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.

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.

Iridium solvent complex as a new sensitive probe to detect benzimidazole pesticides based on photoluminescent signals "switch-on" via coordination mechanism.

An iridium solvent complex (abbreviated as Ir-probe) has been synthesized and reported as a new photoluminescent "switch-on" probe to detect benzimidazole pesticides via coordination mechanism in this work. This new probe could successfully distinguish benzimidazole pesticides from other kinds of common pesticides widely used in agriculture activities. Thiabendazole (TBZ) and carbendazim (CBZ) as the representative benzimidazole pesticides, this probe exhibited good analytical performance with the linear ranges of 0.05 µM to 20 µM for TBZ and 3 µM to 40 µM for CBZ, and the corresponding limit of detection (LOD, 3σ/S) is 0.03 µM and 0.5 µM for analyzing TBZ and CBZ, respectively. In addition, the proposed method in this work also has good recoveries in analyzing TBZ and CBZ residues in the real samples.

Highly sensitive and rapid detection of thiabendazole residues in oranges based on a luminescent Tb3+-functionalized MOF.

Thiabendazole (TBZ), has been extensively employed as a pesticide and/or a fungicide in agriculture, while its residues would threaten to public health and safety. Simple, rapid and sensitive probes for detection of TBZ in real food samples is significantly desirable. In present work, a highly selective and sensitive luminescent sensor for monitoring TBZ in oranges has been constructed based on a Tb3+-functionalized Zr-MOF (Tb3+@1). Tb3+@1 exhibited many attractive sensing properties toward TBZ, including broad linear range (0-80 µM), high selectivity, low LOD (0.271 µM) and rapid response time (less than1 min). Moreover, the probe was employed to determine TBZ in real orange samples, in which good recoveries from 98.41 to 104.48% were obtained. It only takes 35 min for the whole process of detection TBZ in real orange samples combined with QuEChERS method. Therefore, this work provided a reliable and rapid method for monitoring the TBZ in real orange samples.

Experimental and theoretical characterization of the strong effects on DNA stability caused by half-sandwich Ru(II) and Ir(III) bearing thiabendazole complexes.

The synthesis and characterization of two half-sandwich complexes of Ru(II) and Ir(III) with thiabendazole as ancillary ligand and their DNA binding ability were investigated using experimental and computational methods. 1H NMR and acid-base studies have shown that aquo-complexes are the reactive species. Kinetic studies show that both complexes bind covalently to DNA through the metal site and non covalently through the ancillary ligand. Thermal stability studies, viscosity, circular dichroism measurements and quantum chemical calculations have shown that the covalent binding causes breaking of the H-bonding between base pairs, bringing about DNA denaturation and compaction. Additionally, molecular dynamics (MD) simulations and quantum mechanics/molecular mechanics (QM/MM) calculations shed light into the binding features of the Ru(II) and Ir(III) complexes and their respective enantiomers toward double-helical DNA, highlighting the important role played by the NˆN ancillary ligand once the complexes are covalently linked to DNA. Moreover, metal quantification in the nucleus of SW480 colon adenocarcinoma cells were carried out by inductively coupled plasma-mass spectrometry (ICP-MS), both complexes are more internalized than cisplatin after 4 h of exposition. However, in spite of the dramatic changes in the helicity of the DNA secondary structure induced by these complexes and their nuclear localization, antiproliferative studies have revealed that both, Ru(II) and Ir(III) complexes, cannot be considered cytotoxic. This unexpected behavior can be justified by the fast formation of aquo-complexes, which may react with components of the cell culture medium or the cytoplasm compartment in such a way that they may become deactivated before reaching DNA.

Thiabendazole and Thiabendazole-Formic Acid Solvate: A Computational, Crystallographic, Spectroscopic and Thermal Study.

