Dispersive solid phase extraction based on cross-linked hydroxypropyl ß-cyclodextrin polymers for simultaneous enantiomeric determination of three chiral triazole fungicides in water.

An efficient method is presented for simultaneous enantioselective determination of three chiral triazole fungicides (namely paclobutrazol, hexaconazole, and diniconazole) in water samples by DSPE-HPLC-UV. The perfect chiral separation of the enantiomers was achieved on a Chiralpak IH column within 15 min. In order to adsorb and enrich the analytes from water matrices, a cross-linked hydroxypropyl ß-cyclodextrin polymer was synthesized. The prepared material exhibited good adsorption capacity, which was assessed by adsorption kinetic and adsorption thermodynamic experiments. One-variable-at-a-time and the response surface methodology were used to optimize the extraction parameters. Under the optimum sample preparation conditions, good linearity (2.0 ~ 800 µg L-1, R2 ≥ 0.9978), detection limits (0.6 to 1.0 µg L-1), quantitation limits (2.0 to 3.2 µg L-1), recoveries (86.7 ~ 105.8%), and the relative standard deviation (intra-day RSD ≤ 3.7%, inter-day RSD ≤ 5.1%) were obtained, satisfying the requirements of pesticides residues determination. These results demonstrated that the proposed method was applicable for routine determination of chiral triazole fungicide residues in water samples.

Magnetic metal-organic framework MIL-100 (Fe)/polyethyleneimine composite as an adsorbent for the magnetic solid-phase extraction of fungicides and their determination using HPLC-UV.

Fe3O4@MIL-100 (Fe)/PEI are used for the first time as an adsorbent material for the extraction of pesticide residues (epoxiconazole, flusilazole, tebuconazole, and triadimefon) from food matrices. The adsorbent proposed (Fe3O4@MIL-100(Fe)/PEI) was characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), field emission scanning electron microscopy (FE-SEM), thermogravimetric (TG) analysis, and vibrating sample magnetometer (VSM) techniques to evaluate the properties of the sorbent. Then, the Fe3O4@MIL-100 (Fe)/PEI was employed for the quantification of the four triazole fungicides in fruits and vegetables (apple, orange, tomato, cabbage, and cucumber) using HPLC-UV for separation and detection. During the extraction process, the main parameters such as amount of adsorbent, extraction time, pH value, ionic strength, eluting solvent, and eluting volume were optimized. Under the optimum conditions, good linearity of this method was observed for all analytes, with correlation coefficients (R2) ≥ 0.9908. The limits of detection (LODs) ranged from 0.021-3.04 µg kg-1. The extraction recoveries of the four triazole fungicides varied from 73.9 to 109.4% with relative standard deviations (RSD) in the range 0.5 to 6.2%. Compared with other MOFs, the modification of Fe3O4@MIL-100 (Fe) with PEI shows high efficient adsorption due to the combined benefits of MIL-100 (Fe) and PEI. The material is easily synthesized, has good stability, and is of low cost.  Graphical abstract.

Microwave-assisted extraction and high-throughput monolithic-polymer-based micro-solid-phase extraction of organophosphorus, triazole, and organochlorine residues in apple.

A high-throughput micro-solid-phase extraction device based on a 96-well plate was constructed and applied to the determination of pesticide residues in various apple samples. Butyl methacrylate and ethylene glycol dimethacrylate were copolymerized as a monolithic polymer and placed in the cylindrically shaped stainless-steel meshes of 96-micro-solid-phase extraction device and used as an extracting unit. Before the micro-solid-phase extraction, microwave-assisted extraction was employed to facilitate the transfer of the pesticide residues from the apple matrix to liquid media. Then, 1 mL of the aquatic samples was transferred into the 96-well plate and the 96-micro-solid-phase extraction device was applied for the extraction of the selected pesticides. Influential parameters, such as sorbent-to-sorbent reproducibility, microwave-assisted extraction time, ionic strength and micro-solid-phase extraction time, were optimized. The limits of quantitation were below 120 µg/kg, which are lower than the maximum residue limits. The developed method was successfully implemented for the extraction and determination of the selected pesticides from 20 different apple samples gathered from local markets. Phosalone was identified and quantified at the concentration level of 147 (±16.4) µg/kg in one of the samples.

Molecularly imprinted fibers with renewable surface for solid-phase microextraction of triazoles from grape juice samples followed by gas chromatography mass spectrometry analysis.

