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Sample pretreatment is essential for trace analysis of pesticides in complex food and environment matrices. Recently, organic-inorganic hybrid materials have gained increasing attention in pesticide extraction and preconcentration. This review highlighted the common organic-inorganic hybrid materials used as absorbents in sample pretreatment for pesticide detection. Furthermore, the preparation and characterization of organic-inorganic hybrid materials were summarized. To obtain a deep understanding of adsorption toward target analytes, the adsorption mechanism and absorption evaluation were discussed. Finally, the applications of organic-inorganic hybrid materials in sample pretreatment techniques and perspectives in the future are also discussed.

Excessive use of pesticides can cause contamination of the environment and agricultural products that are directly threatening human life and health. Therefore, in the process of food safety supervision, it is crucial to conduct sensitive and rapid detection of pesticide residues. The recognition element is the vital component of sensors and methods for fast testing pesticide residues in food. Improper recognition elements may lead to defects of testing methods, such as poor stability, low sensitivity, high economic costs, and waste of time. We can use the molecular biological technique to address these challenges as a good strategy for recognition element production and modification. Herein, we review the molecular biological methods of five specific recognition elements, including aptamers, genetic engineering antibodies, DNAzymes, genetically engineered enzymes, and whole-cell-based biosensors. In addition, the application of these identification elements combined with biosensor and immunoassay methods in actual detection was also discussed. The purpose of this review was to provide a valuable reference for further development of rapid detection methods for pesticide residues.

Glyphosate (GLYP) is a broad-spectrum, non-selective, organic phosphine post emergence herbicide registered for use on many food and non-food field. Herein, we developed a biosensor (Mbs@dsDNA) based on carboxylated modified magnetic beads incubated with NH2-polyA and then hybridized with polyT-glyphosate aptamer and complementary DNA. Afterward, a quantitative detection method based on qPCR was established. When the glyphosate aptamer on Mbs@dsDNA specifically recognized glyphosate, a complementary DNA is released and then enters the qPCR signal amplification process. The linear range of the method was 0.1-5 μg/mL, and the detection limit was set at 0.1 μg/mL. The recoveries in tap water were ranged from 103.4 ~ 104.9%, and the relative standard deviations (RSDs) were < 1%. The aptamer proposed in this study has a good potential for recognizing glyphosate. The detection method combined with qPCR might have a good application prospect in detecting and supervising other pesticide residues.

Environmental chemical contaminants in food seriously impact human health and food safety. Successful detection methods can effectively monitor the potential risk of emerging chemical contaminants. Among them, molecularly imprinted polymers (MIPs) based on electrochemical biomimetic sensors overcome many drawbacks of conventional detection methods and offer opportunities to detect contaminants with simple equipment in an efficient, sensitive, and low-cost manner. We searched eligible papers through the Web of Science (2000–2022) and PubMed databases. Then, we introduced the sensing mechanism of MIPs, outlined the sample preparation methods, and summarized the MIP characterization and performance. The classification of electrochemistry, as well as its advantages and disadvantages, are also discussed. Furthermore, the representative application of MIP-based electrochemical biomimetic sensors for detecting small molecular chemical contaminants, such as antibiotics, pesticides, toxins, food additives, illegal additions, organic pollutants, and heavy metal ions in food, is demonstrated. Finally, the conclusions and future perspectives are summarized and discussed.

As an important chemical pollutant affecting the safety of agricultural products, the on-site and efficient detection of pesticide residues has become a global trend and hotspot in research. These methodologies were developed for simplicity, high sensitivity, and multiresidue detection. This review introduces the currently available technologies based on electrochemistry, optical analysis, biotechnology, and some innovative and novel technologies for the rapid detection of pesticide residues, focusing on the characteristics, research status, and application of the most innovative and novel technologies in the past 10 years, and analyzes challenges and future development prospects. The current review could be a good reference for researchers to choose the appropriate research direction in pesticide residue detection.

