A molecularly imprinted ratiometric fluorescent sensor for visual detection of 1-naphthol based on fluorescence-enhanced CdTeS QDs via APTES modification.

CdTeS quantum dots (CdTeS QDs) were synthesized using the hydrothermal method and subsequently modified with (3-aminopropyl)triethoxysilane (APTES). This modification resulted in a significant enhancement of the fluorescence intensity, which was observed to be five times stronger than that of unmodified CdTeS QDs at 597 nm. Only after the fluorescence enhancement by APTES modification, the material showed a response to 1-naphthol (1-NP). Based on this, the molecularly imprinted polymers (MIPs) with ratiometric fluorescence were developed for the detection of 1-NP, that is, the synthetic raw material and the metabolite of the pesticide carbaryl. Under the excitation of 365 nm UV, the bright orange-red fluorescence (597 nm) of CdTeS QDs encapsulated in MIPs was quenched by 1-NP in the suspension, and 1-NP showed a gradually increasing blue emission (460 nm) with the increase of its concentration. This sensor has a good linear relationship between fluorescence intensity ratio (F460/F597) and 1-NP concentration (C1-NP) in a large concentration range (6.0-140.0 µM, LOD=0.45 µM, RSD<4.41%). It exhibits a visible fluorescence change from orange-red to blue-purple. Excellent recoveries in real samples were obtained by simulating carbaryl metabolism and demonstrated its potential in detection of 1-NP and carbaryl.

Metabolic engineering of Pseudomonas bharatica CSV86T to degrade Carbaryl (1-naphthyl-N-methylcarbamate) via the salicylate-catechol route.

Pseudomonas bharatica CSV86T displays the unique property of preferential utilization of aromatic compounds over simple carbon sources like glucose and glycerol and their co-metabolism with organic acids. Well-characterized growth conditions, aromatic compound metabolic pathways and their regulation, genome sequence, and advantageous eco-physiological traits (indole acetic acid production, alginate production, fusaric acid resistance, organic sulfur utilization, and siderophore production) make it an ideal host for metabolic engineering. Strain CSV86T was engineered for Carbaryl (1-naphthyl-N-methylcarbamate) degradation via salicylate-catechol route by expression of a Carbaryl hydrolase (CH) and a 1-naphthol 2-hydroxylase (1NH). Additionally, the engineered strain exhibited faster growth on Carbaryl upon expression of the McbT protein (encoded by the mcbT gene, a part of Carbaryl degradation upper operon of Pseudomonas sp. C5pp). Bioinformatic analyses predict McbT to be an outer membrane protein, and Carbaryl-dependent expression suggests its probable role in Carbaryl uptake. Enzyme activity and protein analyses suggested periplasmic localization of CH (carrying transmembrane domain plus signal peptide sequence at the N-terminus) and 1NH, enabling compartmentalization of the pathway. Enzyme activity, whole-cell oxygen uptake, spent media analyses, and qPCR results suggest that the engineered strain preferentially utilizes Carbaryl over glucose. The plasmid-encoded degradation property was stable for 75-90 generations even in the absence of selection pressure (kanamycin or Carbaryl). These results indicate the utility of P. bharatica CSV86T as a potential host for engineering various aromatic compound degradation pathways.IMPORTANCEThe current study describes engineering of Carbaryl metabolic pathway in Pseudomonas bharatica CSV86T. Carbaryl, a naphthalene-derived carbamate pesticide, is known to act as an endocrine disruptor, mutagen, cytotoxin, and carcinogen. Removal of xenobiotics from the environment using bioremediation faces challenges, such as slow degradation rates, instability of the degradation phenotype, and presence of simple carbon sources in the environment. The engineered CSV86-MEC2 overcomes these disadvantages as Carbaryl was degraded preferentially over glucose. Furthermore, the plasmid-borne degradation phenotype is stable, and presence of glucose and organic acids does not repress Carbaryl metabolism in the strain. The study suggests the role of outer membrane protein McbT in Carbaryl transport. This work highlights the suitability of P. bharatica CSV86T as an ideal host for engineering aromatic pollutant degradation pathways.

Investigating open access new approach methods (NAM) to assess biological points of departure: A case study with 4 neurotoxic pesticides.