This paper describes the synthesis and characterization of a new molecularly imprinted solid-phase microextraction fiber able to renew its selective binding sites because of the gradual thermal decomposition of the polymeric network. The injector of the chromatograph operates at 300 °C, and during the desorption step of the analytes (in a short period), the polymeric network is degraded from the surface to the core in volatile compounds that do not interfere with the analysis. The renewable MIP fiber was successfully employed to extract triazole fungicides (triadimenol, tebuconazole, and metconazole) from grape juice samples followed by gas chromatography mass spectrometry analysis. The method was adjusted to the quadratic models from 100 to 2000 µg L(-1), with good precision and accuracy. The limits of quantification (100 µg L(-1) for all analytes) were sufficient to analyze triadimenol, tebuconazole, and metconazole in grape juice samples, where their maximum residue limits in Brazil are 100, 2000, and 1000 µg L(-1), respectively.

Quick synthesis of CoFe-PBA@GO with electrochemical method as a novel, sensitive, and degradable nanocomposite applied in nanofibers for triazole extraction before HPLC-UV analysis.

Today, the wide use of triazole fungicides due to environmental damage and its side effects has raised global concern. Hence, in this research, poly-vinyl alcohol/polyacrylic-acid/CoFe-PBA@GO electrospun nanofiber was synthesized and applied as effective, degradable, and novel adsorbent at pipette-tip microextraction (PT-µSPE) method for the rapid and concurrent extraction of five of triazole fungicides in fruit and vegetable samples prior to quantitative analysis by high-performance liquid chromatography-ultraviolet. The incorporation of CoFe-PBA@GO with superporous structure and abundant functional groups in a polymer medium improves the extraction efficiency of nanofibers due to hydrogen bonding and π-π interactions formed between analytes and synthesized nano-adsorbent. Various important elements that affect the extraction yield of the target analytes were optimized utilizing a time-variable approach. Under the optimum conditions, dynamic range was attained in the range of 0.3-900.0 ng/mL with correlation coefficients ≥ 0.999. The identification limit of the PT-µSPE-HPLC-UV method ranged from 0.1 to 0.3 ng/mL.

Cellulose-based nanocomposite for ultrasonic assisted dispersive solid phase microextraction of triazole fungicides from water, fruits, and vegetables samples.

Herein, an ultrasound-assisted dispersive solid phase microextraction (UA-DSPME) approach has been described for trace level analysis of triazole fungicides in real samples. For this purpose, a new nanosorbent was prepared through modification of carboxymethylcellulose biopolymer with zinc-based metal-organic framework and graphene oxide, and fully characterized. Then, the effect of extraction parameters on extraction efficiency was optimized for the microextraction process. Finally, desorbed triazole fungicides with ethanol were determined using gas chromatography equipped with flame ionization detector. This technique provided good linearity (R2 > 0.99), low detection limits (0.3-1.5 ng mL-1), high preconcentration factors (419-426), good relative recoveries (91.6-102 %), and high repeatability (RSD < 4.1 %) at optimized conditions (amount of sorbent: 15 mg; pH of solution: 7.0; and extraction time; 4 min). Ultimately, this approach was applied to determine triazole fungicides in different water and food samples.

Single and multiple dose pharmacokinetics of maraviroc in saliva, semen, and rectal tissue of healthy HIV-negative men.

BACKGROUND: Antiretroviral pharmacology in seminal plasma (SP) and rectal tissue (RT) may provide insight into antiretroviral resistance and the prevention of sexual transmission of human immunodeficiency virus (HIV). Saliva may be of utility for noninvasively measuring adherence. METHODS: A pharmacokinetic study was performed in 12 HIV-negative men receiving maraviroc 300 mg twice daily for 8 days. Seven time-matched pairs of blood plasma (BP) and saliva samples were collected over 12 h on day 1 (PK1) and days 7 and 8 (PK2). One RT sample from each subject was collected during PK1 and PK2. Two SP samples were collected from each subject during PK1, and 6 SP samples were collected from each subject during PK2. RESULTS: SP AUCs were ∼50% lower than BP. However, protein binding in SP ranged from 4% to 25%, resulting in protein-free concentrations >2-fold higher than BP. RT AUCs were 7.5- to 26-fold higher than BP. Maraviroc saliva AUCs were ∼70% lower than BP, but saliva concentrations correlated with BP (r(2) = 0.58). CONCLUSIONS: More pharmacologically available maraviroc was found in SP than BP. High RT concentrations are promising for preventing rectal HIV acquisition. Saliva correlation with BP suggests that this may be useful for monitoring adherence. CLINICAL TRIALS REGISTRATION: NCT00775294.