Thiabendazole (TBZ) is a substance which has been receiving multiple important applications in several domains, from medicine and pharmaceutical sciences, to agriculture and food industry. Here, a comprehensive multi-technique investigation on the molecular and crystal properties of TBZ is reported. In addition, a new solvate of the compound is described and characterized structurally, vibrationally and thermochemically for the first time. Density functional theory (DFT) calculations were used to investigate the conformational space of thiabendazole (TBZ), revealing the existence of two conformers, the most stable planar trans form and a double-degenerated-by-symmetry gauche form, which is ~30 kJ mol-1 higher in energy than the trans conformer. The intramolecular interactions playing the major roles in determining the structure of the TBZ molecule and its conformational preferences were characterized. The UV-visible and infrared spectra of the isolated molecule (most stable trans conformer) were also calculated, and their assignment undertaken. The information obtained for the isolated molecule provided a strong basis for the understanding of the intermolecular interactions and properties of the crystalline compound. In particular, the infrared spectrum for the isolated molecule was compared with that of crystalline TBZ and the differences between the two spectra were interpreted in terms of the major intermolecular interactions existing in the solid state. The analysis of the infrared spectral data was complemented with vibrational results of up-to-date fully-periodic DFT calculations and Raman spectroscopic studies. The thermal behavior of TBZ was also investigated using differential scanning calorimetry (DSC) and thermogravimetry. Furthermore, a new TBZ-formic acid solvate [2-(1,3-thiazol-4-yl)benzimidazolium formate formic acid solvate] was synthesized and its crystal structure determined by X-ray diffraction. The Hirshfeld method was used to explore the intermolecular interactions in the crystal of the new TBZ solvate, comparing them with those present in the neat TBZ crystal. Raman spectroscopy and DSC studies were also carried out on the solvate to further characterize this species and investigate its temperature-induced desolvation.

Pesticide mediated oxidative stress induces genotoxicity and disrupts chromatin structure in fenugreek (Trigonella foenum - graecum L.) seedlings.

Here we report cytototoxic and genotoxic potentials of four commonly used pesticides, including, tricyclazole, thiabendazole (fungicides), plethora and slash-360 (insecticides) in the non-target tropical crop plant Trigonella foenum - graecum L. (fenugreek). Three different concentrations of the selected pesticides were used. For fungicides, 0.05% and for insecticides, 0.1% concentration represents recommended doses, while, 2X and 4X concentrations of the recommended dose were used to test their phytotoxic effects. Inhibition of germination and seedling growth were clearly observed at 4X concentration of the pesticides. Tricyclazole and plethora showed more pronounced effects than the other two agrochemicals. The pesticides, particularly at 4X concentrations clearly induced oxidative stress and cytotoxic effects in Trigonella seedlings with appreciable reduction in mitotic index, induction of chromosomal abnormalities in root meristematic cell and decreased level of accumulation of some key cell cycle regulators, including CDK1, CDK2 and Cyclin B1.Detection of accumulation of DNA double strand breaks and histone H2AX phosphorylation in pesticide treated seedlings have revealed direct genotoxic effects of the selected pesticides. Overall, our results provide insights into the mechanism of pesticide induced cytotoxic and genotoxic effects in plant genome with future implications for designing pesticides to minimize their deleterious effects on non-target crop plants.

Thiabendazole/bentonites hybrids as controlled release systems.

Clay minerals are commonly used in pharmaceutical products as excipients and active agents. New drug vehicles based on clay minerals have been developed. In this work, sodium (BentNa), calcium (BentCa) and magnesium (BentMg) exchanged bentonites were used for the sorption of thiabendazole (TBZ), and their potential use as controlled release systems was evaluated. Pristine bentonite and exchanged bentonites were characterized by X-ray diffraction, infrared spectroscopy, thermogravimetry and transmission electron microscopy (TEM), and the influence of the different parameters such as pH, contact time and initial concentration of the drug was investigated. The maximum adsorption reached after 45 min period with 2000 mg L-1 of thiabendazole to BentNa and after 105 min with 1300 mg L-1 to BentCa and BentMg, respectively. The maximum adsorbed quantities of thiabendazole were 164.4; 152.3 and 133.3 mg g-1 for BentNa, BentCa and BentMg, respectively. The emission profiles obtained for the bentonite/drug hybrids were similar when simulated body fluids were used and these emission profiles were fitted according to the Korsmeyer-Peppas kinetic model.

Fabrication of gold nanorods for SERS detection of thiabendazole in apple.