Open access new approach methods (NAM) in the US EPA ToxCast program and NTP Integrated Chemical Environment (ICE) were used to investigate activities of four neurotoxic pesticides: endosulfan, fipronil, propyzamide and carbaryl. Concordance of in vivo regulatory points of departure (POD) adjusted for interspecies extrapolation (AdjPOD) to modelled human Administered Equivalent Dose (AEDHuman) was assessed using 3-compartment or Adult/Fetal PBTK in vitro to in vivo extrapolation. Model inputs were from Tier 1 (High throughput transcriptomics: HTTr, high throughput phenotypic profiling: HTPP) and Tier 2 (single target: ToxCast) assays. HTTr identified gene expression signatures associated with potential neurotoxicity for endosulfan, propyzamide and carbaryl in non-neuronal MCF-7 and HepaRG cells. The HTPP assay in U-2 OS cells detected potent effects on DNA endpoints for endosulfan and carbaryl, and mitochondria with fipronil (propyzamide was inactive). The most potent ToxCast assays were concordant with specific components of each chemical mode of action (MOA). Predictive adult IVIVE models produced fold differences (FD) < 10 between the AEDHuman and the measured in vivo AdjPOD. The 3-compartment model was concordant (i.e., smallest FD) for endosulfan, fipronil and carbaryl, and PBTK was concordant for propyzamide. The most potent AEDHuman predictions for each chemical showed HTTr, HTPP and ToxCast were mainly concordant with in vivo AdjPODs but assays were less concordant with MOAs. This was likely due to the cell types used for testing and/or lack of metabolic capabilities and pathways available in vivo. The Fetal PBTK model had larger FDs than adult models and was less predictive overall.

Hinge-like paper-based dual-channel enzyme-free ratiometric fluorescent microfluidic platform for simultaneous visual detection of carbaryl and glyphosate.

On-site multi-pesticide residues detection is particularly urgent and challenging. Here, we fabricated an enzyme-free ratiometric fluorescent detection system in combination with a hinge-like dual-channel 3D microfluidic paper analytical device (3D µPAD) for simultaneous visual detection of carbaryl and glyphosate. Blue-emission 1-naphthol (Em. 470 nm) was hydrolyzed from carbaryl, while yellow-emission 2,3-diaminophenazine (Em. 570 nm) was produced with the aid of Cu2+ for glyphosate sensing. Inner-filter effect between 1-naphthol or 2,3-diaminophenazine and green-emission carbon dots (Em. 510 nm) realized two ratiometric fluorescent detection systems. Remarkable color variation of green-blue for carbaryl (50.00-1100 µΜ) and yellow-green for glyphosate (5.00-600 µΜ) were observed on a dual-channel 3D µPAD without crosstalk. Their detection limits were 1.11 and 0.63 µΜ, respectively. The strategy realized simultaneous visual detection of carbaryl and glyphosate in food/herbal with excellent accuracy (spiked recoveries, 91.00-107.2%), high precision (RSD ≤ 8.43%), and superior selectivity.

Cobalt ferrite/semiconducting single-walled carbon nanotubes based field-effect transistor for determination of carbamate pesticides.

Carbaryl and carbofuran are the carbamate pesticides which have been widely used worldwide to control insects in crops and house. If the pesticides entered in to the food products and drinking water, they could cause serious health effects in humans. Therefore, the development of a rapid, simple, sensitive and selective analytical device for on-site detection of carbamates is crucial to evaluate food and environmental samples. Recently, semiconducting single-walled carbon nanotube-based field effect transistors (s-SWCNT/FETs) have shown several advantages such as high carrier mobility, good on/off ratio, quasi ballistic electron transport, label-free detection and real-time response. Herein, cobalt ferrite (CFO) nanoparticles decorated s-SWCNTs have been prepared and used to bridge the source and drain electrodes. As-prepared CFO/s-SWCNT/FET had been used for the non-enzymatic detection of carbaryl and carbofuran. When used as a sensing platform, the CFO/s-SWCNT hybrid film exhibited high sensitivity, and selectivity with a wide linear range of detection from 10 to 100 fMand the lowest limit of detections for carbaryl (0.11 fM) and carbofuran (0.07 fM) were estimated. This sensor was also used to detect carbaryl in tomato and cabbage samples, which confirmed its practical acceptance. Such performance may be attributed to the oxidation of carbamates by potent catalytic activity of CFO, which led to the changes in the charge transfer reaction on the s-SWCNTs/FET conduction channel. This work presents a novel CFO/s-SWCNT based sensing system which could be used to quantify pesticide residues in food samples.

