Rapid sequential detection of Al3+ and glyphosate using an "Off-On-Off" fluorescent probe based on salicylate modified layered double hydroxides.

A fluorescent probe based on salicylate modified layered double hydroxide (LDH-SA) is presented, enabling the swift sequential detection of Al3+, fosetyl-Al and glyphosate in aqueous environment. The probe was synthesized using a simple co-precipitation procedure, and its properties and synthesis conditions were thoroughly characterized and optimized. A unique "off-on-off" fluorescent response was observed when the probe sequentially interacted with Al3+ and glyphosate, and the detection method based on this phenomenon was established. The limits of detection for Al3+ and glyphosate were determined as 0.03 µmol/L and 0.03 mg/L, respectively, with rapid detection periods of one minute and four minutes. The LDH-SA/Al3+ complex requires Al3+ to generate a chelation-gathered fluorescence effect, which is the mechanism by which it quenches LDH-SA. This is possible due to the inhibition of excited-state intramolecular proton transfer and photoinduced electron transfer processes within LDH-SA after incorporating Al3+. Upon interaction with glyphosate, competitive complexation between glyphosate and Al3+ is initiated, which leads to a recovery of the fluorescence spectrum of LDH-SA and demonstrating the "off-on-off" behavior. An "INHIBIT" logic gate system was devised utilizing the response, indicating potential applications in fluorescence-based devices. Such a rapid, sequential detection capacity is impressive. It attests to the utility of LDH-SA as a probe for Al3+ or glyphosate, and suggests promise for applications in pollutant analysis or environmental monitoring applications.

Rapid visual dual-mode detection of Zr(IV) based on L-histidine functionalized gold nanoparticles.

Heavy metal pollution has always been a great threat to human health and safety. Compared with other heavy metals, although zirconium ion (Zr(IV)) is equally harmful, due to the lack of research on Zr(IV) in the biological systems and environment, its detection does not seem to have received the attention it deserves. Herein, a rapid visual dual-mode detection (colorimetric and chrominance method) of Zr(IV) based on L-histidine functionalized gold nanoparticles (HIS-AuNPs) has been reported. AuNPs and HIS-AuNPs before and after adding Zr(IV) were characterized by UV-Vis, TEM, DLS, Zeta potential, EDS and FT-IR, etc. These results showed that L-histidine was successfully modified on the surface of AuNPs by forming a stable Au-N bond, and its modification had little effect on the dispersion degree of AuNPs. After the addition of Zr(IV), interaction of this metal ion with the imidazolyl group on L-histidine can obviously cause the aggregation of HIS-AuNPs within 12 min, and the dispersion state and particle size of HIS-AuNPs can be significantly changed. These two detection modes were established by means of absorbance and color change of solution, and being used in addition and recovery experiments of Zr(IV) in natural water. Under the optimal conditions, these two modes exhibited good linearity within 15-70 and 20-100 µmol L-1, and limit of detection of 2.62 and 6.25 µmol L-1. The proposed method was highly sensitive and selective, which provided a new convenient way to realize the detection of Zr(IV).

Construction of a three-mode sensor based on gold nanoparticles and carbon quantum dots as probes for the detection of thiosemicarbazone.

In this study, ginkgo leaves were used as a carbon source to synthesize carbon quantum dots (CQDs) with uniform particle size, high fluorescence (FL) intensity and strong stability, using a hydrothermal method. FL could be quenched by the FL resonance energy transfer effect between CQDs and gold nanoparticles (AuNPs), an important FL quenching agent. The electrostatic attraction between thiosemicarbazone (TSC) and citrate on the surface of AuNPs and the formation of a stable Au-S bond between TSC and AuNPs led to the aggregation of AuNPs and thus weakened the quenching effect on CQDs and partly recovered the FL. A sensor in FL mode for the detection of TSC was constructed based on the above-mentioned FL "off" and "on" phenomena. The results showed a good linear correlation in the concentration range 0-1.75 µM, and the limit of detection was as low as 0.05 µM. In addition, the aggregation of AuNPs caused by TSC also led to a change in the absorbance curve and color of the solution; colorimetric and chrominance detection modes were also constructed using these two types of changes, with sensitive responses ranging 0-2.25 µM and 0-1.60 µM and the limits of detection of 0.03 µM and 0.08 µM, respectively. More importantly, these three detection modes obtained satisfactory recovery rates in the detection of the TSC content in river water, liquor and wheat samples, and the detection results were mutually verified (95.18% to 104.96%).

