Zr-based metalloporphyrin MOF probe for electrochemical detection of parathion-methyl.

An electrochemical (EC) sensor based on metalloporphyrin metal-organic framework (MOF) for the detection of parathion-methyl (PM) has been developed. The prepared MOF-525(Fe) exhibits great signal enhancement toward the electrochemical detection of PM owing to its unique structural properties and electrochemical activities. Under optimal experimental conditions, the as-prepared MOF-525(Fe) based EC sensor exhibited excellent PM sensing performance with a wide linear detection range (0.1 µM-100 µM) and low limit of detection (LOD, 1.4 nM). Compared to its corresponding Fe metalloporphyrin (linker), MOF-525(Fe) exhibited a superior sensitivity (28.31 µA cm-2·µM-1), which is 3.7 times higher than the sensitivity of FeTCPP linker (7.56 µA cm-2·µM-1) towards PM. The improved performance is associated with the high specific surface area and the large pore channels of MOF-525(Fe) facilitating a better interaction between PM and the Fe metalloporphyrin active sites, especially in the lower concentration range. Moreover, a possible affinity of the PM molecules toward Zr6 clusters may also contribute to the selective enrichment of PM on MOF-525(Fe). This EC sensor further demonstrated high selectivity in the presence of interfering molecules. The recovery results further confirm accurate PM sensing in actual samples, which suggests promising applications for the rapid detection of environmental organophosphates by metalloporphyrin MOFs.

Enzyme-linked immunoassay for simultaneous detection of methyl parathion and sibutramine in apple cider vinegar.

Methyl parathion, a highly toxic, efficient, and persistent organophosphorus pesticide, is widely used in China. Sibutramine, a non-amphetamine central nervous system depressant, helps lose weight by disrupting hormone regulation, stimulating sympathetic nerves, and suppressing appetite. However, some unethical businesses fail to properly handle raw materials in foods like apple cider vinegar, leading to residual methyl parathion in apples or illegal excessive addition of sibutramine. Therefore, it is imperative to develop an immunoassay for the rapid detection of methyl parathion and sibutramine. The corresponding two haptens were prepared and coupled with the carrier proteins according to methyl parathion-sulfur-bovine serum protein (BSA)/chicken ovalbumin (OVA)-sibutramine (20 : 1 : excess, 15 : 1 : excess, 10 : 1 : excess, and 5 : 1 : excess), and sibutramine-BSA/OVA-methyl parathion (20 : 1 : excess, 10 : 1 : excess: 5 : 1 : excess, and 0 : 1 : excess). The result shows that the inhibition rate of the antibody obtained by methyl parathion-BSA/OVA-sibutramine (20 : 1 : excess) was higher than that of sibutramine-BSA/OVA-methyl parathion, which was 67.93%, and the concentration of methyl parathion was 8.65 ng mL-1 at this inhibition rate. Thus, methyl parathion-BSA/OVA-sibutramine (8.65 : 1 : excess) and the corresponding antibodies were selected for subsequent method establishment. By changing the concentration of the coating and antibody, the inhibition rate was found when the coating was 0.125 ng mL-1 and the antibody was diluted 4000 times. The antibody was used to develop a standard curve for the detection of sibutramine at the half-maximum inhibitory concentration (IC50) is 4.59 ng mL-1, the limit of detection (IC10) is 2.21 ng mL-1, the detection range is 2.89 to 7.28 ng mL-1, methyl p-phosphorus at the half-maximum inhibitory concentration (IC50) is 15.34 ng mL-1, the limit of detection (IC10) is 0.42 ng mL-1, the detection range is ng mL-1. Under these conditions, the recovery rate was between 88% and 102%, within reasonable limits, indicating the successful establishment of a rapid enzyme-linked ELISA assay.

Synergistic Manganese Cobalt Phosphide core-shell for the Electrochemical Detection of Methyl Parathion in Food Sample.