Effect of propiconazole on plastic film microplastic degradation: Focusing on the change in microplastic morphology and heavy metal distribution.

With the rapid increase in the use of plastic films, microplastic (MP) pollution in agricultural soils has become a global environmental problem. Propiconazole is widely used in agriculture and horticulture; however, its role in plastic film degradation remains elusive. Butylene adipate-co-terephthalate (PBAT) and polyethylene (PE) films were used to analyze the effects of propiconazole on plastic film and MP degradation. We identified the surface morphologies of PBAT and PE at different propiconazole concentrations and soil pH values, as well as the adsorption and release characteristics of heavy metals during the degradation process via scanning electron microscopy, Fourier transform infrared spectroscopy and inductively coupled plasma mass spectrometry. Propiconazole accelerated the degradation of MPs, adsorption of heavy metals (Ni and Zn), and release of Sn at low concentrations (≤40 mg/kg); however, these effects were evidently absent at a high concentration (120 mg/kg). Furthermore, MPs were more prone to degradation in acidic or alkaline soils than in neutral soil when they coexisted with propiconazole. Hence, we suggest that PBAT and PE plastic films may not be suitable for application in acidic and alkaline soils with propiconazole, because of shorter rupture time and more heavy metal adsorption. PBAT degraded faster, absorbed and released more heavy metals than PE. Under all tested conditions, the heavy metal contents in MPs gradually approached those in soil, which proves that MPs are carriers of heavy metal pollutants. These results may help in assessing the impact of MPs on soil environments and provide a theoretical basis for the standardized propiconazole and plastic film usage.

Adsorption behavior of azole fungicides on polystyrene and polyethylene microplastics.

Agricultural plastic films and triazole fungicides are widely used in agricultural production process. Exposure to natural environment, agricultural plastic films will degrade into micron plastic particles, which will adsorb pesticide molecules and may affect their toxicity, biological activity and persistence. The long-term coexistence of microplastics (MPs) and triazole fungicides will bring potential harms to the agricultural ecological environment. Therefore, two kinds of triazole fungicides flusilazole (FLU) and epoxiconazole (EPO) were selected as cases and the adsorption behaviors of them on polystyrene and polyethylene were investigated. A series of factors which could affect the adsorption behavior were evaluated. Specifically, the particle size of MPs could affect its adsorption capacity, and the smaller the particle size, the stronger the adsorption capacity. Moreover, with the increase of pH value from 6.0 to 9.0, the adsorption capacity of MPs to target compounds gradually increased. The effect of ionic strength was evaluated by NaCl, and 0.05% of NaCl was beneficial to the adsorption process, while the continuous increase of NaCl concentration inhibited the adsorption. Oxalic acid and humic acid decreased the adsorption capacity of flusilazole on PE by 15.99-32.00% and PS by 35.02-48.67%, respectively. In addition, compared with the single pesticide system, the adsorption capacity of MPs for flusilazole and epoxiconazole in the binary pesticides system decreased by 36.13-37.93% and 44.36-51.35%, respectively, indicating that competitive adsorption occurred between the two pesticides. Meanwhile, the adsorption process was evaluated by adsorption kinetics and adsorption isotherms and were consistent with pseudo-second-order kinetic model and Freundlich isotherm model, respectively. Finally, several characterization analyses were conducted to investigated the adsorption mechanism, and hydrogen, halogen bonding and hydrophobic interaction proved to play an important role. The study on the adsorption behavior and mechanism of pesticide on MPs was the basis of assessing the risk of joint exposure.

Development and validation of an HPLC-UV detection assay for the determination of rufinamide in human plasma and saliva.

The development of a simple and rapid high-performance liquid chromatography (HPLC) method for the determination of the new antiepileptic drug rufinamide (RFN) in human plasma and saliva is reported. Samples (250 µl) are alkalinized with ammonium hydroxide (pH 9.25) and extracted with dichloromethane using metoclopramide as internal standard. Separation is achieved with a Spherisorb silica column (250 × 4.6 mm i.d., 5 µm) at 30 °C using as mobile phase a solution of methanol/dichloromethane/n-hexane 10/25/65 (vol/vol/vol) mixed with 6 ml ammonium hydroxide. The instrument used was a Shimadzu LC-10Av chromatograph and flow rate was 1.5 ml min(-1), with a LaChrom L-7400 UV detector set at 230 nm. Calibration curves are linear [r(2) = 0.998 ± 0.002 for plasma (n = 10) and r(2) = 0.999 ± 0.001 for saliva (n = 9)] over the range of 0.25-20.0 µg ml(-1), with a limit of quantification at 0.25 µg ml(-1). Precision and accuracy are within current acceptability standards. The assay is suitable for pharmacokinetic studies in humans and for therapeutic drug monitoring.