Herein, an indirect SERS sensing assay was developed for the determination of glyphosate (Gly) in tap water. The mechanism of detection was based on relieving the inhibitory effect of l-cysteine (l-cys) on a Au-Pt nanozyme by combining Gly with l-cys through divalent copper ions (Cu2+). In this method, a novel nano-chain-like Au-Ag composite with good repeatability was successfully fabricated to detect SERS signals of oxTMB without disturbing TMB Raman signals. Under optimal conditions, the SERS signal intensity of oxTMB (at 1605 cm-1) was proportional to the concentration of Gly. The results showed a good linear response over the concentration ranges of 10 μg L-1 to 1000 mg L-1. The limit of detection and limit of quantitation of Gly were found to be 5 μg L-1 and 10 μg L-1, respectively. In addition, good anti-interference ability against interfering cations and structural analogues deserves to be mentioned. This SERS assay can be used for detection of Gly in tap water that can meet the needs of practical detection.

Acetylcholinesterase inactivating compounds, such as organophosphate (OP) and carbamate (CM) pesticides, are widely used in agriculture to ensure sustainable production of food and feed. As a consequence of their applications, they would result in neurotoxicity, even death. In this essence, the development of enzyme inhibition methods still shows great significance as rapid detection techniques for on-site large-scale screening of OPs and CMs. Initially, mechanisms and applications of various enzyme-inhibition-based methods and devices, including optical colorimetric assay, fluorometric assays, electrochemical biosensors, rapid test card, and microfluidic device, are highlighted in the present overview. Further, to enhance the enzyme sensitivity for detection; alternative enzyme sources or high yield enrichment methods (such as abzyme, artificial enzyme, and recombinant enzyme), as well as enzyme reactivation and identification, are also addressed in this comprehensive overview.

The core-shell metal-organic framework coated with molecularly imprinted polymers (ZIF-8@MIPs) were successfully synthesized by surface imprinting technique, and applied as adsorbents for solid-phase extraction of strobilurin fungicides. The obtained hybrid complex was characterized in detail, and their adsorbing and recognition performance were evaluated. The results showed that ZIF-8@MIPs presented typically core-shell structure with MIP shell (about 20 nm), and exhibited larger adsorption capacity (102.5 mg g

Herein, a modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) method with multi-walled carbon nanotube (MWCNT) as a dispersive solid-phase extraction was developed for simultaneous determination of pinoxaden (PXD), cloquintocet-mexyl (CLM), clodinafop-propargyl ester (CPE) and its major metabolite (clodinafop, CP) in barley grass powder, barley grain, and soil using liquid chromatography-tandem mass spectrometry (LC-MS/MS). We found that MWCNT as an absorbent could improve the recoveries of the tested analytes, particularly CP, in complex matrices. Under the optimum conditions, the established MWCNT-modified QuEChERS coupled with LC-MS/MS method exhibited excellent linearity (R

In this paper, a flower-like molybdenum disulfide material was prepared by hydrothermal method and firstly used as adsorbents in solid-phase extraction process for enriching N-nitrosoamines. Molybdenum disulfide exhibited three-dimensional petal-like microspheres with about 500 nm in diameter. The relevant analyte extraction and elution parameters (sample volumes, solution pH, washing solvents, elution solvents and elution volumes) were optimized to improve the solid-phase extraction efficiency. The solid-phase extraction process coupled with high-performance liquid chromatography tandem mass spectrometry for determining N-nitrosoamines in environmental water samples was established. The limits of detection were in the range of 0.01-0.05 ng/mL. The satisfactory recoveries (68.9%-106.1%) were obtained at three different spiked concentrations (2, 5 and 8 ng/mL) in water samples, and the relative standard deviations were between 1.96% and 8.38%. This proposed method not only showed high sensitivity and good reusability, but also provided a new adsorbent for enriching trace N-nitrosoamines in environmental water samples. This article is protected by copyright. All rights reserved.