The development of a robust electrocatalyst for the electrochemical sensor for hazardous pesticides will reduce its effects on the ecosystem. Herein, we synthesized the robust manganese cobalt phosphide (MnCoP) - Core-shell as an electrochemical sensor for the determination of hazardous pesticide methyl parathion (MP). The MnCoP- Core-shell was prepared with the sustainable self-template route can help with the larger surface area. The Core-shell structure of MnCoP possesses a higher active surface area which increases the electrocatalytic performance and is utilized to improve the electrochemical MP reduction with the synergism of the core and shell structure. Remarkably, it realizes the higher sensitivity (0.014 µA µM-1 cm-2) of MnCoP- Core-shell/GCE achieves towards MP with lower limit of detection (LoD 50 nM) and exceptional recovery rate of MP in vegetable samples are achieved with the differential pulse voltammetry (DPV) technique. The MnCoP- Core-shell electrode reserved their superior electrochemical performances with high reproducibility and repeatability. This prominent activity of the MnCoP core-shell towards the MP in real sample analysis, makes it a promising electrochemical sensor for the detection of MP.

[Development of a whole-cell biosensor for detecting organophosphorus pesticide methyl parathion in the farmland soil].

The evaluation of the bioavailability of pollutants in soil is crucial to accurately assess the pollution risk, and whole-cell biosensor is one of the important tools for such evaluation. This study aimed to develop a novel whole-cell biosensor for the detection of methyl parathion in soil using. First, a whole-cell biosensor was constructed by the screened methyl parathion hydrolase mpd gene, the existing specific induction element pobR, and the pUC19 plasmid skeleton. Then, the detection method of methyl parathion in soil extracts was established using 96-well microtiter plate as carrier and five whole-cell biosensors as indicator. The method was applied in the detection of methyl parathion in tested and field soil extracts. Taking E. coli DH5α/pMP-AmilCP with the best detection performance as an example, this biosensor had a detection limit of 6.21-6.66 µg/L and a linear range of 10-10 000 µg/L for methyl parathion in four soil extracts. E. coli DH5α/pMP-RFP and E. coli DH5α/pMP-AmilCP methods have good detection performance for the analysis of methyl parathion in soil extract samples. This biosensor method can help to quickly assess the bioavailability of methyl parathion in soil, and thus help to understand the risk of soil pollution caused by organophosphorus pesticide methyl parathion.

Rational design of a novel MOF-based ternary nanocomposite for effectively monitoring harmful organophosphates in foods and the environment.

Methyl parathion (MP) is a widely used organophosphate insecticide that is extremely toxic due to its ability to irreversibly inhibit acetylcholinesterase in the body and persistently accumulate in the environment. Timely detection of MP can prevent harmful residue exposure to humans. Therefore, the development of fast, efficient electrochemical methods to detect trace MP has been highly beneficial for monitoring harmful residues in foods and environment to ensure food safety and ecological conservation. Herein, a novel hybrid metal-organic framework (MOF) nanocomposite composed of Pt nanoparticles (PtNPs), multi-walled carbon nanotubes (MWCNTs), and UiO-66-NH2 (PtNPs/UiO-66-NH2/MWCNTs) was rationally designed and prepared by a facile two-step strategy for the sensitive determination of MP. The synergistic effects are illustrated in detail using XRD, XPS, FTIR, TEM, and SEM studies as well as electrochemical technologies such as CV, EIS, and DPV. In addition, the performance of the ternary nanocomposite for detecting MP was investigated by comparing it with the binary-component one. The results showed that the PtNPs/UiO-66-NH2/MWCNT-based electrochemical sensor exhibited outstanding sensitivity of 21.9 µA µM-1 cm-2, satisfactory low detection limit of 0.026 µM and wide linear range of 0.11-227.95 µM for MP analysis. Furthermore, the fabricated sensor delivered distinguished freedom from interferences, outstanding regeneration ability, and adequate recoveries for fresh foods and river water samples. In conclusion, the proposed PtNPs/UiO-66-NH2/MWCNT-based sensor provides a potentially useful analytical tool for determining hazardous residues of OPs in foods and the environment.