Preparation of biochar-based surface molecularly imprinted polymers and evaluation of their selective adsorption and removal of carbaryl from rice and corn.

The residue of carbaryl in food is a threat to human health. In this study, activated soybean shell biochar (A-SBC) was used as a carrier, methacrylic acid (MAA) was used as a functional monomer, and carbaryl was used as a template molecule to synthesize the activated biochar surface molecularly imprinted polymer (A-SBC@MIP). The synthesized A-SBC@MIP was characterized by SEM, FT-IR, XRD and XPS techniques, and then applied as adsorbent for carbaryl removal. The adsorption capacity of A-SBC@MIP for carbaryl was 8.6 mg‧g-1 and the imprinting factor was 1.49 at the optimum ionic strength and pH. The kinetic and isothermal data indicated that it had fast mass transfer rate and high binding capacity(Qmax=47.9 mg‧g-1). A-SBC@MIP showed good regenerative properties and the adsorption of carbaryl was excellent in its structural analogues. A solid-phase extraction (SPE) column composed of A-SBC@MIP was developed for the detection of rice and corn under optimized conditions, with recoveries of 93-101% for the spiked carbaryl. The limit of detection (LOD) of the method was 3.6 µg‧kg-1 with good linearity (R2=0.994) in the range of 0.01-5.00 mg‧L-1. The results show that the developed MIPs-SPE can enrich carbaryl from food samples as a specific and cost-effective method.

Au nanogap SERS substrate for the carbaryl pesticide determination in juice and milk using chemomterics.

Conventional spectroscopic methods like IR, and Raman are not very effective at detecting low levels of pesticides or harmful chemicals in food matrices. A quick, highly accurate approach that can identify pesticides present in different food products at lower levels must be developed in order to address this problem and ensure food safety. In this study, a highly sensitive and uniform wafer-scale Au nanogap surface-enhanced Raman spectroscopy (SERS) substrate was used for the quantitative analysis of carbaryl pesticide levels in standard solution, mango juice, and milk samples using chemometrics. Carbaryl was detected up to 3 ppb concentration levels for all three group of samples. However, due to the higher sensitivity, uniformity, and enhancement factors of the SERS substrate used in this investigation, the limit of detection (LOD) values for the standard solution, mango juice, and milk were 0.37 ppb, 0.57 ppb, and 0.15 ppb at 1380 cm-1, 1380 cm-1, and 1364 cm-1 wavenumber ranges. In order to predict different carbaryl concentrations (1, 2, 3, 4, and 5 ppb), the variable importance in projection (VIP) method combined with partial least squares regression (PLSR) and attained the coefficient of determination (R2) values of 0.994, 0.989, and 0.978 along with minimum root mean square error (RMSE) values of 0.112, 0.190, and 0.278 ppb for the prediction datasets. Furthermore, PLS-DA was able to distinguish between pure and adulterated samples with the highest classification accuracy of 100 % for a standard solution, and mango juice and 94.4 % for milk samples. Considering this, we can conclude that the SERS Au Nanogap substrate can rapidly and effectively detect carbaryl pesticides quantitatively and qualitatively in mango juice and milk.

First meta-analysis study of cholinesterase inhibition in experimental animals by organophosphate or carbamate insecticides under the influence of diphenhydramine.