Owing to the excellent performances of high sensitivity, high specificity, on-site detection, and multiplexing capability, surface-enhanced Raman scattering (SERS)-based aptasensors have performed prosperous applications and gained impressive progress in food safety. Herein, we reviewed the SERS-based aptasensors from the principles to specific applications in food safety. First, the sensor-working principles, SERS label design and preparation are introduced. Then, the popular platforms in the aptasensors are summarized with their advantages and disadvantages, followed by their representative applications. Further, the specific applications of developing SERS-based aptasensors in food safety are systematically provided. Moreover, the multiplex analysis using SERS labels are highlighted. Finally, challenges and perspectives for improving the SERS-based aptasensor performance are also discussed, aiming to give some proposes for researchers to choose suitable SERS-based aptasensors according to specific applications.

Organophosphate pesticides (OPs) are often used as insecticides and acaricides in agriculture, thus improving yields. OP residues may pose a serious threat, due to inhibition of the enzyme acetylcholinesterase (AChE). Therefore, a competitive bio-barcode immunoassay was designed for simultaneous quantification of organophosphate pesticide residues using AuNP signal amplification technology and Au@Pt catalysis. The AuNP probes were labelled with antibodies and corresponding bio-barcodes (ssDNAs), MNP probes coated with ovalbumin pesticide haptens and Au@Pt probes functionalized with the complementary ssDNAs were then prepared. Subsequently, pesticides competed with MNP probes to bind the AuNP probes. The recoveries of the developed assay were ranged from 71.26 to 117.47% with RSDs from 2.52 to 14.52%. The LODs were 9.88, 3.91, and 1.47 ng·kg−1, for parathion, triazophos, and chlorpyrifos, respectively. The assay was closely correlated with the data obtained from LC-MS/MS. Therefore, the developed method has the potential to be used as an alternative approach for detection of multiple pesticides.

The biomimetic enzyme-linked immunosorbent assay (BELISA) is widely used for detection of small-molecule compounds as a result of low cost and reagent stability of molecularly imprinted polymers (MIPs). However, enzyme labels used in BELISA still suffer some drawbacks, such as high production cost and limited stability. To overcome the drawbacks, a biomimetic nanozyme-linked immunosorbent assay (BNLISA) based on MIPs and nanozyme labels was first proposed. For nanozyme labels, platinum nanoparticles (PtNPs) acted as peroxidase by catalyzing the oxidation of colorless 3,3',5,5'-tetramethylbenzidine (TMB) into an ideal surface-enhanced Raman scattering (SERS) marker. Blue TMB2+ and bovine serum albumin (BSA)-hapten showed superior selectivity when competing with targets for binding sites on MIPs, named the Pt@BSA-hapten probe. The BNLISA method was employed to detect triazophos with a limit of detection of 1 ng mL-1 via colorimetric and SERS methods. Replacing traditional enzymes with nanozymes for combination with MIPs may bring about a new prospect for other compound analyses.

Herein, a novel magnetic molecularly imprinted polymer doped with reticular graphene oxide (Fe3O4@SiO2-GO@MIPs) was synthesized for the selective recognition and extraction of 4 flavonoids (farrerol, taxifolin, kaempferol, and hyperin) from Rhododendrons species. The Fe3O4@SiO2-GO@MIPs with lamellar membranes showed outstanding adsorption capacity. The 3D cavities complementary to the “shape” of farrerol were “imprinted” on the polymer framework after removal of farrerol template. Competitive binding assays showed that the polymer has a higher selectivity for farrerol compared with other analogues and references. The Fe3O4@SiO2-GO@MIPs as solid-phase extraction adsorbents combined with liquid chromatography-tandem quadrupole mass spectrometry (LC–MS/MS) was used for selective determination of four flavonoids from Rhododendrons samples. The limits of detection (LOD) were 0.07, 0.08, 0.06, and 0.08 μg L−1 for farrerol, taxifolin, kaempferol, and hyperin, respectively. These results suggest that the prepared Fe3O4@SiO2-GO@MIPs have the potential applicability to extract, purify, and enrich flavonoids from herbs, supplements, and other natural products.