Development of a whole-cell biosensor for detecting organophosphorus pesticide methyl parathion in the farmland soil / 生物工程学报

The evaluation of the bioavailability of pollutants in soil is crucial to accurately assess the pollution risk, and whole-cell biosensor is one of the important tools for such evaluation. This study aimed to develop a novel whole-cell biosensor for the detection of methyl parathion in soil using. First, a whole-cell biosensor was constructed by the screened methyl parathion hydrolase mpd gene, the existing specific induction element pobR, and the pUC19 plasmid skeleton. Then, the detection method of methyl parathion in soil extracts was established using 96-well microtiter plate as carrier and five whole-cell biosensors as indicator. The method was applied in the detection of methyl parathion in tested and field soil extracts. Taking E. coli DH5α/pMP-AmilCP with the best detection performance as an example, this biosensor had a detection limit of 6.21-6.66 µg/L and a linear range of 10-10 000 µg/L for methyl parathion in four soil extracts. E. coli DH5α/pMP-RFP and E. coli DH5α/pMP-AmilCP methods have good detection performance for the analysis of methyl parathion in soil extract samples. This biosensor method can help to quickly assess the bioavailability of methyl parathion in soil, and thus help to understand the risk of soil pollution caused by organophosphorus pesticide methyl parathion.

Electrochemical Organophosphorus Pesticide Detection Using Nanostructured Gold-Modified Electrodes.

In this study, nanostructured gold was successfully prepared on a bare Au electrode using the electrochemical deposition method. Nanostructured gold provided more exposed active sites to facilitate the ion and electron transfer during the electrocatalytic reaction of organophosphorus pesticide (methyl parathion). The morphological and structural characterization of nanostructured gold was conducted using field-emission scanning electron microscopy (FESEM), X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD), which was further carried out to evaluate the electrocatalytic activity towards methyl parathion sensing. The electrochemical performance of nanostructured gold was investigated by electrochemical measurements (cyclic voltammetry (CV) and differential pulse voltammetry (DPV)). The proposed nanostructured gold-modified electrode exhibited prominent electrochemical methyl parathion sensing performance (including two linear concentration ranges from 0.01 to 0.5 ppm (R2 = 0.993) and from 0.5 to 4 ppm (R2 = 0.996), limit of detection of 5.9 ppb, excellent selectivity and stability), and excellent capability in determination of pesticide residue in real fruit and vegetable samples (bok choy and strawberry). The study demonstrated that the presented approach to fabricate a nanostructured gold-modified electrode could be practically applied to detect pesticide residue in agricultural products via integrating the electrochemical and gas chromatography coupled with mass spectrometry (GC/MS-MS) analysis.

Proteomic analysis of Burkholderia zhejiangensis CEIB S4-3 during the methyl parathion degradation process.

Methyl parathion is an organophosphorus pesticide widely employed worldwide to control pests in agricultural and domestic environments. However, due to its intensive use, high toxicity, and environmental persistence, methyl parathion is recognized as an important ecosystem and human health threat, causing severe environmental pollution events and numerous human poisoning and deaths each year. Therefore, identifying and characterizing microorganisms capable of fully degrading methyl parathion and its degradation metabolites is a crucial environmental task for the bioremediation of pesticide-polluted sites. Burkholderia zhejiangensis CEIB S4-3 is a bacterial strain isolated from agricultural soils capable of immediately hydrolyzing methyl parathion at a concentration of 50 mg/L and degrading the 100% of the released p-nitrophenol in a 12-hour lapse when cultured in minimal salt medium. In this study, a comparative proteomic analysis was conducted in the presence and absence of methyl parathion to evaluate the biological mechanisms implicated in the methyl parathion biodegradation and resistance by the strain B. zhejiangensis CEIB S4-3. In each treatment, the changes in the protein expression patterns were evaluated at three sampling times, zero, three, and nine hours through the use of two-dimensional polyacrylamide gel electrophoresis (2D-PAGE), and the differentially expressed proteins were identified by mass spectrometry (MALDI-TOF). The proteomic analysis allowed the identification of 72 proteins with differential expression, 35 proteins in the absence of the pesticide, and 37 proteins in the experimental condition in the presence of methyl parathion. The identified proteins are involved in different metabolic processes such as the carbohydrate and amino acids metabolism, carbon metabolism and energy production, fatty acids ß-oxidation, and the aromatic compounds catabolism, including enzymes of the both p-nitrophenol degradation pathways (Hydroquinone dioxygenase and Hydroxyquinol 1,2 dioxygenase), as well as the overexpression of proteins implicated in cellular damage defense mechanisms such as the response and protection of the oxidative stress, reactive oxygen species defense, detoxification of xenobiotics, and DNA repair processes. According to these data, B. zhejiangensis CEIB S4-3 overexpress different proteins related to aromatic compounds catabolism and with the p-nitrophenol  degradation pathways, the higher expression levels observed in the two subunits of the enzyme Hydroquinone dioxygenase, suggest a preferential use of the Hydroquinone metabolic pathway in the p-nitrophenol degradation process. Moreover the overexpression of several proteins implicated in the oxidative stress response, xenobiotics detoxification, and DNA damage repair reveals the mechanisms employed by B. zhejiangensis CEIB S4-3 to counteract the adverse effects caused by the methyl parathion and p-nitrophenol exposure.