Synthesis and application of a novel molecularly imprinted polymer-coated stir bar for microextraction of triazole fungicides in soil.

The preparation, characteristics and application of a sorptive stir bar coated with molecularly imprinted polymer (MIP) using triadimefon as the template molecule are described here. Raw glass capillary was coated with MIP through chemical bonding. The synthesis method was effective and reproducible with the batch-to-batch RSD within 7.8%. Scanning electron micrographs of the stir bar revealed a highly porous coating with average thickness of 15 µm. The synthesized stir bar was proved to be highly stable in most of the solvent for use. Extraction performance showed the fabricated stir bar has excellent molecular recognition abilities for triadimefon and the structure-related compounds, such as triadimenol, diniconazole, flutriafol, hexaconazole, tebuconazole, paclobutrazol and uniconazole, and thus can be applied for simultaneous determination of these triazole fungicides from complex samples by coupling with high-performance liquid chromatography. The variables that influence extraction were optimized with 10.0 µg/L standard solutions of triazole fungicides, and the analytical method was established for the determination of triazole fungicides in soil. The detection limits were in the range of 0.14-0.34 µg/L, and the recoveries were from 86.7 to 114.6% for spiked soil sample.

Chromatographic analysis and residue degradation of phenamacril and difenoconazole on strawberries.

Strawberries are widely cultivated and highly consumed globally, but pests and diseases can severely affect yields. Phenamacril and difenoconazole are high-efficacy pesticides and the mixture of these two pesticides offers a satisfactory option for disease control. In this study, an optimised QuEChERS method combined with dispersive solid-phase extraction purification before injection for simultaneously determining the residues of phenamacril-difenoconazole mixture on strawberries was developed and validated using ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). Average recoveries of phenamacril and difenoconazole in the strawberry matrices ranged from 100% to 104% and 99% to 104%, with relative standard deviations of 2.6%-5.3% and 2.2%-5.5%, respectively. The degradation half-lives of phenamacril and difenoconazole were 3.5-6.6 days and 2.2-3.4 days on strawberries, respectively. Final residues of phenamacril and difenoconazole on strawberries at eight different cultivation regions were 0.033-0.66 mg kg-1 and <0.02-0.089 mg kg-1 after spraying at the maximum dosage recommended by the company of 300 mg a.i. kg-1 twice, respectively. Overall, this study is the first report of phenamacril and difenoconazole residue analysis in strawberries. Therefore, it could provide the reference data for safe management and proper use of phenamacril and difenoconazole in China.

Application of polydopamine functionalized magnetic graphene in triazole fungicides residue analysis.

In this work, a new analytical method based on polydopamine functionalized magnetic graphene (PDA@MG) adsorbent material has been developed to determine three triazole fungicides in water samples. As previous step, a novel polydopamine functionalized PDA@MG adsorbent material has been successfully prepared, which was characterized by fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), transmission electron microscope (TEM), and vibrating sample magnetometer (VSM). Based on this novel material, a new magnetic solid phase extraction (MSPE) method coupled with high performance liquid chromatography (HPLC) has been established for the determination of triazole fungicides in water samples. The main factors which could affect the experimental results were optimized. Under the optimal conditions, good linarites has been achieved in the range of 0.2-50 µg L-1, with the correlation coefficients (R2) were between 0.9962 and 0.9996. The limits of detections (LODs) were 0.0048-0.0084 µg L-1, and the relative standard deviations (RSDs) were between 1.7% and 4.8%. In addition, enrichment factors (EFs) were 572-916 times, which showed triazole fungicides residues could be accurately extracted and analyzed in this way. In the final experiment, the established method was applied to the detection of target analyzes in water samples. Satisfied results could be obtained for tebuconazole, propiconazole, and flusilazole. The recoveries of five water samples were between 69.4% and 106.4%, and the RSD were between 1.0% and 6.5%. The development method is more easy, effective, green and environmental-friendly, and has potential for application.