Promising adsorbent for dye detoxification: Exploring the potential of chitosan sodium carboxymethylcellulose silk fibroin aerogel.

The main goal of this study is to create a CS-CMC-SF aerogel consisting of chitosan sodium carboxymethylcellulose and silk fibroin. The aerogel is designed to remove types of dyes from water while also being environmentally friendly. This innovative adsorbent has been optimized for extracting both cationic and anionic dyes from solutions. It incorporates chitosan sodium carboxymethylcellulose and silk filament fibers to enhance its strength. Experimental data illustrates that the CS-CMC-SF aerogel possesses remarkable adsorption capabilities - 5461.77 mg/g for Congo Red (CR), 2392.83 mg/g for Malachite Green (MG), and 1262.20 mg/g for Crystal Violet (CV). A kinetic study aligns with the pseudo-second-order kinetic model suggesting predominant chemisorption phenomena occur during adsorption process. Isotherm analysis further identifies multilayered adsorption occurring on irregularly shaped surfaces of the aerogel while thermodynamic assessments validate exothermic and spontaneous characteristics inherent in its absorption mechanism. Several analytical methods such as SEM, FT-IR, XRD, and XPS were employed to examine physicochemical attributes tied to this unique material design conceptually; identifying mechanisms including pore filling, π-π interactions, ion exchange activity, electrostatic connections along with hydrogen bonding inducing overall superior performance output. Furthermore substantial soil biodegradability alongside compostable features associated with our proposed CS-CMC-SF aerogels established it's potential suitability within applications demanding sustainable options thereby validating its underlying ecological credibility.

An 'on-off-on' fluorescent switch based on a luminous covalent organic framework for the rapid and selective detection of glyphosate.

Glyphosate, the most used herbicide in the world, has a residue problem that cannot be ignored. However, glyphosate itself does not have fluorescence emission and lacks the conditions for fluorescence detection. In this work, a rapid and selective fluorescence detection method of glyphosate was designed by an 'on-off-on' fluorescent switch based on a luminous covalent organic framework (L-COF). Only the fixed concentration of Fe3+ as an intermediate could trigger the fluorescent switch and no incubation step was required. The proposed method showed good accuracy with a correlation coefficient of 0.9978. The method's limits of detection and quantitation were 0.88 and 2.93 µmol/L, which were lower than the maximum allowable residue limits in some regulations. Environmental water samples and tomatoes were selected as actual samples to verify the application in a complex matrix. A satisfactory mean recovery from 87% to 106% was gained. Furthermore, Fe3+ could induce fluorescence quenching of L-COF through the photo-induced electron transfer (PET) effect, while the addition of glyphosate could block the PET effect to achieve detection. These results demonstrated the proposed method had abilities to detect glyphosate and broaden the application of L-COF.

Phenylboronic acid-functionalized magnetic metal-organic framework nanoparticles for magnetic solid phase extraction of five benzoylurea insecticides.

This research involves the construction of a phenylboronic acid-functionalized magnetic UiO-66 metal-organic framework (MOF) nanoparticle (CPBA@UiO-66@Fe3O4). Its design is primarily for the magnetic solid phase extraction (MSPE) of benzoylurea insecticides. An organic ligand, 2-amino terephthalic acid (2-ATPA), facilitated the introduction of amino groups while keeping the original crystal structure of UiO-66 intact. The constructed UiO-66 MOF showcases a porous structure and extensive surface area, thereby providing an optimal platform for further functionalization. The employment of 4-carboxylphenylboronic acid as a modifier notably amplified the extraction efficiency for benzoylureas. This improvement was due to the formation of B-N coordination and other secondary interactions. By integrating this with high-performance liquid chromatography (HPLC), we established a quantitative analytical method for benzoylurea insecticides. This method achieved a wide linear range (2.5-500 µg L-1 or 5-500 µg L-1), satisfactory recoveries (83.3-95.1%), and acceptable limits of detection (LODs: 0.3-1.0 µg L-1). The developed method proved successful when applied to six tea infusion samples, representing China's six major tea categories. Semi-fermented and light-fermented tea samples demonstrated relatively higher spiking recoveries.

