Machine Learning-Assisted Eu(III)-Functionalized HOF-on-HOF Composite-Based Sensor Platform for Precise and Visual Identification of Multiple Pesticides.

Precise and rapid identification of pesticides is crucial to ensure a green environment, food safety, and human health. However, complex sample environments often hinder precise identification, especially for simultaneous differentiation of multiple pesticides. Herein, we first synthesize a Eu(III)-functionalized HOF-on-HOF composite (Eu@PFC-1@MA-TPA) and then utilize principal component analysis (PCA) and a machine learning (ML) algorithm to achieve simultaneous identification of the pesticides 2,6-dichloro-4-nitroaniline (DCN) and thiabendazole (TBZ) and their mixtures. Eu@PFC-1@MA-TPA displays high quantitative identification ability, which can distinguish single DCN and TBZ as low as 1 µM and their mixtures at 5 µM through PCA. In addition, the hydrogel film Eu@PFC-1@MA-TPA/AG is fabricated to monitor DCN and TBZ in drinking water, tap water, river water, and apple juice with high sensitivity. Furthermore, based on the obvious fluorescence color variance of pesticides, Eu@PFC-1@MA-TPA/AG achieves visual and in situ imaging detection of single DCN and TBZ and their mixtures. More importantly, we construct an intelligent artificial vision platform integrating Eu@PFC-1@MA-TPA/AG with a DenseNet algorithm, which can identify the concentrations and types of DCN and TBZ and their mixtures within 1 s with over 98% accuracy. This work develops a precise and rapid analysis method for simultaneous identification of multiple pesticides through combining a visualized fluorescence sensor and an ML algorithm.

Cloud point method applied to the extraction and preconcentration of thiabendazole pesticide from whole grape juice samples and amperometric detection by HPLC.

A cloud point method was developed and applied for the first time to extract and preconcentrate thiabendazole (TBZ) from commercial whole grape juice samples, with determination by high performance liquid chromatography coupled to electrochemical detection (HPLC/EC), using a cathodically pretreated boron-doped diamond electrode (BDD). The best conditions for extraction and preconcentration of TBZ by cloud point extraction (CPE) were performed at pH 6.0, by adding 1 mL of the surfactant Tergitol TMN-6 at 10% (mass-to-mass ratio), without heating (at 27 °C) and ultrasonic stirring time of (20 kHz) for 60 min. The HPLC/EC determination was duly validated in a C8 column, in mobile phase with a 69 : 31 ratio (V/V) of phosphate buffer (pH 7.0):ACN, at a flow rate of 1.2 mL min-1 and electrochemical detection with BDD electrode by applying 1.40 V × Ag/AgCl (3.0 mol L-1). Under these conditions, the procedure showed a preconcentration factor (FC) of 21.7, and limits of detection (LOD) and quantification (LOQ) of 6.64 × 10-9 mol L-1 (or 1.33 µg L-1) and 1.66 × 10-8 mol L-1 (or 3.34 µg L-1), respectively. The method provided a percent recovery of 81% to 98%, with a coefficient of variation between 3% and 15%.

Acoustofluidic one-step production of plasmonic Ag nanoparticles for portable paper-based ultrasensitive SERS detection of bactericides.

SERS measurements for monitoring bactericides in dairy products are highly desired for food safety problems. However, the complicated preparation process of SERS substrates greatly impedes the promotion of SERS. Here, we propose acoustofluidic one-step synthesis of Ag nanoparticles on paper substrates for SERS detection. Our method is economical, fast, simple, and eco-friendly. We adopted laser cutting to cut out appropriate paper shapes, and aldehydes were simultaneously produced at the cutting edge in the pyrolysis of cellulose by laser which were leveraged as the reducing reagent. In the synthesis, only 5 µL of Ag precursor was added to complete the reaction, and no reducing agent was used. Our recently developed acoustofluidic device was employed to intensely mix Ag+ ions and aldehydes and spread the reduced Ag nanoparticles over the substrate. The SERS substrate was fabricated in 1 step and 3 min. The standard R6G solution measurement demonstrated the excellent signal and prominent uniformity of the fabricated SERS substrates. SERS detection of the safe concentration of three bactericides, including tetracycline hydrochloride, thiabendazole, and malachite green, from food samples can be achieved using fabricated substrates. We take the least cost, time, reagents, and steps to fabricate the SERS substrate with satisfying performance. Our work has an extraodinary meaning for the green preparation and large-scale application of SERS.