Hydroxyl-containing porous organic framework coated stir bar sorption extraction combined with high performance liquid chromatography-diode array detector for analysis of triazole fungicides in grape and cabbage samples.

In this work, a hydroxyl-containing porous organic framework (HC-POF) was prepared by a simple solvothermal reaction with 1,4-phthalaldehyde and phloroglucinol as monomers. Sol-gel method was used to coat HC-POF on the glass stir bar. The prepared HC-POF coated stir bar shows better extraction performance for six triazole fungicides (TFs) compared to commercial polydimethylsiloxane and ethylene glycol-silicone coated stir bars. Fourier transform infrared Spectrometry and X-ray photoelectron Spectrometry were used to explore interactions between HC-POF coating and TFs. It is assumed that the coating mainly adsorbs TFs through π-π interactions, hydrogen bonding and hydrophobic interactions. Based on this fact, a new method of HC-POF coated stir bar sorptive extraction combined with high performance liquid chromatography-diode array detector was developed for the determination of six TFs in grape and cabbage samples. A series of extraction and desorption conditions were carefully optimized, including salt concentration, sample solution pH, stirring rate and desorption solvent. Under the optimized experimental conditions, the proposed method displayed limits of detection in the range of 0.022 -0.071 µg L-1, which is the lowest among the reported SBSE methods for target TFs analysis. The linear range for six TFs was 0.1/0.2-500 µg L-1 and the recoveries for the spiked grape and cabbage were 81.0-109% and 80.7-111%, respectively.

Azo-linked porous organic polymers/polydimethylsiloxane coated stir bar for extraction of benzotriazole ultraviolet absorbers from environmental water and soil samples followed by high performance liquid chromatography-diode array detection.

With 4,4'-diaminoterphenyl and phloroglucinol as the monomers, Azo-linked porous organic polymer (PP) was prepared by a green mild azo reaction. Azo-PP is rich in phenolic hydroxyl groups and benzene rings, which can form intermolecular hydrogen bonds with the phenolic hydroxyl groups in interest benzotriazoles (BZTs). The π-π interaction between the benzene ring and the triazole ring would promote the adsorption of target BZTs on Azo-PP. Azo-PP/polydimethylsiloxane (PDMS) coated stir bar was prepared via sol-gel technique for the extraction of target BZTs. Compared with commercial stir bar, Azo-PP coated stir bar showed superior extraction efficiency (75-88% vs 45-65%) under similar conditions and kinetics (50 min vs 120 or 360 min). A method of stir bar sorptive extraction (SBSE) combined with high performance liquid chromatography (HPLC)-diode array detector (DAD) was developed to analyze six target BZT UltraViolet (UV) absorbers. The optimization of SBSE conditions for extraction of interest BZTs was performed by single-factor test. Under the optimized conditions, the limits of detection within 0.12-0.33 µg/L were achieved for six BZT UV absorbers, with the linear range within 0.5-100 µg/L. The method was applied to detect six BZT UV absorbers in the East Lake water, Yangtze River water, and campus soil samples. No BZT was detected in any of the samples. The recoveries of target BZTs in spiked samples were found in the range of 94.9-118%, 96.2-118%, and 88.2-119%.

Rapid quantitative analysis of letrozole, fluoxetine and their metabolites in biological and environmental samples by MEKC.

A micellar electrokinetic chromatographic method has been developed to analyze biological (human serum, saliva and urine) and environmental samples (three different water samples) for letrozole (LE), fluoxetine and their main metabolites. For this purpose a 20 mM borate buffer (pH 9.5) containing 20 mM SDS and 12% v:v 2-propanol was used as the background electrolyte. The samples were hydrodynamically injected for 6 s, separated in a fused-silica capillary at 25 kV and 50 degrees C and detected at 230 nm. Under these conditions, the migration times for all the studied compounds ranged from 3.0 up to 8.0 min. Linearity ranges were determined as 125-1500 ng/mL, whereas detection limits were from 37 to 120 ng/mL in biological samples and a value of 6 ng/mL in water samples. According to the validation study, the developed method was proved to be accurate, precise, sensitive, specific, rugged and robust. This method was applied to the analysis of different biological fluids at clinical levels, including two urine samples from patients undergoing treatment with LE or fluoxetine, and also to environmental samples at potentially polluting level. Prior to the determination, the samples were purified and pre-concentrated by means of an extraction-preconcentration step with a C18 cartridge and by eluting the compounds with methanol.

Removal and transformation pathways of benzothiazole and benzotriazole in membrane bioreactors treating synthetic municipal wastewater.