Thiabendazole (TBZ) is a kind of pesticide that is widely used in agriculture, and its residue may pose a threat to human health. In order to measure TBZ residues in food samples, a surface-enhanced Raman spectroscopy (SERS) method combined with a homogeneous and reusable gold nanorods (GNR) array substrate was proposed. GNR with a high uniformity was synthesized and then applied to the self-assembly of a GNR vertically aligned array. The relative standard deviation (RSD) of the array for SERS could reach 15.4%, and the array could be reused for more than seven times through the treatment of plasma etching. A logarithmic correlation between TBZ concentration and Raman intensity was obtained, with the best determination coefficient (R2) and the corresponding limit of detection (LOD) of 0.991 and 0.037 mg/L in methanol solution, and 0.980 and 0.06 ppm in apple samples, respectively. The recoveries of TBZ in apple samples ranged from 76% to 107%. This study provided a rapid and sensitive approach for detecting TBZ in apples based on SERS coupled with GNR array substrate, showing great potential for analyzing other trace contaminants in food matrices.

Kinetic and equilibrium adsorption of two post-harvest fungicides onto copper-exchanged montmorillonite: synergic and antagonistic effects of both fungicides' presence.

The simultaneous adsorption of both imazalil (IMZ) and thiabendazole (TBZ) fungicides in a Cu2+-exchanged Mt was studied in this work. Kinetic studies were used to determine the rate law which describes the adsorption of individual fungicides onto the adsorbent. Adsorption isotherm of individual and combined fungicides was done to evaluate synergic or antagonistic effects. The Mt-Cu material considerably improved TBZ and/or IMZ adsorption from aqueous suspensions with respect to raw Mt, leading to removal efficiencies higher than 99% after 10 min of contact time for TBZ and IMZ Ci = 15 and 40 mg/L, respectively, when a solid dosage = 1 g/L was used. The adsorption sites involved were determined by a combination of X-ray diffraction (XRD) determinations and electron paramagnetic resonance (EPR), indicating that fungicides were bonded to Cu2+ cations, while the rate limiting step was the formation of coordination bonds. The adsorption mechanism proposed is that of ligand exchange between water and fungicide molecules in the metal coordination sphere. The single-crystal structure for the IMZ-Cu2+ complex indicated that four molecules were bounded to the copper centers, while two molecules of TBZ are bounded to copper explaining the higher IMZ uptake capacity for the Mt-Cu material. Graphical abstract.

Molecularly imprinted polymer monolith containing magnetic nanoparticles for the stir-bar sorptive extraction of thiabendazole and carbendazim from orange samples.

In this work, a novel molecularly imprinted stir-bar was developed for the stir-bar sorptive extraction (SBSE) of thiabendazole (TBZ) and carbendazim (CBZ) from orange samples. Magnetic nanoparticles were surface modified with oleic acid and then encapsulated by a silica shell using a conventional sol-gel procedure. Subsequently, nanoparticles were functionalized with methacrylate functionalities by grafting onto the particles surface. Finally, the modified magnetic nanoparticles were entrapped in a polymer monolith synthetized by copolymerization with the imprinting polymerization mixture using a glass vial insert as a mold. Variables affecting the polymerization and rebinding conditions of target analytes were optimized. The uptake capacity for the template (TBZ) was evaluated as well as the cross-reactivity for the related compound CBZ by rebinding experiments. Finally, the proposed magnetic imprinted monolith was applied to the SBSE of TBZ and CBZ from orange sample extracts providing a remarkable clean-up ability. The calculated detection limit were 0.13 and 0.10 mg kg-1 for CBZ and TBZ respectively, low enough to satisfactory analysis of both compounds in orange samples according to current European Union regulations.

Thiabendazole-based Rh(III) and Ir(III) biscyclometallated complexes with mitochondria-targeted anticancer activity and metal-sensitive photodynamic activity.