Background and Aim: Diphenhydramine is an H1-antihistamine that counteracts the toxic effects of organophosphate and carbamate insecticides that inhibit cholinesterase (ChE) activity. This meta-analysis aimed to investigate the effects of diphenhydramine on ChE inhibition induced by these insecticides in the plasma, erythrocytes, or whole brain of experimental animals. Materials and Methods: A data search was performed on erythrocyte, plasma, and brain ChE inhibition caused by organophosphate and carbamate insecticides in experimental animals (mice, rats, and chicks) treated with the antihistamine diphenhydramine in accordance with preferred reporting items for systematic reviews and meta-analysis, which was done by the two-group random-effects model meta-analysis. The meta-analysis included 18 records extracted from six studies that, appeared from 1996 to 2022. Results: Using the random-effects model, a two-group meta-analysis revealed that the combined effect size (ChE inhibition) was significantly more favorable in the control group than in the diphenhydramine intervention, as shown by a forest plot. The combined effect size (standardized mean difference) was 0.67, with a standard error of 0.3, a lower limit of 0.04, and an upper limit of 1.29 (p = 0.025). The heterogeneity was moderate, as I2 of the combined effect size was 74%, with a significant Cochrane Q-test result (Q = 65, p < 0.0001). Subgroup analysis indicated that, with brain ChE inhibition, the heterogeneity (I2) became 5%, which was lower than ChE inhibition in plasma (84%) and erythrocytes (78%). No publication bias was identified using the funnel plot and Egger's test. Conclusion: This meta-analysis suggests that, in addition to its documented antidotal action against ChE-inhibiting insecticides, diphenhydramine can also reduce the extent of ChE inhibition, especially in the brain, which is the main site of toxicity of these insecticides. There is a need for additional studies to assess such enzyme inhibition in different parts of the brain.

Deashed Wheat-Straw Biochar as a Potential Superabsorbent for Pesticides.

Biochar activation methods have attracted extensive attention due to their great role in improving sorptive properties of carbon-based materials. As a result, chemically modified biochars gained application potential in the purification of soil and water from xenobiotics. This paper describes changes in selected physicochemical properties of high-temperature wheat-straw biochar (BC) upon its deashing. On the pristine and chemically activated biochar (BCd) retention of five pesticides of endocrine disrupting activity (carbaryl, carbofuran, 2,4-D, MCPA and metolachlor) was studied. Deashing resulted in increased sorbent aromaticity and abundance in surface hydroxyl groups. BCd exhibited more developed meso- and microporosity and nearly triple the surface area of BC. Hydrophobic pesticides (metolachlor and carbamates) displayed comparably high (88-98%) and irreversible adsorption on both BCs, due to the pore filling, whereas the hydrophilic and ionic phenoxyacetic acids were weakly and reversibly sorbed on BC (7.3 and 39% of 2,4-D and MCPA dose introduced). Their removal from solution and hence retention on the deashed biochar was nearly total, due to the increased sorbent surface area and interactions of the agrochemicals with unclogged OH groups. The modified biochar has the potential to serve as a superabsorbent, immobilizing organic pollutant of diverse hydrophobicity from water and soil solution.

Waste self-heating bag derived iron-based composite with abundant oxygen vacancies for highly efficient Fenton-like degradation of micropollutants.

In this study, iron-rich waste self-heating bag was reutilized as the raw material to prepare oxygen vacancies (OV) functionalized iron-based composite (iron oxide (Fe3O4)-carbon-vermiculite, viz. OV-ICV), which exhibited excellent performance in the Fenton-like degradation of micropollutants via peroxydisulfate (PDS) activation. Above 95% of 1.0 mg/L carbaryl (CB) was efficiently eliminated in the presence of 0.1 g/L of OV-ICV and 0.5 mmol/L of PDS over a wide pH range of 3-10 within 30 min. Besides, OV-ICV also showed acceptable adaptability, stability, and renewability. Imbedding OV into Fe3O4 structure significantly generated more active iron sites and localized electrons, promoted the charge transfer ability, and assisted the redox cycle of ≡Fe(III)/≡Fe(II) for PDS activation. Mechanism investigation demonstrated that superoxide radicals (O2•-) derived from the activation of molecular oxygen mediated the generation of H2O2, and both of them further enhanced the formation of more sulfate radicals (SO4•-) and hydroxyl radicals (•OH), which led to the efficient degradation and mineralization of CB. Furthermore, the degradation pathways of CB were proposed based on the intermediates identification. This work lays a foundation for the rational reutilization of iron-containing wastes modified with defect engineering in heterogeneous Fenton-like catalysis for the remediation of micropollutants wastewater.

Seed treatment with chlorantraniliprole and carbaryl mixture for managing fall armyworm on maize: systemic synergism, control efficiency and synergistic mechanism.