Recombinant organophosphorus hydrolase (OPH) expression in E. coli for the effective detection of organophosphate pesticides.

Accumulation and exposure of organophosphate pesticides are of great concern today owing to their abundant usage and potential health hazards. Harmful effects of organophosphate pesticide exposure and limitations of the available treatment methods necessitate the development of reliable, selective, cost-effective, and sensitive methods of detection. We developed a novel biosensor based on the enzymatic action of recombinant organophosphorus hydrolase (OPH) expressed in E. coli. We report the development of colorimetric biosensors made of His-Nus-OPH as well as His-Nus-OPH loaded alginate microspheres. The colorimetric detection method developed using solution-phase and alginate-encapsulated His-Nus-OPH exhibited detection limits of 0.045 and 0.039 mM, respectively, for ethyl paraoxon, and 0.101 and 0.049 mM, respectively, for methyl parathion. Additionally, fluorescence measurement using pH-sensitive fluorescein isothiocyanate (FITC) was used to sense the quantity of organophosphorus pesticides. The fluorometric detection method using solution-phase His-Nus-OPH, with ethyl paraoxon and methyl parathion as the substrate, reveals the lower limit of detection as 0.014 mM and 0.044 mM, respectively. Our results demonstrate the viability of His-Nus-OPH for OP detection with good sensitivity, LOD, and linear range. We report the first use of N-terminal His-NusA-tagged OPH, which enhances solubility significantly and presents a significant advance for the scientific community.

Graphene oxide@Ce-doped TiO2 nanoparticles as electrocatalyst materials for voltammetric detection of hazardous methyl parathion.

A sensitive voltammetric sensor has been developed for hazardous methyl parathion detection (MP) using graphene oxide@Ce-doped TiO2 nanoparticle (GO@Ce-doped TiO2 NP) electrocatalyst. The GO@Ce-doped TiO2 NPs were prepared through the sol-gel method and characterized by various physicochemical and electrochemical techniques. The GO@Ce-doped TiO2 NP-modified glassy carbon electrode (GCE) addresses excellent electrocatalytic activity towards MP detection for environmental safety and protection. The developed strategy of GO@Ce-doped TiO2 NPs at GCE surfaces for MP detection achieved excellent sensitivity (2.359 µA µM-1 cm-2) and a low detection limit (LOD) 0.0016 µM with a wide linear range (0.002 to 48.327 µM). Moreover, the fabricated sensor shows high selectivity and long-term stability towards MP detection; this significant electrode further paves the way for real-time monitoring of environmental quantitative samples with satisfying recoveries.

Ultrasonic-assisted preparation of halloysite nanotubes/zirconia/carbon black nanocomposite for the highly sensitive determination of methyl parathion.

Herein, a cost-effective and scalable ultrasound assisted approach was proposed to prepare the nanocomposite of halloysite nanotubes/zirconia/carbon black (Hal/ZrO2/CB), which was used to fabricate a novel electrochemical sensor for the highly sensitive determination of methyl parathion (MP). In the Hal/ZrO2/CB nanocomposite, Hal with large specific surface area and numerous active sites could enhance the adsorption capacity and accelerate the redox reaction of MP; ZrO2 nanoparticles with high affinity toward the phosphate group could contribute to good recognition performance for MP; CB nanoparticles with good dispersibility formed an interconnected pearl-chain-like conductive network. Benefitting from the synergistic effect of the three components, the Hal/ZrO2/CB/GCE (glassy carbon electrode) sensor showed a remarkably low detection limit of 5.23 nM in a good linear MP detection range of 0.01-10 µM. The Hal/ZrO2/CB/GCE sensor possessed a pretty decent practicality with satisfactory RSD and recovery results for the determination of MP in peach, pear, and apple juices. Therefore, the Hal/ZrO2/CB/GCE sensor has important implication on the quite sensitive detection of MP.