Construction of multiple modes using gold nanoparticles as probes for the rapid detection of fenpyroximate.

Herein, three patterns for the detection of fenpyroximate based on the response signal of gold nanoparticles are described. The strong interaction between the guanidine group of arginine-modified gold nanoparticles and the ester group of fenpyroximate led to the aggregation of the nanoparticles and to a variation of ultraviolet-visible light spectrum and color of the solution. Sensors were constructed based on the correlation of the concentration of fenpyroximate with the absorbance ratio (A650/A525) and the R value was obtained by extracting the color of the test solution by using a smartphone to take a photo of the solution, which was then analyzed by colorimeter software. The absorbance ratio increased linearly in the range of 0.225-0.375 mg L-1 and the limit of detection was 0.215 mg L-1, while the R value declined linearly in the range of 0.20-0.40 mg L-1 and the limit of detection was 0.21 mg L-1. Further, the gold nanoparticles could cause a fluorescence quenching of fluorescent dyes, such as rhodamine B, and it was found that the fluorescence could be quenched and then restored after aggregation; therefore, a fluorescence method based on fluorescence "off-on" was constructed, and the fluorescence quenching was found to increase linearly in the range of 0.0-1.0 mg L-1 and the limit of detection was 0.013 mg L-1. These three patterns indicated highly selective and sensitive response signals for fenpyroximate, and all were applied to the detection of fenpyroximate in apple juice, pear juice, and environmental water samples, with the results showing that the three methods could be mutually verified, with the recoveries ranging from 94.15% to 110.65%.

Bimetallic metal-organic frameworks-based ratiometric fluorescence sensor for the quantitative detection of thiram in fruits samples.

The identification of residual thiram (Tr) in foods is vital in view of its harmful effects on human health. Herein, a ratiometric fluorescence sensor (I435/I590) based on rhodamine B/NH2-MIL-53(Al0.75Fe0.25) was constructed for the detection of Tr. Interestingly, the probe RhB/NH2-MIL-53(Bim) assisted by Cu2+ could rapidly and sensitively recognize Tr with a low detection limit of 0.11 µg/mL in 10 min. The fluorescence sensing mechanism was investigated using fluorescence spectra, UV-Vis absorption spectra, the fluorescence lifetime and quantum yield. The results showed that the excellent sensing performance was attributed to fluorescence resonance energy transfer, electrostatic interaction, and photoinduced electron transfer. In addition, the practical application of this platform showed acceptable relative recoveries for Tr (84.03-107.81 %), and precisions were also achieved (relative standard deviation ≤ 8.69 %, n = 3). These results show that the presented herein can be applied to monitor the Tr content in real fruit samples.

Enhanced cyanogen chloride formation after UV/PS and UV/H2O2 pre-oxidation and chlorination in natural river water.

Ultraviolet/persulfate (UV/PS) and Ultraviolet/hydrogen peroxide (UV/H2O2) have attracted much attention in recent years as advanced oxidation processes for water treatment. However, it is not all clear how these two methods affect the formation of cyanogen chloride (CNCl) in the subsequent water chlorination process. In this study, it was found that both UV/H2O2 and UV/PS pre-oxidation promoted the formation of CNCl in six actual water samples collected from urban rivers. Glycine, uric acid, arginine and histidine were investigated as the model compounds to explore the effects of different methods on the production of CNCl. The results showed that compared with chlorination alone, pre-oxidation by UV/H2O2 and UV/PS can reduce the production of CNCl for glycine and uric acid by up to 95% during post-chlorination process. However, they can greatly promote the formation of CNCl for arginine and histidine by up to 120-fold. In a more detailed investigation, pre-oxidation of histidine formed highly reactive intermediates to chlorine, leading to increased CNCl formation and chlorine consumption. The results showed that the precursors of CNCl was altered after pre-oxidation, and need to be re-evaluated.