BACKGROUND: Fall armyworm (Spodoptera frugiperda) is one of the major invasive pests in China, and has been widely controlled by labor-intensive foliar sprays of agrochemicals in maize (Zea mays L.). RESULTS: Systemic bioassay showed that mixtures of chlorantraniliprole (Chlor) and carbaryl (Carb) had dramatically synergistic effect on toxicity to S. frugiperda. Particularly, a mixture of Chlor with Carb at a mass ratio of 2:1 (MCC) exhibited the highest toxicity to S. frugiperda. Therefore, seed treatment of Chlor mixed with Carb was studied as a simple, accurate, efficient and low-cost control technology. Our results showed that MCC treatment shortened the median lethal time and 90% lethal time to S. frugiperda compared to Chlor- and Carb-alone treatments. Meanwhile, smaller leaf consumption by S. frugiperda was recorded under MCC treatment compared to Chlor- and Carb-alone treatments. In field trial, maize-seed treatment with MCC showed efficacy up to 39 days post-emergence in preventing S. frugiperda foliar damage at a low infestation pressure. Moreover, chemical quantification by ultrahigh-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) showed that Chlor residues were more absorbed and concentrated in maize leaves of MCC treatment, compared to that of Chlor-alone treatment. CONCLUSION: These results suggested that seed treatment with MCC can be applied to increase the control efficacy and reduce the cost of Chlor-alone treatment for controlling S. frugiperda. The present study provided evidence of an enhanced translocation and accumulation of Chlor residues in maize leaves under MCC treatment, which likely contributed to a synergistic effect against S. frugiperda. © 2022 Society of Chemical Industry.

Head lice: an inexpensive bioassay for use as guidance for healthcare workers monitoring treatment failures for insecticide resistance (1994-1999).

Head lice, Pediculus humanus capitis De Geer (Psocodea: Pediculidae) that failed to respond to pyrethroid insecticide-based treatment products were first identified in London and Cambridge, UK, in 1993 after which reports of treatment failure arose throughout the UK. There was a need amongst healthcare workers for a rapid detection method for resistance that could be used at the community level. A laboratory service was set up so that health professionals could send lice by overnight post for bioassay testing for resistance. In addition, test kits were provided so that testing could either be conducted on site or lice could be shipped to the laboratory on pre-treated test papers so that insecticide exposure could proceed while lice were in transit to the laboratory. Between 1994 and 1999, over 350 samples from 145 locations were tested and during this time populations of lice resistant to pyrethroids, malathion, and carbaryl were identified from all parts of the country, both urban and rural. In some areas, lice were only resistant to one of the insecticides available but in other places lice showed tolerance to all three insecticides used at the time.

Synergistic effects of structural, crystalline, and chemical defects on the photocatalytic performance of Y-doped ZnO for carbaryl degradation.

In this study, a photocatalytic material consisting of ZnO and yttrium-doped ZnO (YZO) nanoparticles was obtained via a facile precipitation conducted under ambient pressure whereby crystalline ZnO was successfully doped with yttrium. YZO had a hexagonal wurtzite polycrystalline structure with smaller crystal and grain sizes than ZnO, which in turn meant larger specific surface area and pore volume. Chemical defects were also produced, which facilitated photocatalytic activity, because such defects can act as reaction centers. The optical band gap magnitude and the diamagnetic nature of YZO were also determined. The structural, crystalline, and chemical defects of YZO synergistically enhanced the photocatalytic degradation of carbaryl; indeed, the kinetic rate constant of this reaction catalyzed by YZO was 11.17 × 10-2 min-1 under natural sunlight irradiation, higher than the value measured for ZnO (8.68 × 10-2 min-1). Evidence thus indicates that yttrium-doping effectively modified some properties of ZnO nanoparticles so that YZO nanoparticles proved a suitable photocatalytic material for carbaryl degradation.

Phytoextraction Potential of Sunn Hemp, Sunflower, and Marigold for Carbaryl Contamination: Hydroponic Experiment.