MPH-GST sensing microplate for easy detection of organophosphate insecticides.

OBJECTIVE: To develop a convenient and efficient means for organophosphate (OP) insecticide detection, a simple, cost-effective, and easy-to-use absorbance-based sensing device was generated using methyl parathion hydrolase fused with glutathione-S-transferase (MPH-GST) covalently immobilized onto a chitosan film-coated microplate. RESULTS: With methyl parathion (MP) as a representative substrate, this MPH-GST sensing microplate had the detection limit of 0.1 µM and the linear range of 0.1-50 µM. Despite its highest stability at 4 °C, it was considerably stable at 25 °C with high activity for 30 days. It was also most stable at pH 8.0 and could be efficiently reused up to 100 rounds. The device revealed a high percentage of recovery for tap water spiked with a known concentration of MP, which was also comparable to the result obtained from gas chromatography-mass spectrometry. It also showed a high recovery of 82-100% with MP spiked agricultural products and satisfactory results with non-spiked samples. This immobilized enzyme sensing system was more sensitive and efficient than the whole cell system from our previous work. CONCLUSIONS: All of the advantages of the MPH-GST sensing microplate developed have rendered it suitable for rapid and convenient OP screening, and for being a bio-element for fabricating a potential optical biosensor in the future.

A dual-mode nanoprobe for the determination of parathion methyl based on graphene quantum dots modified silver nanoparticles.

We developed a highly sensitive and selective method for double-signal analysis (fluorescence and ultraviolet-visible spectrophotometry) of organophosphorus pesticides (OPs), based on reversible quenching of graphene quantum dots (GQDs; fluorophores) with silver nanoparticles (AgNPs; absorbers). We used acetylcholinesterase to catalytically convert acetylthiocholine into thiocholine. In turn, by competitive binding to the AgNPs, the produced thiocholine displaces AgNPs from the GQDs and thus induces fluorescence recovery. However, OP analytes inhibit the activity of acetylcholinesterase and, in so doing, retain the silver-graphene nanoparticle complex and fluorescence quenching. The degree of quenching is proportional to the concentration of OPs; the detection limit is as low as 0.017 µg/L. The ultraviolet-visible absorption of GQDs/AgNPs at 390 nm decreases-because of AgNP aggregation that occurs after desorption from the GQDs-and the absorbance is linearly proportional to the OP concentration. Our system has good selectivity to substances that are commonly present in water and vegetables. We successfully applied our method to OP analysis in water, apple, and carrot samples.

Flexible paper-based SERS substrate strategy for rapid detection of methyl parathion on the surface of fruit.

Herein, we reported a simple, flexible and sensitive surface-enhanced Raman scattering (SERS) substrate to detect methyl parathion residues in real life. The substrate was fabricated by filter paper and gold nanoparticles (Au NPs) with excellent reproducibility and stability. First, Au NPs were synthesized by the seed mediated growth method and assembled to the filter paper through immersion. The Raman probe molecule 4-MBA was used to evaluate performance of the substrate for an optimized signal using a portable Raman spectrometer coupled with 785 nm laser. Then, the paper-based substrate was applied to detect methyl parathion standard solution whose detection limit was down to 0.011 µg/cm2, and the linear range was between 0.018 µg/cm2 and 0.354 µg/cm2. Afterwards, actual sample (apple) spiked with methyl parathion was taken to verify the practicality of the substrate by a simple way of "press-peel off". The recovery rate was ranged from 94.09% to 98.72%, indicating that this method is reliable in actual sample detection without complicated pretreatment steps. This work demonstrates that the flexible paper-based substrate combined with portable Raman instruments can be potentially applied to on-site detection of hazardous substances in the field of food safety.