Dual-mode detection of fluorine-containing pesticides (bifenthrin, flufenoxuron, diflubenzuron) via ratiometric fluorescence and the Tyndall Effect of fluorescent organic nanoparticles.

The Tyndall Effect assay (TEA) has been applied into colorimetric metal ion detection since 2019. However, the TEA-based sensor for pesticide detection has never been reported till now. Herein, a facile fluorescent organic nanoparticle (FON)-based sensor is firstly developed for fluorine-containing pesticide detection through ratiometric fluorescence assay (FLA) and TEA. For FLA, the intensity of the second-order Tyndall scattering peak (STS590nm) and the fluorescence peak of the FON-based sensor would increase and remain unchanged respectively when adding bifenthrin, flufenoxuron, and diflubenzuron. The detection limits were respectively 9.34, 6.91, and 3.60 µg/kg. For TEA, the increased STS590nm intensity displayed a bright and visible light beam. An economical, simple, and portable device was then constructed to visually monitor the analytes. The sensor was successfully used to detect the analytes in teas through FLA and TEA with the recoveries and RSD ranging from 86.27-100.00 %, and 0.00-5.68 %, respectively.

[Polyamidoamine dendrimer-functionalized silica nanocomposite with polydopamine coating for dispersive micro solid-phase extraction of benzoylurea insecticides in water samples].

Pesticides are used in the agricultural production process to ensure the yield and quality of agricultural products. However, in recent years, environmental pollution issues caused by pesticide residues have sparked widespread concern in society. It is important to develop convenient and efficient approaches to detect and monitor pesticide residues. In this study, targeting benzoylurea insecticides (BUs), polyamidoamine dendrimer-functionalized silica nanocomposite with polydopamine coating (SiO2-PAMAM-PDA) was designed and successfully synthesized. First, monodisperse silica nanoparticles were prepared by the hydrolysis of tetraethyl orthosilicate (TEOS) in mixed solution of ethanol, water and ammonia. The silane coupling agent (3-aminopropyl)triethoxysilane was then employed to introduce amino groups into the silica. Silica with the zeroth generation of polyamidoamine (PAMAM) modification (SiO2-PAMAM-G0) was obtained through Michael addition reaction of methyl acrylate. Ethylenediamine was added to polymerize with methyl acrylate using an amidation reaction to form the first-generation PAMAM (SiO2-PAMAM-G1). Finally, by polymerizing dopamine under alkaline conditions (pH=8.5), the SiO2-PAMAM-G1 was coated with PDA. Thus, the final product named SiO2-PAMAM-PDA was obtained. The composite was characterized using a transmission electron microscope (TEM) and an increase in surface roughness indicated the successful grafting of PDA coating. Dopamine structure contains abundant benzene rings and amino and hydroxyl groups. It could bind with BUs through multiple secondary interactions, such as hydrogen bond and π-π stacking interaction. Therefore, the introduction of PDA could effectively enhance the affinity of the material toward benzoylurea insecticides. The prepared nanocomposites were used as sorbents in a dispersive micro solid-phase extraction approach (D-µ-SPE). The established approach was employed to extract and enrich the BUs in water samples before high-performance liquid chromatography (HPLC) analysis. Diflubenzuron, triflumuron, hexaflumuron, and teflubenzuron were chosen as target analytes. The following was a typical D-µ-SPE procedure. The prepared adsorbents measuring 40 mg were first dispersed in an 8-mL sample solution containing 150 g/L NaCl. The dispersion was assisted by 120-s vortexing to ensure full contact between the SiO2-PAMAM-PDA and the targets. Next, the adsorbents were separated from the liquid phase by 4-min centrifugation (5000 r/min). Thereafter, the adsorbed benzoylureas were eluted using 1 mL acetonitrile as desorption solvent by 120-s vortexing. Separated by centrifugation, the eluate was dried under a mild nitrogen stream. The solid remains were redissolved in 0.1 mL of acetonitrile, filtered by filter membrane (0.22 µm), and then analyzed by HPLC. The experimental conditions in the D-µ-SPE process could have a great impact on the extraction efficiency. Experimental conditions were optimized using a single factor optimization approach to further enhance the extraction recoveries. The optimized conditions included adsorbent amount, extraction time, desorption solvent type, desorption solvent volume, desorption time, and NaCl addition amount. Under the optimal conditions, a linearity range of 10-500 µg/L and limits of detection (LODs, S/N=3) of 1.1-2.1 µg/L were obtained. The extraction recoveries and relative standard deviations (RSDs) of the four BUs were 82.8%-94.1% and 2.1%-8.0%, respectively. The established approach was compared with reported approaches targeting benzoylurea insecticides. It was discovered that this approach consumed less sample, material, organic solvent, and pretreatment time. It provided a more rapid and green choice for the determination of benzoylurea pesticides. To determine the applicability, the proposed approach was applied to analyze the four benzoylurea insecticides in three river water samples. The real water samples were pretreated using the developed approach ahead of instrumental analysis, and no benzoylurea pesticides residue was detected. Next, standard addition experiments were performed under three spiking levels, including 15, 50, and 200 µg/L. The established approach had good accuracy and feasibility with satisfactory recoveries (69.5%-99.4%) and RSDs (0.2%-9.5%).