Rapid and specific detection of thiabendazole: enzymatic digestion-enabled fluorescent aptasensor.

Thiabendazole, a widely used broad-spectrum fungicide in agriculture, poses risks to human health. To monitor its presence in water, we propose a fluorescent aptasensor utilizing Escherichia coli exonuclease I (Exo I). The findings demonstrate a linear correlation between thiabendazole concentrations and digestion percentage, with a detection limit (LOD) exceeding 1 µM and a determination coefficient (R2) of 0.959. This aptamer-based fluorescence spectroscopy detection system holds promise for a rapid, specific, and sensitive analysis of thiabendazole in environmental waters and food matrices.

Cobalt-Modified Black Phosphorus Nanosheets-Enabled Ferrate (VI) Activation for Efficient Chemiluminescence Detection of Thiabendazole.

The development of chemiluminescence-based innovation sensing systems and the construction of a sensing mechanism to improve the analytical performance of compounds remain a great challenge. Herein, we fabricated an advanced oxidation processes pretreated chemiluminescence (AOP-CL) sensing system via the introduction of cobalt-modified black phosphorus nanosheets (Co@BPNs) to achieve higher efficient thiabendazole (TBZ) detection. Co@BPNs, enriched with lattice oxygen, exhibited a superior catalytic performance for accelerating the decomposition of ferrate (VI). This Co@BPNs-based ferrate (VI) AOP system demonstrated a unique ability to selectively decompose TBZ, resulting in a strong CL emission. On this basis, a highly selective and sensitive CL sensing platform for TBZ was established, which exhibited strong resistance to common ions and pesticides interference. This was successfully applied to detecting TBZ in environmental samples such as tea and kiwi fruits. Besides, the TBZ detection mechanism was explored, Co@BPNs-based ferrate (VI) AOP system produced a high yield of ROS (mainly 1O2), which oxidized the thiazole-based structure of TBZ, generating chemical energy that was transferred to Co@BPNs via a chemical electron exchange luminescence (CIEEL) mechanism, leading to intense CL emission. Notably, this study not only proposed an innovative approach to enhance the chemical activity and CL properties of nanomaterials but also offered a new pathway for designing efficient CL probes for pollutant monitoring in complex samples.

O-nitrobenzyl Caged Molecule Enables Photo-controlled Release of Thiabendazole.

Pesticides are essential in agricultural development. Controlled-release pesticides have attracted great attentions. Base on a principle of spatiotemporal selectivity, we extended the photoremovable protective group (PRPG) into agrochemical agents to achieve controllable release of active ingredients. Herein, we obtained NP-TBZ by covalently linking o-nitrobenzyl (NP) with thiabendazole (TBZ). Compound NP-TBZ can be controlled to release TBZ in dependent to light. The irradiated and unirradiated NP-TBZ showed significant differences on fungicidal activities both in vitro and in vivo. In addition, the irradiated NP-TBZ displayed similar antifungal activities to the directly-used TBZ, indicating a factual applicability in controllable release of TBZ. Furthermore, we explored the action mode and microcosmic variations by SEM analysis, and demonstrated that the irradiated NP-TBZ retained a same action mode with TBZ against mycelia growth.

Food and environmental safety monitoring platform based on Tb(III) functionalized HOF hybrids for ultrafast detection of thiabendazole and 2-chlorophenol.

Development of efficient and intelligent method for detecting harmful agrochemicals in resource-limited settings remains an urgent need to ensure food and environmental safety. Herein, a novel dual-emitting Tb3+-modified hydrogen-bonded organic framework (Tb@TBTC, TBTC is the ligand of HOF-TBTC.) with visible green fluorescence has been prepared through coordination post-synthetic modification. Tb@TBTC can be designed as a fluorescence sensor for the identification of two harmful carcinogenic pesticides, thiabendazole (TBZ) and 2-chlorophenol (2-CP) with high sensitivity, high efficiency and excellent selectivity. Tb@TBTC can also adsorb 2-CP with high adsorption rate. In realistic fruit juice and river water samples, the detection limits of Tb@TBTC toward TBZ and 2-CP are as low as 2.73 µM and 2.18 µM, respectively, demonstrating the feasibility in practical application. Furthermore, an intelligent real-time and on-site monitoring platform for 2-CP detection is constructed based on Tb@TBTC-agarose hydrogel films with the assistance of back propagation neural network, which can efficiently and accurately determine the concentration of 2-CP from fluorescence images through human-machine interaction. This work presents a facile pathway to prepare Tb@HOF fluorescent sensor for food and ecological environment safety, which is highly promising for preventing human disease and improving global public health.

