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.

Effect of the Combination of Synthetic Anthelmintics with Carvacryl Acetate in Emulsions with and without a Sodium Alginate Matrix on Haemonchus contortus.

The present study aimed to evaluate the effect of nanoemulsions using combined synthetic anthelmintics, thiabendazole (TBZ), levamisole (LEV), and ivermectin (IVM), with carvacryl acetate (CA) against Haemonchus contortus, and also tested the presence and absence of alginate (ALG). The anthelmintic effect of the CA/TBZ nanoemulsion was evaluated in the egg hatch test (EHT). The effects of CA/IVM and CA/LEV nanoemulsions were evaluated in the larval development test (LDT). The emulsions CA/TBZ/ALG and CA/TBZ showed a multimodal profile, with most particles on the nanometric scale. The encapsulation efficiency in CA/TBZ/ALG was 80.25%, and that in CA/LEV/ALG was 89.73%. In the EHT, CA/TBZ and CA/TBZ/ALG showed mean combination indices (CIs) of 0.55 and 0.36, respectively, demonstrating synergism in both. In LDT, CA/IVM had an average CI of 0.75, and CA/LEV and CA/LEV/ALG showed CI values of 0.4 and 0.93, respectively. It was concluded that CA/TBZ showed a synergistic interaction, and CA/TBZ/ALG showed an enhanced effect. In addition, the matrix brought stability to the product, encouraging its improvement to obtain higher efficacy.

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.

The ABCG2 protein in vitro transports the xenobiotic thiabendazole and increases the appearance of its residues in milk.

Thiabendazole (TBZ) is a broad-spectrum anthelmintic and fungicide used in humans, animals, and agricultural commodities. TBZ residues are present in crops and animal products, including milk, posing a risk to food safety and public health. ABCG2 is a membrane transporter which affects bioavailability and milk secretion of xenobiotics. Therefore, the aim of this work was to characterize the role of ABCG2 in the in vitro transport and secretion into milk of 5-hydroxythiabendazole (5OH-TBZ), the main TBZ metabolite. Using MDCK-II polarized cells transduced with several species variants of ABCG2, we first demonstrated that 5OH-TBZ is efficiently in vitro transported by ABCG2. Subsequently, using Abcg2 knockout mice, we demonstrated that 5OH-TBZ secretion into milk was affected by Abcg2, with a more than 2-fold higher milk concentration and milk to plasma ratio in wild-type mice compared to their Abcg2-/- counterpart.

Co-detection of azoxystrobin and thiabendazole fungicides in mold and mildew resistant wallboards and in children.

The study measured the levels of azoxystrobin (AZ) and thiabendazole (TBZ) in wallboards and metabolite levels of these fungicides in children. The paper covering of wallboard samples contained a higher concentration of AZ and TBZ than the gypsum core, and similar amounts (w/w) of these two fungicides were present in the samples. These data suggest that commercial products containing a 1:1 (w/w) amount of AZ and TBZ, such as Sporgard® WB or Azo Tech™, were applied to the wallboard paper. This is the first detection of TBZ in mold-and-mildew resistant wallboards. The TBZ metabolite, 5OH-TBZ, was detected in 48% of urine samples collected from children aged 40-84 months, and was co-detected with AZ-acid, a common AZ metabolite, in 37.5% of the urine samples. The detection frequency of 5OH-TBZ was positively associated with the detection frequency of AZ-acid. These findings suggest that certain types of wallboards used in homes and commercial buildings may be a potential source of co-exposure to AZ and TBZ in humans.

Highly Sensitive and Wide-Range Detection of Thiabendazole via Surface-Enhanced Raman Scattering Using Bimetallic Nanoparticle-Functionalized Nanopillars.