An ultralow concentration of Al-MOFs for turn-on fluorescence detection of aflatoxin B1 in tea samples.

A turn-on fluorescent sensing platform based on an ultralow concentration of Al-metal organic frameworks for the detection of aflatoxin B1 has been developed for the first time. This fluorescence turn-on sensor exhibits the largest fluorescence enhancement (or quenching) constant value of 179404 M-1 among all luminescence-based chemical sensors reported till date. Moreover, the sensor afforded a rapid detection of aflatoxin B1, with a linear response in the concentration range of 0.05-9.61 µM and a low detection limit of 11.67 ppb. Additionally, the fabricated sensor showed good repeatability, reproducibility, stability, and selectivity. Most importantly, the practical application of this sensor has been demonstrated by detecting aflatoxin B1 in complex tea samples with low relative standard deviation (≤7.72%; n = 3) and satisfactory recoveries. In summary, the proposed method has great potential as a simple, sensitive and selective strategy for monitoring aflatoxin B1 in food samples.

A fluorescent organic nanoparticles-based sensor synthesized through hydrothermal process and its application in sensing Hg2+ of real samples and fast visual detection.

The fluorescent organic nanoparticles (FONs)-based sensor has been attracting great attention in recent years. There are still big challenges in the preparation and application of FONs-based sensor. In this study, a FONs-based sensor was designed and developed through facile hydrothermal process using 3-perylenecarboxaldehyde (PlCA) as the fluorophore and L-methionine (Met) as the recognition site for mercury ions. According to the experimental results, the fluorescence intensity of the as-prepared PlCA-M would decrease when adding Hg2+ and the mechanism was extrapolated to be photoinduced electron transfer inducing by specific coordination interaction. The acquired PlCA-M-based sensor was used to monitor Hg2+ in several real samples (environmental water, tea, and apple) with the limit of detection being 60 nM. Remarkably, a visual detection device based on FONs, SDS-PAAG (sodium dodecyl sulfate polyacrylamide gel) @PlCA-M was firstly constructed and successfully used to Hg2+ semi-quantitation by naked eyes. In addition, the acquired FONs was applied into imaging tool for security information detection and identified as solid-state luminescent material for the first time.

Optimizing Photochirogenic Performance by Solvent-Driven Conformational Fixation in Enantiodifferentiating Photoisomerization of (Z)-Cyclooctene Mediated by Sensitizing ß-Cyclodextrin Hosts.

Catalytic enantiodifferentiating photoisomerization of cyclooctene (1Z) included and sensitized by regioisomeric 6-O-(o-, m-, and p-methoxybenzoyl)-ß-cyclodextrins (CDs) was performed under a variety of solvent conditions for higher enantioselectivities. The enantiomeric excess (ee) of chiral (E)-isomer (1E) produced was a critical function of all the internal and external factors examined, in particular, the sensitizer structure and the solvent conditions, to afford (R)-1E in record-high ee's of up to 67% upon sensitization with the meta-substituted ß-CD host in water and salt solutions but neither in 50% aqueous ethanol nor with the ortho- and para-substituted hosts. The mechanistic origin of the sudden ee enhancement achieved under the specific conditions is discussed on the basis of the circular dichroism spectral behaviors upon substrate inclusion and the compensatory enthalpy-entropy relationship of the activation parameters for the enantiodifferentiating photoisomerization.