Analysis and experimental assessment of an optimized SERS substrate used to detect thiabendazole in apples with high sensitivity.

Pesticides that linger in the environment and ecosystems for an extended period can cause severe and dangerous health problems in humans. To detect pesticides in foods, the development of high-sensitivity and quick screening technologies was required. This research investigated the performance of Au@Ag NPs with varying thicknesses of the silver shell for detecting trace quantities of thiabendazole (TBZ) in apples using surface-enhanced Raman spectroscopy (SERS). The Au@Ag NPs were synthesized by coating 32 nm gold seeds with different thicknesses of silver shell ranging from 2.4 to 8.7 nm, achieved by adjusting the incorporation of AgNO3 and ascorbic acid. The optimized Au@Ag NPs with a 7.3 nm silver shell demonstrated outstanding SERS activity, high sensitivity, and a detection limit of 0.05 µg/mL for TBZ. The R2 values, representing the goodness of fit, were found to be 0.990 and 0.986 for standard and real TBZ samples, respectively, indicating a strong correlation between the measured signal and the TBZ concentration. The recovery analysis showed a reliable and accurate detection capability (96 to 105%), suggesting good reliability and accuracy of the SERS-based detection using the optimal Au@Ag NPs. Overall, this research highlights the potential of SERS with optimal Au@Ag NPs for rapid and effective monitoring of pesticides in the food industry.

Quantifying the effect of non-ionic surfactant alkylphenol ethoxylates on the persistence of thiabendazole on fresh produce surface.

BACKGROUND: Understanding the role of adjuvants in pesticide persistence is crucial to develop effective pesticide formulations and manage pesticide residues in fresh produce. This study investigated the impact of a commercial non-ionic surfactant product containing alkylphenol ethoxylates (APEOs) on the persistence of thiabendazole on apple and spinach surfaces against the 30 kg m-3 baking soda (sodium bicarbonate, NaHCO3 ) soaking, which was used to remove the active ingredient (AI) in the cuticular wax layer of fresh produce through alkaline hydrolysis. Surface-enhanced Raman scattering (SERS) mapping method was used to quantify the residue levels on fresh produce surfaces at different experimental scenarios. Four standard curves were established to quantify surface thiabendazole in the absence and presence of APEOs, on apple and spinach leaf surfaces, respectively. RESULTS: Overall, the result showed that APEOs enhanced the persistence of thiabendazole over time. After 3 days of exposure, APEOs increased thiabendazole surface residue against NaHCO3 hydrolysis on apple and spinach surfaces by 5.39% and 10.47%, respectively. CONCLUSION: The study suggests that APEOs led to more pesticide residues on fresh produce and greater difficulty in washing them off from the surfaces using baking soda, posing food safety concerns. © 2023 Society of Chemical Industry.

Integrated surface-enhanced Raman spectroscopy and convolutional neural network for quantitative and qualitative analysis of pesticide residues on pericarp.

Pesticide residue poses a significant global public health concern, necessitating improved detection methods. Here, a novel platform was introduced based on surface-enhanced Raman spectroscopy (SERS) to detect ten distinct types of pesticides. Notably, the sensitivity of this approach is exemplified by detecting trace amounts of 50 pM (10 ppt) thiabendazole. The correlation between the characteristic peak intensity of coexisting pesticides and their concentrations displays an exceptional linear relationship (R2 = 0.9999), underscoring its utility for quantitative mixed pesticide detection. Additionally, qualitative analysis of five mixed pesticides was conducted leveraging distinctive peak labeling. Harnessing machine learning techniques, a model for classifying and predicting pesticides on pericarps was developed. Remarkably, the convolutional neural network achieved classification accuracy of 100 % and prediction accuracy of 99.62 %. This innovative approach accurately identifies and quantifies diverse pesticides, thus offering a feasible scheme for in-situ detection of pesticide residues. Ultimately, this strategy contributes to ensuring food safety and public health.

