave risk to organisms, potentially causing acute and chronic diseases when their levels surpass the maximum residual limits (MRLs) for human consumption. This study targeted to detect non-electroactive organophosphate pesticides (OPPs), including malathion, dimethoate, chlorpyrifos, monocrotophos, and glyphosate using a zirconium-terephthalic acid combined metal organic framework (Zr-BDC) by electrochemical impedance spectroscopy (EIS). Comprehensive analysis of the synthesized Zr-BDC showed an extensive specific surface area of 868 m2g−1. Nyquist plots and equivalent circuit models confirmed the higher adsorption of OPPs with P = S and P-S (malathion, dimethoate, chlorpyrifos) onto glassy carbon modified by Zr-BDC (Zr-BDC/GCE), in contrast to OPPs with P = O (monocrotophos, glyphosate, and non-OPPs). The Zr-BDC/GCE displayed a linear detection range of 5.0 nM to 70.0 μM, with limit of detections (LODs) of 3.6, 4.1, 4.5, 3.8, and 4.3 nM for malathion, dimethoate, chlorpyrifos, monocrotophos, and glyphosate respectively. The sensor exhibited notable recovery 91.0 – 98.6 % and RSDs 1.19 – 1.97 % (n = 3) when tested with real samples (apple and cabbage) and demonstrating substantial reproducibility and long-term stability. [ABSTRACT FROM AUTHOR]

Methyl paraoxon (MP) is a highly toxic, efficient and broad-spectrum organophosphorus pesticide, which poses significant risks to ecological environment and human health. Many detection methods for MP are based on the enzyme catalytic or inhibition effect. But natural biological enzymes are relatively expensive and easy to be inactivated with a short service life. As a unique tool of nanotechnology with enzyme-like characteristics, nanozyme has attracted increasing concern. However, a large proportion of nanozymes lack the intrinsic specificity, becoming a main barrier of constraining their use in biochemical analysis. Here, we use a one-pot reverse microemulsion polymerization combine the gold nanoclusters (AuNCs) with molecularly imprinted polymers (MIPs), polydopamine (PDA) and hollow CeO 2 nanospheres to synthesize the bright red-orange fluorescence probe (CeO 2 @PDA@AuNCs-MIPs) with high phosphatase-like activity for selective detection of MP. The hollow structure possesses a specific surface area and porous matrix, which not only increases the exposure of active sites but also enhances the efficiency of mass and electron transport. Consequently, this structure significantly enhances the catalytic activity by reducing transport distances. The introduced MIPs provide the specific recognition sites for MP. And Ce (III) can excite aggregation induced emission of AuNCs and enhance the fluorescent signal. The absolute fluorescence quantum yield (FLQY) of CeO 2 @PDA@AuNCs-MIPs (1.41 %) was 12.8-fold higher than that of the GSH-AuNCs (0.11 %). With the presence of MP, Ce (IV)/Ce (III) species serve as the active sites to polarize and hydrolyze phosphate bonds to generate p -nitrophenol (p-NP), which can quench the fluorescent signal through the inner-filter effect. The as-prepared CeO 2 @PDA@AuNCs-MIPs nanozyme-based fluorescence method for MP detection displayed superior analytical performances with wide linearities range of 0.45–125 nM and the detection limit of 0.15 nM. Furthermore, the designed method offers satisfactory practical application ability. The developed method is simple and effective for the in-field detection. [Display omitted] • AuNCs coated on molecularly imprinted hollow CeO 2 nanospheres was developed. • The fluorescence probe (CeO 2 @PDA@AuNCs-MIPs) with high phosphatase-like activity. • Ce (III) could excite aggregation induced emission of AuNCs and enhanced the fluorescent signal. • A highly selective fluorescence assay of MP was developed. • The proposed sensor presented a good sensitivity in real samples detection. [ABSTRACT FROM AUTHOR]