A facile and total water-soluble fluorescent organic nanoparticles-based sensor for Hg2+ detection and its application in tea samples.

In this study, a novel FONs-based sensor P-M(w) was synthesized using 1-Pyrenecarboxaldehyde and L-methionine through facile hydrothermal strategy. The fluorescence emission peaks of the acquired P-M(w) would show specific changes after the addition of Hg2+ due to interfering the PET process and inducing nano-structure conformational rigidification of P-M(w). Notably, the water-soluble FONs-based sensor was firstly used to detect Hg2+ in tea samples providing a new material choice for the fluorescence sensor construction of metal ion detection. Besides, the qualitative and quantitative analysis of Hg2+ could be carried out with P-M (w) at a very low concentration (1 µg/mL) meaning that the acquired P-M(w) synthesized by few grams of reactants may satisfy the detection of approximate fifty thousand samples.

Phenylboronic acid-functionalized cross-linked chitosan magnetic adsorbents for the magnetic solid-phase extraction of benzoylurea pesticides.

In this study, a 4-formylphenylboronic acid-modified cross-linked chitosan magnetic nanoparticle (FPBA@CCHS@Fe3 O4 ) was fabricated. The synthesized material was utilized as the magnetic solid-phase extraction adsorbent for the enrichment of six benzoylurea pesticides. In addition to B-N coordination, FPBA@CCHS@Fe3 O4 interacts with benzoylureas through hydrogen bonds and π-π stacking interaction on account of rich active groups (amino and hydroxyl) and aromatic rings in structure. Compared to traditional extraction methods, less adsorbent (20 mg) and reduced extraction time (3 min) were achieved. The adsorbent also exhibited good reusability (no less than 10 times). Coupled with a high-performance liquid chromatography-diode array detector, satisfactory recoveries (89.1-103.9%) and an acceptable limit of detection (0.2-0.7 µg/L) were obtained. Under optimized conditions, the established method was successfully applied to the tea infusion samples from six major tea categories with acceptable recoveries ranging from 76.8 to 110%, indicating its application potential for the quantitative detection of pesticides in complex matrices.

Colorimetric assay based on arginine-functionalized gold nanoparticles for the detection of dibutyl phthalate in Baijiu samples.

In this paper, a simple and innovative colorimetric method is established, which is based on DBP-induced aggregation of arginine functionalized gold nanoparticles (ARG-AuNPs), and can be used for the sensitive determination of dibutyl phthalate (DBP) in Baijiu samples. The morphological characteristics and the color changes of ARG-AuNPs caused by aggregation show good sensitivity, and can be observed through ultraviolet-visible spectroscopy, Fourier transform infrared (FT-IR) spectroscopy, transmission electron microscopy (TEM), dynamic light scattering (DLS) and zeta potential technology. The color change of ARG-AuNPs from red to blue is due to the strong non-covalent interactions between DBP and ARG-AuNPs (electrostatic, van der Waals force and hydrogen bonding), which leads to the reduction of the electrostatic repulsion between the nanoparticles and aggregation. A two-stage linear equation was established between the absorption ratio (A690/A530) and the DBP concentration (0.0-2.8 mg L-1); the correlation coefficient (R2) was 0.9914-0.9940, and the detection limit (LOD) was estimated at 0.05 mg L-1. The designed ARG-AuNPs acting as a dependable sensor for the detection of Baijiu samples equally acquired satisfactory recoveries. When the concentration of DBP in the solution is more than 1.0 mg L-1, the color change can be clearly observed by the naked eye; so there is no need for sample preparation techniques and tedious operations to quickly and semi-quantitatively detect DBP. The successful application of the proposed method in Baijiu samples indicates its potential to detect DBP in more complex environment samples.

Perfluoro octanoic acid-modified magnetic hyperbranched polyamideamine as a sorbent for the extraction of fluorine-containing pesticides from water samples.