Thiabendazole (TBZ) is a benzimidazole; owing to its potent antimicrobial properties, TBZ is extensively employed in agriculture as a fungicide and pesticide. However, TBZ poses environmental risks, and excessive exposure to TBZ through various leakage pathways can cause adverse effects in humans. Therefore, a method must be developed for early and sensitive detection of TBZ over a range of concentrations, considering both human and environmental perspectives. In this study, we used silver nanopillar structures (SNPis) and Au@Ag bimetallic nanoparticles (BNPs) to fabricate a BNP@SNPi substrate. This substrate exhibited a broad reaction surface with significantly enhanced surface-enhanced Raman scattering hotspots, demonstrating excellent Raman performance, along with high reproducibility, sensitivity, and selectivity for TBZ detection. Ultimately, the BNP@SNPi substrate successfully detected TBZ across a wide concentration range in samples of tap water, drinking water, juice, and human serum, with respective limits of detection of 146.5, 245.5, 195.6, and 219.4 pM. This study highlights BNP@SNPi as a promising sensor platform for TBZ detection in diverse environments and contributes to environmental monitoring and bioanalytical studies.

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.

Dual-emission carbon dots for ratiometric fluorescence sensing of thiabendazole in fruits.

Quantitative determination of pesticides in fruits and vegetables is essential for human healths. Herein, a new dual-emission carbon dots with high fluorescence stability at a pH range of 4-10 and a temperature range of 0-60 °C was synthesized. And a novel ratiometric fluorescence probe was proposed to detect thiabendazole (TBZ) residue with a wide linear range (0-1000 µM) and low detection limit (0.15 µM). The emission at 512 nm exhibited a special "turn-off" fluorescence sensing of TBZ due to internal filter effect, while that at 361 nm barely changed and worked as reference. Furthermore, the ratiometric fluorescence strategy was successfully applied for determining TBZ in fruits with good recoveries (96.73%-111.17 %, 93.29%-120.78 % and 96.28%-100.57 %, respectively). Notably, the constructed ratiometric fluorescence probe had comparable accuracy to HPLC in detecting unknown concentrations of TBZ in pear juice, demonstrating dual-emission carbon dots possess wide and promising applicability for fluorescence sensing pesticides in the future.

Soluble thiabendazolium salts with anthelminthic properties.

Thiabendazole is an anthelmintic drug used to treat strongyloidiasis (threadworm), cutaneous and visceral larva migrans, trichinosis, and other parasites. The active pharmaceutical ingredient is typically administered orally as tablets that should be chewed before swallowing. Current formulations combine the active ingredient with excipients, including sodium saccharinate as a sweetener. Thiabendazole's low aqueous solubility hinders fast dissolution and absorption through the mucous membranes. We sought to reformulate this medicine to improve both solubility and palatability. We utilized the possibility of protonation of the azole nitrogen atom and selected four different hydrogen donors: saccharin, fumaric, maleic, and oxalic acids. Solvothermal synthesis resulted in salts with each co-former, whereas neat and liquid-assisted grinding enabled the synthesis of additional formulations. Product formation was observed by powder X-ray diffraction. To better understand the structural basis of the proton transfer, we solved the crystal structures of the salts with saccharin, maleic acid, and oxalic acid using single-crystal X-ray diffraction. The structure of the salt with fumaric acid was solved by powder X-ray diffraction. We further characterized the salts with vibrational spectroscopic and thermoanalytical methods. We report a broad tunability of the aqueous solubility of thiabendazole by salt formation. Reformulation with maleic acid provided a 60-fold increase in solubility, while saccharin and oxalic acid gave a modest improvement. Fumaric acid resulted in a solid with only slightly higher solubility. Furthermore, saccharin is a sweetener, while the acids taste sour. Therefore, the salts formed also result in an intrinsic improvement of palatability. These results can inform new strategies for oral and chewable tablet formulations for treating helminthic infections.

3D SERS Substrate of Z-Shaped Ag Nanorod Array for Thiabendazole Detection.

Ag nanoparticles sputtered on silicon wafer are used as masks for the fabrication of silicon columns by ion etching, which induces the growth of the inclined Ag nanorod by inclined Ag sputtering. V-shaped and Z-shaped Ag nanorods can be obtained by varying incline angles and deposition times. SERS detection and FDTD simulation are used to compare and investigate the enhanced electromagnetic coupling of incline nanorod arrays with different shapes in three-dimensional space, which indicates that Z-shaped nanorods show good SERS properties. The Z-shaped Ag nanorod array is used as a SERS substrate for the detection of thiabendazole with a concentration down to 10-11 M.