The phytoextraction ability and responses of sunn hemp, sunflower, and marigold plants were investigated toward carbaryl insecticide at 10 mg L-1 and its degradative product (1-naphthol). All test plants exhibited significant carbaryl removal capability (65-93%) with different mechanisms. Marigold had the highest translocation factor, with carbaryl taken up, translocated and accumulated in the shoots, where it was biotransformed into 1-naphthol. Consequently, marigold had the least observable toxicity symptoms caused by carbaryl and the highest bioconcentration factor (1848), indicating its hyperaccumulating capability. Sunflower responded to carbaryl exposure differently, with the highest carbaryl accumulation (8.7 mg kg-1) in roots within 4 days of cultivation, leading to a partial toxicity effect. Sunn hemp exhibited severe toxicity, having the highest carbaryl accumulation (91.7 mg kg-1) that was biotransformed to 1-naphthol in the sunn hemp shoots. In addition, the different models were discussed on plant hormone formation in response to carbaryl exposure.

Structural and Optical Properties of Graphene Quantum Dots-Polyvinyl Alcohol Composite Thin Film and Its Potential in Plasmonic Sensing of Carbaryl.

In this study, graphene quantum dots (GQDs) and polyvinyl alcohol (PVA) composite was prepared and then coated on the surface of gold thin film via the spin coating technique. Subsequently, Fourier transform infrared spectroscopy (FT-IR), atomic force microscopy (AFM), and ultraviolet-visible spectroscopy (UV-Vis) were adopted to understand the structure, surface morphology, and optical properties of the prepared samples. The FT-IR spectral analysis revealed important bands, such as O-H stretching, C=O stretching, C-H stretching, and O=C=O stretching vibrations. The surface roughness of the GQDs-PVA composite thin film was found to be increased after exposure to carbaryl. On the other hand, the optical absorbance of the GQDs-PVA thin film was obtained and further analysis was conducted, revealing a band gap Eg value of 4.090 eV. The sensing potential of the thin film was analyzed using surface plasmon resonance (SPR) spectroscopy. The findings demonstrated that the developed sensor's lowest detection limit for carbaryl was 0.001 ppb, which was lower than that previously reported, i.e., 0.007 ppb. Moreover, other sensing performance parameters, such as full width at half maximum, detection accuracy, and signal-to-noise ratio, were also investigated to evaluate the sensor's efficiency.

Development of a Sensitive and Fast Determination Method for Trace Carbaryl Residues in Food Samples Based on Magnetic COF (TpPa-NH2)@Fe3O4 Nanoparticles and Fluorescence Detection.

Developing a simple and effective method for measuring carbaryl residues in food is urgent due to its widespread use and the associated health risks in agriculture, as well as various defects in existing detection techniques. The COF (TpPa-NH2)@Fe3O4 nanocomposite (amino modification) was synthesized via a two-step method and used as an adsorbent for the extraction of carbaryl from food samples in this study. The results indicated that COF (TpPa-NH2)@Fe3O4 can rapidly and successfully capture carbaryl directly from samples via π-π stacking and hydrophobic interactions, achieving maximum adsorption within 5 min under a small adsorbent quantity using a fluorescence spectrophotometer. Under the optimized conditions, carbaryl exhibited good linearity in the range of 0.2-120 µg·kg-1, and the limit of detection was 0.012 µg·kg-1. The recoveries of the samples were 96.0-107.4%. This method has broad application prospects for the monitoring of carbaryl in food.

A Novel Paper-Based Electrochemical Biosensor Based on N,O-Rich Covalent Organic Frameworks for Carbaryl Detection.

A new N,O-rich covalent organic framework (COFDHNDA-BTH) was synthesized by an amine-aldehyde condensation reaction between 2,6-dialdehyde-1,5-dihydroxynaphthalene (DHNDA) and 1,3,5-phenyltriformylhydrazine (BTH) for carbaryl detection. The free NH, OH, and C=O groups of COFDHNDA-BTH not only covalently couples with acetylcholinesterase (AChE) into the pores of COFDHNDA-BTH, but also greatly improves the catalytic activity of AChE in the constrained environment of COFDHNDA-BTH's pore. Under the catalysis of AChE, the acetylthiocholine (ATCl) was decomposed into positively charged thiocholine (TCl), which was captured on the COFDHNDA-BTH modified electrode. The positive charges of TCl can attract anionic probe [Fe(CN)6]3-/4- on the COFDHNDA-BTH-modified electrode to show a good oxidation peak at 0.25 V (versus a saturated calomel electrode). The carbaryl detection can inhibit the activity of AChE, resulting in the decrease in the oxidation peak. Therefore, a turn-off electrochemical carbaryl biosensor based on a flexible carbon paper electrode loaded with COFDHNDA-BTH and AChE was constructed using the oxidation peak of an anionic probe [Fe(CN)6]3-/4- as the detection signal. The detection limit was 0.16 µM (S/N = 3), and the linear range was 0.48~35.0 µM. The sensor has good selectivity, repeatability, and stability, and has a good application prospect in pesticide detection.