Lab-scale membrane bioreactors (MBRs), with aerated activated sludge and internal microfiltration module, were used for the treatment of municipal wastewater containing high, yet environmentally relevant, concentrations of benzothiazole (BT) and benzotriazole (BTA). These high production volume compounds are commonly used in the industry and households, and therefore occur ubiquitously in municipal wastewater and the aquatic environment. The aim of this study was to assess the removal of BT and BTA from synthetic municipal wastewater in MBRs and to estimate the contribution of elimination processes and to identify potential biotransformation products. The overall removal of BT and BTA was high, and after the adaptation period, it reached 99.8% and 97.2%, respectively, but recurring periods of unstable BTA removal occurred. The removal due to biotransformation was 88% for BT and 84% for BTA and the disposal with waste sludge accounted for only <1% of the removed load. The remaining fraction of the removed load of BT and BTA was attributed to be retained by phenomena associated with membrane fouling. The adaptation process was reflected in multifold increase in biodegradation kinetic coefficient (kbiol) for BT (reported for the first time) and BTA. Biodegradation was attributed to catabolic mechanism rather than to cometabolism. Hydroxylation was observed to be the main transformation reaction for BT, whereas for BTA hydroxylation, methylation and cleavage of benzene ring were noted. This study has shown the feasibility of treating municipal wastewater with high concentrations of BT and BTA in MBRs and identified potential challenges for the removal of BTA.

A new composite based on graphene oxide-poly 3-aminophenol for solid-phase microextraction of four triazole fungicides in water and fruit juices prior to high-performance liquid chromatography analysis.

An environmentally friendly method which is based on preparation and use of a new composite consisting of poly 3-aminophenol and graphene oxide for solid-phase microextraction of triazole fungicides from natural water and juices is introduced. The composite was synthesized by in-situ polymerization of 3-aminophenol and graphene oxide in weak alkaline media. By using the obtained results from the characterization, a suitable mechanism for polymerization and a proper structure for the polymer were proposed. Under optimal conditions, there are linear relationships between concentration of triazoles and their HPLC peak areas in the range of 0.5-100 µg L-1. The recovery percentages, pre-concentration factors and LOQ for all triazoles were 95.2-98.0%, about 200 and 0.2-0.4 µg L-1, respectively. The offered method was applied for extraction and determination of triazoles from natural water, some juices and it represents a promising alternative method for analysis of triazoles.

Aerobic dissipation of the novel cyanoacrylate fungicide phenamacril in soil and sludge incubations.

The cyanoacrylate ethyl (2Z)-3-amino-2-cyano-3-phenylacrylate (phenamacril), has been introduced as an effective agent against several fungi species belonging to the Fusarium genus. However, in current literature, knowledge about the environmental behavior of this fungicide is limited and there are no data on the degradation in the environment. By performing tests on inherent degradability as well as degradation studies in soils this study provides the only published information regarding the environmental stability and degradation kinetics of this compound. Tests for inherent/ready biodegradation revealed the phenamacril is inherently degradable with zero order kinetics, even though the degradation is comparatively slow. Degradation of phenamacril in soil was found to occur following first order kinetics with a final plateau with a half live of 17.1 days (i.e. more rapidly than tebuconazole but less rapidly than octylisothiazolinone).

Assessment of magnetic core-shell mesoporous molecularly imprinted polymers for selective recognition of triazoles residual levels in cucumber.

Functional magnetic nanomaterials based on molecular imprinting technique were successfully prepared on the surface of modified Fe3O4. Transmission electron microscopy (TEM), Fourier-transform infrared spectroscopy (FTIR), X-ray diffractometer, and vibrating sample magnetometry were applied for characterization of the synthesized magnetic nanoparticles. The magnetic molecularly imprinted polymers (MMIPs) exhibited satisfactory magnetic response, specific recognition, and excellent adsorption capacity toward triazoles (maximum adsorption capacity of 9202.9 µg g-1 for triadimefon). The obtained MMIPs were further used as magnetic dispersive solid-phase extraction (MDSPE) coupled with liquid chromatography-tandem mass spectrometry (LC-MS/MS) for detection of 20 triazoles in cucumber spiked at different levels. The mean recoveries were ranged from 79.9% to 110.3% and relative standard deviations (RSDs) were <11.2% (n = 5). Herein, we report a simple, rapid, environmentally friendly, and magnetic stuff recyclable approach for triazoles residual analysis in complicated agricultural products.