Two pairs of Rh(III) and Ir(III) biscyclometallated complexes with thiabendazole (L1), named [Ir-a]Cl and [Rh-a]Cl, and N-benzyl-thiabendazole (L2), named [Ir-b]Cl and [Rh-b]Cl, have been designed and synthesized to explore the photophysical and biological effects that arise from changing both the metal center and the ancillary ligand. In the dark, the four metal complexes exhibit greater cytotoxicity than cisplatin against human colon (SW480) and human lung (A549) adenocarcinoma cell lines. Moreover, the pair of complexes bearing the ligand L2 is markedly more cytotoxic and present higher uptake values than complexes with L1, thereby their biological properties were studied further to determine their mechanism of action. Interestingly, in spite of the different metal center both the [Ir-b]Cl and [Rh-b]Cl complexes are responsible for the loss of mitochondrial functionality and the activation of apoptotic cell death pathways. Moreover, the photodynamic activity of the four complexes, [Ir-a,b]Cl and [Rh-a,b]Cl, was tested using visible blue light (460 nm) under soft irradiation conditions (20 min, 5.5 mW cm-2). While the Rh complexes are not photopotentiated, the phototoxicity index (IC50 non-irradiated/IC50 irradiated) of [Ir-a]Cl and [Ir-b]Cl complexes was 15.8 and 3.6, respectively. We also demonstrate that only the Ir derivatives are capable of photocatalyzing the oxidation of S-containing l-amino acids under blue light irradiation, [Ir-a]Cl being more active than [Ir-b]Cl, which provides a reasonable mechanism for their biological action (oxidative stress could be selectively promoted through a photocatalytic action) upon irradiation. This different PDT behaviour depending on the metal center and the ancillary substituent may be useful for future rational design of metal-based photosensitizers.

Sorption of thiabendazole in sub-tropical Brazilian soils.

Thiabendazole (TBZ) is an ionizable anthelmintic agent that belongs to the class of benzimidazoles. It is widely used in veterinary medicine and as a fungicide in agriculture. Sorption and desorption are important processes influencing transport, transformation, and bioavailability of xenobiotic compounds in soils; data related to sorption capacity are therefore needed for environmental risk assessments. The aim of this work was to assess the sorption potential of TBZ in four Brazilians soils (sandy, sandy-clay, and clay soils), using batch equilibrium experiments at three pH ranges (2.3-3.0, 3.8-4.2, and 5.5-5.7). The Freundlich sorption coefficient (K F) ranged from 9.0 to 58 µg1-1/n  (mL) 1/n  g-1, with higher values generally observed at the lower pH ranges (2.3-3.0 and 3.8-4.2) and for clay soils. The highest organic carbon-normalized sorption coefficients (KOC) obtained at pH 3.8-5.7 (around the natural pH range of 4.1-5.0) for both clay soils and sandy-clay soil were 3255 and 2015 mL g-1, respectively. The highest correlations K F vs SOM (r = 0.70) and K F vs clay content (r = 0.91) were observed at pH 3.8-4.2. Our results suggest that TBZ sorption/desorption is strongly pH dependent and that its mobility could be higher in the studied soils than previously reported in soils from temperate regions.

Development and validation of a method to determine thiabendazole and o-phenylphenol in wastewater using micellar liquid chromatography-fluorescence detection.

A micellar liquid chromatographic method to determine thiabendazole (TBZ) and o-phenylphenol in wastewater is described here. The sample was directly injected without any additional treatment other filtration. The pesticides were resolved in <11 min, using a mobile phase of 0.10 M SDS-6% 1-pentanol buffered at pH 3 running through a C18 column at 1 mL/min. The detection was performed by fluorescence at 305/360 and 245/345 nm excitation/emission wavelengths for TBZ and o-phenylphenol, respectively. The method was validated following the directives of the Validation and Peer Review of U.S. Environmental Protection Agency Chemical Methods of Analysis guidelines in terms of selectivity, quantitation range (0.01-0.02 to 2 mg/L), detection limit (0.005-0.008 mg/L), trueness (92.1-104.2%), precision (<13.9%), robustness (<6.6%), and stability under storage conditions. The procedure was applied to the screening of TBZ and o-phenylphenol in wastewater samples from citrus packing plants, agricultural gutters, urban sewage, as well as in influent and effluent wastewater treatment plants.

Spectrofluorometric and thermal gravimetric study on binding interaction of thiabendazole with hemoglobin on epoxy-functionalized magnetic nanoparticles.