Reduced graphene oxide nanosheets modified with nickel disulfide and curcumin nanoparticles for non-enzymatic electrochemical sensing of methyl parathion and 4-nitrophenol.

A method was designed for simultaneous voltammetric determination of methyl parathion pesticide (MP) and 4-nitrophenol (4-NP). Curcumin nanoparticles were deposited on reduced graphene oxide nanosheets that were modified with nickel disulfide. The material was placed on a screen-printed carbon electrode and then displayed high electrocatalytic activities toward MP and 4-NP, with a peak potential near -0.9 and - 0.7 V (vs. pseudo Ag/AgCl), respectively. Figures of merit include (a) good electrochemical sensitivities (7.165 and 6.252 µA·µM-1·cm-2), (b) wide linear ranges (from 0.25 to 80 µM), (c) low limits of detection (8.7 and 6.9 nM at S/N = 3) for MP and 4-NP, respectively, and (d) good selectivity, repeatability, reproducibility, and storage stability. The method was applied in the determination of MP and 4-NP in tomato and apple juices and spiked river water. Graphical abstract A novel electrocatalysis platform based on reduced graphene oxide-nickel disulfide nanosheets decorated with curcumin nanoparticles for simultaneous quantification of methyl parathion and 4-nitrophenol in various vegetarian juices and water samples.

Electrochemical biosensor for methyl parathion based on single-walled carbon nanotube/glutaraldehyde crosslinked acetylcholinesterase-wrapped bovine serum albumin nanocomposites.

Semiconducting single-walled carbon nanotubes (s-SWCNTs) have been demonstrated as an excellent material for transistors, miniaturized devices and sensors due to their high carrier mobility, stability, scattering-free ballistic transport of carriers etc. Herein, we have designed a biosensor to selectively detect methyl parathion (MP, organophosphorus pesticide) using glutaraldehyde (Glu) cross-linked with acetylcholinesterase (AChE) immobilized on s-SWCNTs wrapped with bovine serum albumin (BSA). The fabricated biosensor was characterized and confirmed by Fourier-transform infrared spectroscopy (FT-IR), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and square wave voltammetry (SWV). In the presence of MP, the effective interaction between AChE and MP favours the accumulation of MP-AChE complex on the glassy carbon electrode (GCE) surface which reduces the electron transfer property. Based on this interaction, detection of various concentration of MP was demonstrated by SWV using BSA/AChE-Glu-s-SWCNTs composite modified electrode. The proposed biosensor exhibited a wide linear range (WLR) for MP target in 100 mM phosphate buffered saline solution (PBS) (pH 7.4) from 1 × 10-10 M to 5 × 10-6 M with a limit of detection (LOD) of 3.75 × 10-11 M. In addition, the BSA/AChE-Glu-s-SWCNTs/GCE biosensor showed good repeatability and reproducibility for MP detection. Moreover, the proposed biosensor showed better electrode stability when stored at 4 °C. This new electrochemical biosensor is also exhibited high selectivity and sensitivity for MP, which made it possible to test MP in real strawberry and apple juices. Furthermore, the BSA/AChE-Glu-s-SWCNTs/GCE offered a favourable electron transfer between the acetylthiocholine chloride (ATCl) and electrode interface than BSA/AChE-s-SWCNTs/GCE, s-SWCNTs/GCE and bare GCE.

Electrochemical co-deposition synthesis of Au-ZrO2-graphene nanocomposite for a nonenzymatic methyl parathion sensor.

For the first time, a simple electrochemical co-deposition was utilized to synthesis the gold and zirconia nanocomposites modified graphene nanosheets on glassy carbon electrode (Au-ZrO2-GNs/GCE) for electrocatalytic analysis of methyl parathion (MP). According to Field-Emission Scanning Electron Microscopy (FE-SEM), Transmission Electronic Microscopy (TEM) and X-Ray Diffraction (XRD), the gold nanoparticles were uniformly distributed on the surface of graphene-based nanocomposite. The Au-ZrO2-GNs/GCE based sensor exhibited superior capacity for MP detection, ascribed to the strong affinity of zirconia towards the phosphoric group, as well as the high catalytic activity and good conductivity of Au-GNs. The best fabrication and work conditions were then obtained by systematically optimization of the electrodeposition process, pH value and enrichment time. Compared to the gold nanoparticles, zirconia or graphene modified electrodes, AuZrO2-GNs/GCE sensor displayed superior electro-catalytic response toward MP oxidation. The sensor response current of square wave voltammetry was highly linearly correlated with the MP concentrations range of 1-100 ng mL-1 and 100-2400 ng mL-1 with the detection limit of 1 ng mL-1. The Au-ZrO2-GNs/GCE nanocomposite sensor showed excellent accuracy and reproducibility for detection of MP in Chinese cabbage samples, providing a new method for efficient pesticide detection in practical applications.