Salidroside is one of the bio-active compounds found in Rhodiola crenulata. To find an easy, time saving and efficient way to extract, purify and enrich salidroside from Rhodiola and other natural plants, we prepared a highly selective molecularly imprinted polymer (MIP) for extraction and preconcentration of salidroside using salidroside (SD) as a template, acrylamide (AM) as a functional monomer, ethylene glycol dimethacrylate (EDMA) as a crosslinking monomer, and dimethyl formamide (DMF) as a porogen. The performance of the MIPs was evaluated through selective recognition capacity and adsorption isotherms and kinetics. The results showed that MIPs possessed excellent specific recognition toward SD and could effectively discriminate its structural analogue. The application of the developed MIPs as a selective sorbent for solid-phase extraction (SPE) of SD was also investigated. Under the optimum conditions, a rapid, economical, and efficient method based upon MIP-SPE coupled with high-performance liquid chromatography (HPLC) was developed for the determination of SD in Rhodiola crenulata. The method showed satisfactory recoveries (from spiked real samples at 3 fortification levels of 0.5, 1 and 10 mg L−1) of 88.74%- 97.64% with relative standard deviations (RSDs) ranging from 2.05%–3.54%. Furthermore, MIP-SPE was successfully used to separate and purify SD from different parts in Rhodiola crenulata and it should be available for determination of salidroside in others herbs.

Herein, we introduced a rapid detection method for residual trace levels of triazophos in water and agricultural products using an immunoassay based on catalytic hairpin self-assembly (CHA). The gold nanoparticles (AuNPs) surface was modified with triazophos antibody and sulfhydryl bio-barcode, and an immune competition reaction system was established between triazophos and its ovalbumin-hapten (OVA-hapten). The bio-barcode served as a catalyst to continuously induce the CHA reaction to achieve the dual signal amplification. The method does not rely on the participation of enzymes, and the addition of fluorescent materials in the last step avoids interfering factors, such as a fluorescence burst. The emitted fluorescence was detected at 489/521 nm excitation/emission wavelengths. The detection range of the developed method was 0.01-50 ng/mL for triazophos, and the limit of detection (LOD) was 0.0048 ng/mL. The developed method correlates well with the results obtained by LC-MS/MS, with satisfactory accuracy (expressed as recovery %) and sensitivity. In sum, the designed method is reliable; meanwhile, it provides a new approach to detect pesticide residues rapidly and quantitatively.

Magnetic relaxation switching (MRS) sensors have shown great potential in food safety monitoring due to their high signal-to-noise ratio and simplicity, but they often suffer from insufficient sensitivity and stability due to the lack of excellent magnetic nanoprobes. Herein, dumbbell-like Au-Fe

A bio-barcode immunoassay based on droplet digital polymerase chain reaction (ddPCR) was developed to simultaneously quantify triazophos, parathion, and chlorpyrifos in apple, cucumber, cabbage, and pear. Three gold nanoparticle (AuNP) probes and magnetic nanoparticle (MNP) probes were prepared, binding through their antibodies with the three pesticides in the same tube. Three groups of primers, probes, templates, and three antibodies were designed to ensure the specificity of the method. Under the optimal conditions, the detection limits (expressed as IC10) of triazophos, parathion, and chlorpyrifos were 0.22, 0.45, and 4.49 ng mL–1, respectively. The linear ranges were 0.01–20, 0.1–100, and 0.1–500 ng mL–1, and the correlation coefficients (R2) were 0.9661, 0.9834, and 0.9612, respectively. The recoveries and relative standard deviations (RSDs) were in the ranges of 75.5–98.9 and 8.3–16.7%. This study provides the first insights into the ddPCR for the determination of organophosphate pesticides. It also laid the foundation for high-throughput detection of other small molecules., This study was financially supported by the National Key Research Program of China (No. 2019YFC1604503), the NIEHS Superfund Research Program (No. P42 ES04699), the Central Public-interest Scientific Institution Basal Research Fund for the Chinese Academy of Agricultural Sciences (No. Y2021PT05), and the Ningbo Innovation Project for Agro-Products Quality and Safety (No. 2019CXGC007).