Biosensor Based on Covalent Organic Framework Immobilized Acetylcholinesterase for Ratiometric Detection of Carbaryl.

A ratiometric electrochemical biosensor based on a covalent organic framework (COFThi-TFPB) loaded with acetylcholinesterase (AChE) was developed. First, an electroactive COFThi-TFPB with a two-dimensional sheet structure, positive charge and a pair of inert redox peaks was synthesized via a dehydration condensation reaction between positively charged thionine (Thi) and 1,3,5-triformylphenylbenzene (TFPB). The immobilization of AChE on the positively charged electrode surface was beneficial for maintaining its bioactivity and achieving the best catalytic effect; therefore, the positively charged COFThi-TFPB was an appropriate support material for AChE. Furthermore, the COFThi-TFPB provided a stable internal reference signal for the constructed AChE inhibition-based electrochemical biosensor to eliminate various effects which were unrelated to the detection of carbaryl. The sensor had a linear range of 2.2-60 µM with a detection limit of 0.22 µM, and exhibited satisfactory reproducibility, stability and anti-interference ability for the detection of carbaryl. This work offers a possibility for the application of COF-based materials in the detection of low-level pesticide residues.

Integrated adsorption and biological removal of the emerging contaminants ibuprofen, naproxen, atrazine, diazinon, and carbaryl in a horizontal tubular bioreactor.

Groundwater and surface water bodies may have contaminants from urban, industrial, or agricultural wastewater, including emerging contaminants (ECs) or micropollutants (MPs). Frequently, they are not efficiently removed by microbial action due to their minimal concentration in water and the low microbiota affinity for complex compounds. This work developed a process allowing the adsorption of contaminants and their simultaneous biodegradation using horizontal tubular fixed-bed biofilm reactors (HTR). Each HTR has two zones: an equalizer-aerator of the incoming liquid flow and a fixed bed zone. This zone was packed with a mixed support material consisting of granular bio-activated carbon (Bio-GAC) and porous material that increases the bed permeability, thus decreasing the pressure drop. Five microbial communities were acclimated and immobilized in granular activated carbon (GAC) to obtain different specialized Bio-GAC particles able to remove the micropollutants ibuprofen, naproxen, atrazine, carbaryl, and diazinon. The Bio-GAC particles were transferred to HTRs continuously run in microaerophilia at several MPs loading rates. Under these conditions, the removal efficiencies of MPs, except atrazine and carbaryl, were around 100.

Electrochemical Synthesis of Reduced Graphene Oxide/Gold Nanoparticles in a Single Step for Carbaryl Detection in Water.

In this study, an in situ synthesis approach based on electrochemical reduction and ion exchange was employed to detect carbaryl species using a disposable, screen-printed carbon electrode fabricated with nanocomposite materials. Reduced graphene oxide (rGO) was used to create a larger electrode surface and more active sites. Gold nanoparticles (AuNPs,) were incorporated to accelerate electron transfer and enhance sensitivity. A cation exchange Nafion polymer was used to enable the adhesion of rGO and AuNPs to the electrode surface and speed up ion exchange. Cyclic voltammetry (CV), energy dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS), electrical impedance spectroscopy (EIS), atomic force microscopy (AFM) and scanning electron microscopy (SEM) were performed to study the electrochemical and physical properties of the modified sensor. In the presence of differential pulse voltammetry (DPV), an rGO/AuNP/Nafion-modified electrode was effectively used to measure the carbaryl concentration in river and tap water samples. The developed sensor exhibited superior electrochemical performance in terms of reproducibility, stability, efficiency and selectivity for carbaryl detection with a detection limit of 0.2 µM and a concentration range between 0.5µM and 250 µM. The proposed approach was compared to capillary electrophoresis with ultraviolet detection (CE-UV).