Combining LAESI Imaging and Tissue Spray Ionization Mass Spectrometry To Unveil Pesticides Contaminants in Fruits.

There is an increasing need for developing a strategy to analyze the penetration of pesticides in cultures during postharvest control with minimal or no sample preparation. This study explores the combined use of laser ablation electrospray ionization mass spectrometry imaging (LAESI imaging) and tissue spray ionization mass spectrometry (TSI-MS) to investigate the penetration of thiabendazole (TBZ) in fruits, simulating a postharvest procedure. Slices of guava and apple were prepared, and an infrared laser beam was used, resulting in the ablation of TBZ directly ionized by electrospray and analyzed by mass spectrometry. The experiments were conducted for 5 days of fruit storage after TBZ administration to simulate a postharvest treatment. During postharvest treatment, TBZ is applied directly to the fruit peel after harvesting. Consequently, TBZ residues may remain on the peel if the consumer does not wash the fruit properly before its consumption. To evaluate the effectiveness of household washing procedures, TSI-MS was employed as a rapid and straightforward technique to monitor the remaining amount of TBZ in guava and apple peels following fruit washing. This study highlights the advantages of LAESI imaging for evaluating TBZ penetration in fruits. Moreover, the powerful capabilities of TSI-MS are demonstrated in monitoring and estimating TBZ residues after pesticide application, enabling the comprehensive unveiling of pesticide contaminants in fruits.

Rapid detection of thiabendazole residues in apple juice by surface-enhanced Raman scattering coupled with silver coated gold nanoparticles.

In recent years, the excessive use of pesticides has posed significant hazards to the ecological environment and human health in the pursuit of high crop yields. In this work, we developed a simple, sensitive, and eco-friendly approach for rapid detection of thiabendazole in apple juice using surface-enhanced Raman scattering (SERS) coupled with silver-coated gold nanoparticles (Au@Ag NPs). The developed Au@Ag NPs exhibited excellent sensitivity, allowing for the detection of thiabendazole in standard solutions at a minimum concentration of 50 ng/mL. Furthermore, two sample preparation methods were compared for detecting thiabendazole in apple juice. As the direct detection method for SERS analysis failed to detect thiabendazole at levels below the maximum residue limit based on the Chinese standard (3000 ng/mL), the effects of main matrix components in apple juice on the detection of thiabendazole were further investigated. The results revealed that both sugars and organic acids in apple juice interfered with the SERS measurement to varying degrees. Consequently, we optimized the QuEChERS method for sample preparation and achieved a higher sensitivity with a minimum detectable concentration of 250 ng/mL, a limit of detection of 0.06 mg/L and the recoveries of spiked samples were ranged from 80.2 % to 108.6 %. This study demonstrated the feasibility of proposed SERS method for pesticide residue analysis, addressing the need for food safety monitoring.

Detoxification of the post-harvest antifungal pesticide thiabendazole by cold atmospheric plasma.

Cold atmospheric plasma (CAP) irradiation has a sterilizing effect without thermal denaturation or the production of residual substances. Hence, it is considered to be a safe sterilization technology with minimal damage for fresh foods. In addition, its decomposition effect on chemical substances has also been confirmed, and the application of CAP in the food and agricultural domains is increasing. In this study, we examined the potential of CAP to detoxify pesticide residues. Post-harvest chemical treatments using pesticides, such as fungicides, are frequently employed in imported agricultural products and are often disapproved by consumers. Therefore, we assessed the detoxification of thiabendazole (TBZ), a widely used post-harvest pesticide, using low-cost air plasma irradiation. We found that CAP irradiation conditions that detoxified TBZ caused little damage to the edible parts of mandarin oranges. The results of the present study suggest that CAP irradiation is useful for detoxifying and degrading pesticide residues without damaging agricultural products and that CAP irradiation is an effective means of maintaining food safety.

Qualitative and quantitative analysis of four benzimidazole residues in food by surface-enhanced Raman spectroscopy combined with chemometrics.