Perfluoro octanoic acid was modified on the surface of magnetic hyperbranched polyamideamine by acid amine condensation. The morphology and chemical composition of perfluoro octanoic acid-modified magnetic hyperbranched polyamideamine was characterized by transmission electron microscopy, Fourier transform infrared spectroscopy, zeta potential, particle size analysis, Brunauer-Emmett-Teller measurement, and X-ray photoelectron spectroscopy. Perfluoro octanoic acid-modified magnetic hyperbranched polyamideamine was applied in magnetic solid phase extraction for the separation and enrichment of four fluorine-containing pesticides (indoxacarb, metaflumizone, cyflumetofen, and cyhalothrin). The magnetic solid phase extraction method based on perfluoro octanoic acid-modified magnetic hyperbranched polyamideamine has low method detection limits (0.30-0.49 µg/L), a satisfactory coefficient of determination (0.9995-0.9999), wide linear ranges (2.5-250 µg/L), and good repeatability (intraday: 2.6-4.7%; interday: 1.1-7.9%). The enrichment factors and extraction efficiences varied from 55 to 76 and 69 to 96%, respectively. The sorbent-to-sorbent reproducibility was in the range of 3.2-7.6%, indicating that the synthesis of the sorbent was reliable. For the detection of actual water samples, the relative recoveries were in the range from 80.1 to 114.4% with relative standard deviations less than 9.6%. The calculation results of quantum chemistry calculations showed that after the modification of perfluoro octanoic acid, the interaction between the sorbent and four fluorine-containing pesticides was stronger.

1-Octyl-3-methylimidazolium hexafluorophosphate-functionalised magnetic poly ß-cyclodextrin for magnetic solid-phase extraction ofpyrethroids from tea infusions.

In this study, a novel sorbent, 1-octyl-3-methylimidazolium hexafluorophosphate functionalised magnetic poly ß-cyclodextrin, was successfully synthesised and applied to magnetic solid-phase extraction for the determination of pyrethroids in tea infusions. The sorbent was characterised by transmission electron microscopy, energy-dispersive spectroscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, vibrating sample magnetometer and Brunauer-Emmett-Teller measurement. All factors affecting extraction efficiency, such as sorbent amount, extraction time, ionic strength and desorption conditions, were optimised individually. Under the chosen conditions, wide linearity (2.5-500 µg L-1) with determination coefficients ranging from 0.9995 to 0.9999, low limits of detection of 0.32-0.54 µg L-1 and good precision (intra-day: 2.6-7.0%; inter-day: 3.5-7.6%) were achieved for four pyrethroids in tea infusions. The relative recoveries of target analytes in real tea infusion samples were from 70% to 101% with relative standard deviations lower than 9.1%. We conclude that the proposed method is promising in the detection of pyrethroids in tea infusions.

Use of 1-octyl-3-methylimidazole hexafluorophosphate modified magnetic hyperbranched polyamideamine as sorbent for the extraction of pyrethroid insecticides from tea infusion.

Magnetic hyperbranched polyamideamine was carboxylated using succinic anhydride and modified further with 1-octyl-3-methylimidazole hexafluorophosphate successively. The morphology and chemical composition of the prepared material was characterized by transmission electron microscopy, scanning electron microscopy, Fourier transform infrared spectroscopy, Brunauer-Emmett-Teller measurement, X-ray photoelectron spectroscopy, etc. 1-Octyl-3-methylimidazole hexafluorophosphate modified magnetic hyperbranched polyamideamine was used as sorbent in the magnetic solid-phase extraction for the separation and enrichment of five pyrethroid insecticides from tea infusion. The magnetic solid-phase extraction method proposed in this article has low method detection limits (0.53-0.71 ng/mL), acceptable coefficient of determination (0.9992-0.9998), wide linear ranges (2.5-500.0 ng/mL), and good repeatability (intraday: 1.2-6.3%; interday: 1.6-5.4%). In the detection of five pyrethroid insecticides in tea infusion, relative recoveries were in the range from 87.7 to 114.7% with satisfactory relative standard deviations (0.2-7.4%). With the aid of quantum chemistry calculations, the interaction energy between the sorbent and five pyrethroid insecticides was calculated, which proved the necessity of the modification of 1-octyl-3-methylimidazole hexafluorophosphate.