Hypersensitive and selective biosensing based on microfiber interferometry and molecular imprinted nanoparticles.

The molecular imprinting techniques with interferometric platform are promising for next-generation optical sensors for online and remote biosensing and device applications. This technique has shown a tremendous potential to provide a highly specific detection of target analyte/molecule with artificial complementary scaffolds in the polymeric nanostructures relay with tunable aspect ratio, low cost synthesis procedure and applicability in harsh environment. To date, no molecular imprinted nanoparticles has been integrated with optical microwire platform in the literature. Here, we report the synthesis of a molecularly imprinted nanocarrier using hydrothermal process that act as receptors and combines optical microwire as transducing support. The detailed sensing process for one of the widely used pesticides (parathion methyl) in the detection range of 10-12 to 10-4 M with hyper-sensitivity and detection limit of 1.30 × 1012 nm/M and 79.43 fM respectively have been achieved. The compact sensing probe tested with real water samples collected from various sources show percentage recovery of around 100%. We strongly believe that the process for probe development will open a new gateway for next generation selective biosensing for biomedical research applications.

Rapid and fingerprinted monitoring of pesticide methyl parathion on the surface of fruits/leaves as well as in surface water enabled by gold nanorods based casting-and-sensing SERS platform.

An effective, simple and portable gold nanorod (Au NR) based casting-and-sensing surface enhanced Raman scattering (SERS) platform was developed for rapid and fingerprinted detection of pesticide methyl parathion. Monodispersed Au NRs with an average length of 60 nm and an aspect ratio of ca. 3 were synthesized through a seed mediated method and then systematically characterized. After a proof-of-concept detection for methyl parathion in DI water and on solid surface, the sensing platform was further applied to real samples (lake water, orange, apple and plant leave) contaminated with methyl parathion. The results show that the sensitivity of the SERS sensor for methyl parathion was satisfactory for real application, with detection limits of 1 µM in spiked lake water and 110-440 ng/cm2 on the surface of various fruits and plant leaves. This study indicates that the developed casting-and-sensing SERS sensor shows great promise to secure agricultural, food and environmental safety.

Activation of manganese dioxide with bisulfite for enhanced abiotic degradation of typical organophosphorus pesticides: Kinetics and transformation pathway.

Organophosphorus pesticides (OPPs), a kind of effective insecticide, have attracted extensive attention of researchers because of the high toxicity and refractory character of their degradation products. Given the ubiquity of manganese dioxide (MnO2) and bisulfite (HSO3-) in environmental media, the abiotic degradation of several typical OPPs by the MnO2-HSO3- reaction system was investigated in batch experiments. As a representative OPP, methyl parathion (MP) was chosen to be the focus of the study. The removal rate of MP was remarkably improved by adding bisulfite (HSO3-) to the MnO2 single-reaction system, and the oxidation product methyl paraoxon was below the detection limit. The primary active substances generated from the reaction system were determined to be Mn(III) species by adding excess radical scavengers or complexants (methanol and pyrophosphate) to the reaction system. On the basis of the metabolic products of MP identified by liquid chromatography-high-resolution mass spectrometry (LC/HRMS) and gas chromatography-mass spectrometry (GC/MS), the transformation pathway of MP in the MnO2-HSO3- reaction system was elicited, which included the predominant processes of hydrolysis and oxidation. Furthermore, the typical OPPs with different structures were also degraded efficiently by the reaction system because of the oxidative degradation of Mn(III). This study offers significative information related to the abiotic oxidation of manganese minerals and the fate and dissipation of OPPs in the actual environment.