In this study, surface-enhanced Raman spectroscopy (SERS) combined with chemometric methods were developed for qualitative and quantitative analysis of four benzimidazole (BMZs) residues in corn. Sulfhydryl functionalized Fe3O4@SiO2@Ag-SH magnetic SERS substrates were prepared to obtain the SERS spectra of four BMZs for chemometric analysis. The partial least squares regression discrimination analysis (PLS-DA) model performed best, with a recall rate upwards 99.17%, and could successfully distinguish four BMZs. Under the support vector machine regression (SVR) model, the detection limits of carbendazim, benomyl, thiophanate-methyl and thiabendazole were 0.055 mg/L, 0.056 mg/L, 0.067 mg/L and 0.093 mg/L, respectively; the average recovery was in the range of 85.6%-107.5%. Furthermore, the method verified by HPLC, and the results showed that there was no significant difference between two methods (p > 0.05). Therefore, the strategy based on SERS coupling chemometrics can be served as a promising tool for rapid determination of BMZs residues in food.

Understanding the impact of a non-ionic surfactant alkylphenol ethoxylate on surface-enhanced Raman spectroscopic analysis of pesticides on apple surfaces.

Pesticide active ingredients (AIs) are often applied with adjuvants to facilitate the stability and functionality of AIs in agricultural practice. The objective of this study is to investigate the role of a common non-ionic surfactant, alkylphenol ethoxylate (APEO), on the surface-enhanced Raman spectroscopic (SERS) analysis of pesticides as well as its impact on pesticide persistence on apple surfaces, as a model fresh produce surface. The wetted areas of two AIs (thiabendazole and phosmet) mixed with APEO were determined respectively to correct the unit concentration applied on apple surfaces for a fair comparison. SERS with gold nanoparticle (AuNP) mirror substrates was applied to measure the signal intensity of AIs with and without APEO on apple surfaces after a short-term (45 min) and a long-term (5 days) exposure. The limit of detection (LOD) of thiabendazole and phosmet using this SERS-based method were 0.861 ppm and 2.883 ppm, respectively. The result showed that APEO decreased the SERS signal for non-systemic phosmet, while increased SERS intensity of systemic thiabendazole on apple surfaces after 45 min pesticide exposure. After 5 days, the SERS intensity of thiabendazole with APEO was higher than thiabendazole alone, and there was no significant difference between phosmet with and without APEO. Possible mechanisms were discussed. Furthermore, a 1% sodium bicarbonate (NaHCO3) washing method was applied to test the impact of APEO on the persistence of the residues on apple surfaces after short-term and long-term exposures. The results indicated that APEO significantly enhanced the persistence of thiabendazole on plant surfaces after a 5-day exposure, while there was no significant impact on phosmet. The information obtained facilitates a better understanding of the impact of the non-ionic surfactant on SERS analysis of pesticide behavior on and in plants and helps further develop the SERS method for studying complex pesticide formulations in plant systems.

Review of Characteristics and Analytical Methods for Determination of Thiabendazole.

Thiabendazole (TBZ) is a fungicide and anthelmintic drug commonly found in food products. Due to its toxicity and potential carcinogenicity, its determination in various samples is important for public health. Different analytical methods can be used to determine the presence and concentration of TBZ in samples. Liquid chromatography (LC) and its subtypes, high-performance liquid chromatography (HPLC) and ultra-high-performance liquid chromatography (UHPLC), are the most commonly used methods for TBZ determination representing 19%, 18%, and 18% of the described methods, respectively. Surface-enhanced Raman spectroscopy (SERS) and fluorimetry are two more methods widely used for TBZ determination, representing 13% and 12% of the described methods, respectively. In this review, a number of methods for TBZ determination are described, but due to their limitations, there is a high potential for the further improvement and development of each method in order to obtain a simple, precise, and accurate method that can be used for routine analysis.

Controllable assembly of high sticky and flexibility surface-enhanced Raman scattering substrate for on-site target pesticide residues detection.