Highly sensitive detection of aflatoxin B1 (AFB1) is of great significance because of its high toxicity and carcinogenesis. We propose a magnetic relaxation sensing method based on gold nanoparticles (Au NPs)-assisted triple self-assembly cascade signal amplification for highly sensitive detection of AFB1. Both AFB1 antibody and initiator DNA (iDNA) are labeled on Au NPs to form Ab-Au-iDNA probe. iDNA is enriched by Au NPs to achieve first signal amplification. Different amounts of Ab-Au-iDNA were bound with AFB1 antigen by indirect competitive immunoassay, and then hybridization chain reaction event was initiated by iDNA to produce long hybridization chain reaction products to enrich more horseradish peroxidase-streptavidin for the second signal amplification. Dopamine could be rapidly converted to polydopamine by HRP catalysis, which is used as the third signal amplification. The Fe3+ solution, providing paramagnetic ions with a strong magnetic signal, could be adsorbed by the polydopamine due to the formation of coordination bonds of phenolic hydroxyl groups with Fe3+. This effective interaction between polydopamine and Fe3+ significantly changes the transverse relaxation time signal of Fe3+ supernatant solution, which can be used as a magnetic probe for highly sensitive detection of AFB1. The sensor exhibited high specificity and sensitivity with a detection limit of 0.453 pg/mL owing to the Au NP-assisted triple self-assembly cascade signal amplification strategy. It has been successfully employed for AFB1 detection in animal feed samples with consistent results of enzyme linked immune sorbent assay and high-performance liquid chromatography.

Herein, a novel core-shell-shell magnetic nanosphere denoted as Fe

A surface-enhanced Raman scattering (SERS) sensor is reported for the determination of dichlorvos, an organophosphate pesticide (OP), in pears. Platinum coated gold nanoparticles (Au@PtNPs) were used as secondary catalysts to provide signal amplification. Acetylcholinesterase (AChE) catalyzed the hydrolysis of acetylthiocholine to form thiocholine. Thiocholine causes the accumulation of Au@PtNPs, which changes the particle size and prevents their peroxidase-mimicking activity. Dynamic light scattering was used to characterize the particle size. Following the addition of dichlorvos, the AChE activity was inhibited, the production of thiocholine and aggregation were reduced, and the peroxidase mimicing property was retained. In the presence of 3,3���,5,5���-tetramethylbenzidine (TMB), a blue product was produced that provided strong SERS signals. The SERS method showed a linear relationship for dichlorvos concentrations from 20 to 2000 ��g/L. The developed protocol had a limit of detection of 20 ��g/L. This SERS sensor assay was successfully applied for the quantification of dichlorvos in pears with satisfactory recoveries from 80.25 to 94.86%.

Surface-enhanced Raman spectroscopy (SERS) is a powerful and high-speed detection technology. It provides information on molecular fingerprint recognition with ultrahigh sensitive detection. However, it shows poor anti-interference capacity against complex matrices. Molecularly imprinted polymers (MIPs) can achieve specific recognition of targets from complex matrices. Through introducing the MIP separation system, the MIP-SERS chemical sensor can effectively overcome the limitation of complex matrix interference, and further improve the stability of sensors for detection. Herein, the materials and structures of integrated MIP-SERS sensors are systematically reviewed, and its application as a sensor for chemical detection of hazardous substances in environmental and food samples has been addressed as well. To broaden the prospects of application, we have discussed the current challenges and future perspectives that would accelerate the development of versatile MIP-SERS chemical sensors.

Here, we developed a novel non-enzymatic rapid testing method for determination of organophosphate pesticide (malathion) in water. In principle, target molecule can block the Fluorescence resonance energy transfer (FRET) between chemical fluorescent probe (energy donor) and β-cyclodextrin-coated silver nanoparticles (@AgNP) (receptor). The effects of malathion on the dynamics of fluorescent probe and β-cyclodextrin@AgNP were evaluated and their properties were further characterized. The current methodology showed a good sensitivity of 0.01 μg/mL represented as a limit of detection (LOD) and the calibration curve was linear over the concentration range of 0.1–25 μg/mL. Recovery rate from water samples spiked at 3 different concentration levels (0.3, 0.4, and 0.6 μg/mL) showed satisfactory range between 83% and 101%.