The interaction of thiabendazole (Tbz) with hemoglobin (Hb) on epoxy-functionalized iron oxide nanoparticles was presented in this study. The binding capacity of Tbz was determined by measuring at an excitation wavelength of 299 nm using fluorescence spectroscopy. The thermodynamic parameters of the Hb-Tbz interaction were calculated from Stern-Volmer and van't Hoff equations. The values of enthalpy change, ∆H, and entropy change, ∆S, were found to be 0.20 kJ mol(-1) and 0.70 J mol(-1) K(-1), respectively, which indicates that the hydrophilic interaction plays a main role in the binding process. The interaction ability was confirmed by Fourier transform infrared spectroscopy (FT-IR) and scanning electron microscopy (SEM). Also, the thermal behavior of the Hb-Tbz interaction on functionalized iron oxide nanoparticles was studied by using the thermogravimetric analysis (TGA) technique in the temperature range of 25-950 °C, and then the kinetic parameters for the thermal decomposition were determined using the Horowitz-Metzger method.

Synthesis and antifungal activity of ethers, alcohols, and iodohydrin derivatives of sclareol against phytopathogenic fungi in vitro.

This study synthesized 20 sclareol derivatives. The antifungal activities of these derivatives were evaluated in vitro against five phytopathogenic fungi using the mycelium growth rate method. Among all the tested compounds, compound 16 with one iodine atom and three hydroxyl groups displayed higher fungicidal activities against all the tested phytopathogenic fungi than precursor sclareol. Compound 16 also showed more pronounced antifungal activities against Curvularia lunata (IC50=12.09 µg/mL) and Alternaria brassicae (IC50=14.47 µg/mL) than the positive control, a commercial agricultural fungicide thiabendazole.

Cu(II)-dipeptide complexes of 2-(4'-thiazolyl)benzimidazole: synthesis, DNA oxidative damage, antioxidant and in vitro antitumor activity.

Two new Cu(II)-dipeptide complexes of 2-(4'-thiazolyl)benzimidazole, [Cu(Gly-Gly)(TBZ)(Cl)]·4H2O (1) and [Cu(Gly-l-Leu)(TBZ)(Cl)]·H2O (2) (Gly-Gly=glycyl-glycine anion, Gly-l-Leu=glycyl-l-leucine anion and TBZ=2-(4'-thiazolyl)benzimidazole) have been synthesized and characterized by elemental analyses, molar conductance measurements and spectroscopy methods (IR, UV-visible, electrospray ionization mass spectra (ESI-MS) and EPR). The DNA binding and cleavage properties of the complexes monitored by multi-spectroscopic techniques (UV absorption, fluorescence and circular dichroism), viscosity determination and agarose gel electrophoresis indicated that the complexes bound to calf thymus (CT)-DNA via a partial intercalative mode with considerable intrinsic binding constants (Kb=1.64×10(5)M(-1) for 1 and 2.59×10(5)M(-1) for 2), and cleaved pBR322 DNA efficiently in the mediation of ascorbic acid (AA), probably via an oxidative damage mechanism induced by OH. The antioxidant activities of the complexes have been evaluated by means of modified nitroblue tetrazolium (NBT) photoreduction and cellular antioxidant activity (CAA) assays using HepG2 cells as a model, and it was found that IC50 values of 1 and 2 for dismutation of O2(-) were 0.172 and 0.247µM, respectively, and the CAA50 values were 10.57 and 10.74µM. In addition, the complexes were subjected to in vitro cytotoxicity against three human carcinoma cell lines (HeLa, A549 and HepG2), which revealed that the complexes exhibited effective cytotoxicity (IC50 values varying from 33.17 to 100µM) and selective inhibition toward HeLa cell lines. These findings indicate that the complexes have the potential to act as effective metallopeptide chemotherapeutic agents.

PREPARATION OF B-CYCLODEXTRIN-THIABENDAZOLE-PIPERONYL BUTOXIDE SUPRAMOLECULAR COMPLEX AND ITS ACTIVITY AGAINST BLUE AND GREEN MOULD DECAY ON INOCULATED SATSUMA FRUIT.