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.

Tannins Can Have Direct Interactions with Anthelmintics: Investigations by Isothermal Titration Calorimetry.

Plant tannins are known for their anthelmintic and antiparasitic activities and have been increasingly studied to battle the ever-growing problem of anthelmintic resistance. While tannins have been shown to exhibit these activities on their own, one approach would be to use them as complementary nutrients alongside commercial anthelmintics. So far, research on the interactions between tannins and anthelmintics is limited, and few studies have reported both synergistic and antagonistic effects depending on the type of tannin and the method used. These interactions could either strengthen or weaken the efficacy of commercial anthelmintics, especially if tannin-rich diets are combined with anthelmintics used as oral drenches. To study these interactions, a series of hydrolysable tannins (HTs) was selected, and their direct interactions with thiabendazole (TBZ) were evaluated by isothermal titration calorimetry (ITC), which allowed the detection of the exothermic interaction but also the roles and significances of different structural features of HTs in these interactions. Our results show that HTs can have a direct interaction with the benzimidazole anthelmintic TBZ and that the interaction is strengthened by increasing the number of free galloyl groups and the overall molecular flexibility of HTs.

Melamine-Ag with dual functions of electrochemiluminescence luminophore and coreactant accelerators: Construction of MIP/M-Ag@MoS2-QDs sensing platform for specific detection of thiabendazole.

A novel self-enhancement molecularly imprinted electrochemiluminescence (ECL) sensor (MIP/M-Ag@MoS2-QDs/GCE) was constructed to detect thiabendazole (TBZ) in food. Melamine was used as template to chelate Ag+ to prepare composite nanomaterials (M-Ag). M-Ag possesses both ECL properties and coreactant catalytic properties, which can realize the self-enhancement of ECL luminophore. MoS2-QDs with excellent edge activity and electrochemical reaction catalytic activity were used to accelerate the reaction rate of the microsystem and further enhance the ECL intensity. The specific detection method of TBZ was established by investigating the ECL response mechanism and specific recognition mechanism of MIP/M-Ag@MoS2-QDs/GCE. The ECL intensity was proportioned to the lg C(TBZ) in the linear range 5 × 10-8 mol L-1-5 × 10-5 mol L-1 with a limit detection of 1.42 × 10-8 mol L-1. The satisfactory recovery rate (83.57%-101.03%) was obtained in sample analysis, which was in good agreement with the analysis result of HPLC.

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.

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.

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.

Developmental defects induced by thiabendazole are mediated via apoptosis, oxidative stress and alteration in PI3K/Akt and MAPK pathways in zebrafish.

Thiabendazole, a benzimidazole fungicide, is widely used to prevent yield loss in agricultural land by inhibiting plant diseases derived from fungi. As thiabendazole has a stable benzimidazole ring structure, it remains in the environment for an extended period, and its toxic effects on non-target organisms have been reported, indicating the possibility that it could threaten public health. However, little research has been conducted to elucidate the comprehensive mechanisms of its developmental toxicity. Therefore, we used zebrafish, a representative toxicological model that can predict toxicity in aquatic organisms and mammals, to demonstrate the developmental toxicity of thiabendazole. Various morphological malformations were observed, including decreased body length, eye size, and increased heart and yolk sac edema. Apoptosis, reactive oxygen species (ROS) production, and inflammatory response were also triggered by thiabendazole exposure in zebrafish larvae. Furthermore, PI3K/Akt and MAPK signaling pathways important for appropriate organogenesis were significantly changed by thiabendazole. These results led to toxicity in various organs and a reduction in the expression of related genes, including cardiovascular toxicity, neurotoxicity, and hepatic and pancreatic toxicity, which were detected in flk1:eGFP, olig2:dsRED, and L-fabp:dsRed;elastase:GFP transgenic zebrafish models, respectively. Overall, this study partly determined the developmental toxicity of thiabendazole in zebrafish and provided evidence of the environmental hazards of this fungicide.