Pesticide residues in fruit and vegetable constitute a great threat to mankind's health, and a technique of rapid, cost-effective, ultra-sensitive and non-destructive analysis is especially critical for on-site detection in practical application. A strategy was utilized to fabricate highly viscous and flexible WPU@AgNPs sticky tape for the rapid extraction and Surface-enhanced Raman Scattering (SERS) assay of thiabendazole residues on the surface of fruits. Simply put, the novel WPU@AgNPs tapes were constructed by decorating the waterborne polyurethane (WPU) film with silver nanoparticles (AgNPs), and demonstrated excellent sensitivity with 4-Mercaptopyridine (4-Mpy) as the probe molecule. Meanwhile, the enhancement factor of the novel SERS substrate could reach 7.01 × 106, which was consistent with the finite difference time domain (FDTD) theoretical simulation results. What's more, the high viscosity and flexibility of WPU@AgNPs sticky tapes allowed them to detect the thiabendazole residues on the pear, apple and banana surfaces by a straightforward "paste and peel off" approach. The results showed that the detection limit could reach 1.44, 1.12 and 1.63 ng/cm2. This strategy would be as a common method for prompt, on-site and ultra-sensitive assay of thiabendazole residues in chemical and biological fields.

EC-SERS detection of thiabendazole in apple juice using activated screen-printed electrodes.

Thiabendazole (TBZ), a benzimidazole fungicide used for post-harvest treatment, may be a trace contaminant of food matrices. In this work, we report the first EC-SERS (electrochemical-surface enhanced Raman spectroscopy) detection of TBZ in spiked apple juice using electrochemically (EC) roughened, gold-based screen-printed electrodes (AuSPEs) and portable instrumentation. Polarizing the substrate (-0.8 V vs Ag/AgCl) improves the recorded SERS signal of TBZ, allowing to reach a limit of detection (LOD) in juice of 0.061 ppm with a relatively wide linear range (0.5-10 µM) and good intermediate precision (%RSD < 10). The recovery of TBZ from unprocessed juice was found to be more than 82 %. Furthermore, a proof-of-concept integration of AuSPEs with a miniaturized flow cell for the preconcentration of TBZ and the controlled delivery of sample and reagents has been demonstrated. This approach paves the way for integrated, portable analytical systems applicable for on-site sample collection, processing, and analysis.

Ultrasensitive indirect electrochemical sensing of thiabendazole in fruit and water by the anodic stripping voltammetry of Cu2+ with hierarchical Ti3C2Tx-TiO2 for signal amplification.

The development of effective electrochemical methods for the determination of pesticide residues is highly desirable for food safety requirements. Herein, a novel electrochemical sensing strategy for indirect detection of thiabendazole (TBZ) was achieved by monitoring the anodic stripping peak signal change of media Cu2+ induced by a significant activity difference between active Cu2+ and inactive Cu2+-TBZ complexes. In this sensing system, a heterostructured Ti3C2Tx-TiO2 composite synthesized via a simple in-situ-oxidization strategy is used as the electrode material to boost the anodic stripping peak signal. After optimizing various conditions, the developed sensor presents satisfactory analytical performance for TBZ assay with a linear range from 0.3 to 100.0 nM and a limit of detection as low as 0.1 nM (S/N = 3). Furthermore, the proposed sensing platform also exhibits outstanding anti-interference, repeatability, and stability, which is effective for the determination of TBZ in fruit and water samples.

Machine Learning-Assisted Synchronous Fluorescence Sensing Approach for Rapid and Simultaneous Quantification of Thiabendazole and Fuberidazole in Red Wine.

Rapid analysis of components in complex matrices has always been a major challenge in constructing sensing methods, especially concerning time and cost. The detection of pesticide residues is an important task in food safety monitoring, which needs efficient methods. Here, we constructed a machine learning-assisted synchronous fluorescence sensing approach for the rapid and simultaneous quantitative detection of two important benzimidazole pesticides, thiabendazole (TBZ) and fuberidazole (FBZ), in red wine. First, fluorescence spectra data were collected using a second derivative constant-energy synchronous fluorescence sensor. Next, we established a prediction model through the machine learning approach. With this approach, the recovery rate of TBZ and FBZ detection of pesticide residues in red wine was 101% ± 5% and 101% ± 15%, respectively, without resorting complicated pretreatment procedures. This work provides a new way for the combination of machine learning and fluorescence techniques to solve the complexity in multi-component analysis in practical applications.