The supramolecular complex of ß-cyclodextrin-thiabendazole-piperony butoxide (ßCD-TBZ/PBO) was prepared and its structure was characterized by 1H NMR. Additionally, the antifungal activity of ßCD-TBZ/PBO was investigated in comparison with the commercially available thiabendazole (TBZ) fungicide by in vitro tests and on artificially inoculated 'Okitsu' satsuma fruit dipped in water at 20 degrees C or at 50 degrees C to control postharvest blue (Penicillium italicum) and green mould (P. digitatum). ß-CD-TBZ/PBO is stable for several months when stored as powder in a dark bottle. At pH 7.0 the water solubility of the ßCD-TBZ/PBO complex was consistently higher than free TBZ. Water dip at 20 degrees C did not affect decay incidence caused by blue mould but favoured the development of green mould during 4-8 days of storage at 20 degrees C with respect to untreated (control) fruit. Water at 50 degrees C effectively reduced the incidence of blue mould and totally suppressed green mould during the first 4 days but lost its efficacy afterwards. By contrast, both TBZ and ßCD-TBZ/PBO had a lasting effect and were equally effective in controlling green and blue mould decay when applied at 20 degrees C and 60 mg L(-1) active ingredient (a.i.). When applied at 50 degrees C and 20 mg L(-1) a.i. the activity of the complex against blue mould was inferior than the corresponding treatment with TBZ. In vitro assays revealed a significant effectiveness of ßCD-TBZ/PBO complex at low concentration compared to commercial formulation of TBZ.

New approach to solar photo-Fenton operation. Raceway ponds as tertiary treatment technology.

The photo-Fenton process has proven its efficiency in the removal of micropollutants. However, the high costs usually associated with it prevent a spread of this technology. An important factor affecting costs is the kind of photoreactor used, usually tubular with a reflecting surface. Tubular reactors like compound parabolic collectors, CPCs, involve high capital costs. In comparison, the application of less costly reactors such as the extensive raceway ponds (RPRs) would help to spread the use of the photo-Fenton process as tertiary treatment at commercial scale. As far as the authors know, RPRs have never been used in advanced oxidation processes (AOPs) applications. This work is aimed at studying the applicability of RPRs to remove micropollutants with solar photo-Fenton. For this purpose, a pesticide mixture of commercial acetamiprid (ACTM) and thiabendazole (TBZ) (100µg/L each) was used in simulated secondary effluent. Iron concentration (1, 5.5 and 10mg/L) and liquid depth (5, 10 and 15cm) were studied as process variables. TBZ was removed at the beginning of the treatment (less than 5min), although ACTM removal times were longer (20-40min for the highest iron concentrations). High treatment capacity per surface area was obtained (48mg/hm(2) with 5.5mg Fe/L and 15cm liquid depth), proving the feasibility of using RPRs for micropollutant removal.

Novel metal-ion-mediated, complex-imprinted solid-phase microextraction fiber for the selective recognition of thiabendazole in citrus and soil samples.

A novel metal-ion-mediated complex-imprinted-polymer-coated solid-phase microextraction (SPME) fiber used to specifically recognize thiabendazole (TBZ) in citrus and soil samples was developed. The complex-imprinted polymer was introduced as a novel SPME coating using a "complex template" constructed with Cu(II) ions and TBZ. The recognition and enrichment properties of the coating in water were significantly improved based on the metal ion coordination interaction rather than relying on hydrogen bonding interactions that are commonly applied for the molecularly imprinting technique. Several parameters controlling the extraction performance of the complex-imprinted-polymer-coated fiber were investigated including extraction solvent, pH value, extraction time, metal ion species, etc. Furthermore, SPME coupled with HPLC was developed for detection of TBZ, and the methods resulted in good linearity in the range of 10.0-150.0 ng/mL with a detection limit of 2.4 ng/mL. The proposed method was applied to the analysis of TBZ in spiked soil, orange, and lemon with recoveries of 80.0-86.9% and RSDs of 2.0-8.1%. This research provides an example to prepare a desirable water-compatible and specifically selective SPME coating to extract target molecules from aqueous samples by introducing metal ions as the mediator.