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Several hyperbranched polysilicon (HBPS) materials with different end group modifications were designed and synthesized and the structures were characterized. The modified HBPS polymers were applied to the adsorption of benzoylurea insecticides (BUs). The binding mode and binding energy between the HBPS and BUs were quantified and the results of an adsorption kinetics study and an adsorption thermodynamics experiment were verified by calculation and mutual verification. The adsorption mechanism of BUs onto HBPS was also discussed. The theoretical results show that the most effective way to combine the adsorbent and BUs is via hydrogen bonding when the end group is an amino group. Moreover, the most effective combination when the end group is β-cyclodextrin is the interaction of the BUs with the interior of the cavity to form a host–guest coating. The theoretical results of other end group-modified HBPS materials were also obtained and verified by adsorption experiments. In this work, an experimental method for obtaining the binding mode by theoretical calculations and then verifying it according to adsorption experiments was established.

A new microextraction technique named in-syringe low-density ionic liquid dispersive liquid–liquid microextraction (LDIL-DLLME) followed by separation using high performance liquid chromatography has been developed to determine the levels of four pyrethroid insecticides (i.e., deltamethrin, fenvalerate, permethrin, and bifenthrin) in environmental water samples. In the developed method, an ionic liquid (IL) was used for the first time instead of an organic solvent, which is most often used in low-density solvent-based microextraction methods. The IL was placed in a long syringe needle using a microsyringe. It was then dispersed by drawing the sample solution into the syringe. The extraction was finished in the syringe, taking full advantage of the low-density property, and making this method easier and quicker. Several parameters affecting the experimental efficiency of LDIL-DLLME, such as the needle's inner diameter, salt addition, the volume of IL and sample, rotation speed and duration of centrifugation and ultrasound were thoroughly studied. Under optimized conditions, in the range of 1 to 500 μg L−1, good linearity was obtained, with coefficients of determination greater than 0.9994. Three spiked water samples were studied, and recovery ranged from 88.0 to 102.8%, with relative standard deviations (RSDs) ranging from 0.3 to 6.7%. The limits of detection (LODs) for the four pyrethroid insecticides were in the range of 0.88–1.71 μg L−1 and enrichment factors (EFs) were in the range of 242 to 257. The proposed method provides an inexpensive, rapid, simple and eco-friendly process for evaluating pyrethroid insecticides in environmental samples, making it a potential method for the pretreatment of experimental samples.

A novel and simple method for effervescence-assisted dispersive liquid–liquid microextraction based on the solidification of a floating ionic liquid using a special collection method combined with high-performance liquid chromatography is developed for the determination of four benzoylureas in water samples. In this method, the ionic liquid (IL), trihexyl(tetradecyl)phosphonium tetrafluoroborate, is used rather than organic drops, which have limitations, as the extraction solvent for the first time in dispersive liquid–liquid microextraction based on the solidification of floating organic drops (DLLME-SFO). Due to the high viscosity of the IL, it can be quickly collected in the lid of the centrifuge tube after solidification, which combines the advantages of both dispersive liquid–liquid microextraction and liquid phase microextraction based on the solidification of a floating IL. Furthermore, effervescence is used to disperse the IL, thereby avoiding the use of an organic dispersant. The influence of various experimental factors, such as the form of the effervescent material, IL quantity, base to acid ratio in the effervescent tablet, weight ratio of IL to effervescent tablet, ultrasonication time, centrifugation time, extraction temperature, sample pH, extraction time and salt addition, are optimized using a central composite design and the one-factor-at-a-time approach. Under the optimal conditions, good linearity was obtained for the four BUs from 2 to 500 μg L−1, with correlation coefficients ranging from 0.9994 to 0.9995. The recoveries were 90.2–100.2% with relative standard deviations ranging from 1.3–4.4%. The limits of detection for the analytes were between 0.77 to 1.58 μg L−1, and the enrichment factors ranged from 206 to 228. Additionally, this method was successfully applied for the determination of four BUs in real water samples.

A novel dispersive liquid–liquid microextraction (DLLME) method is proposed for the detection of five acaricides (clofentezine, fenpyroximate, diafenthiuron, pyridaben and spirodiclofen) in tea infusions prior to analysis by high-performance liquid chromatography (HPLC). For this method, a nanofluid prepared by dispersing magnetic zinc oxide nanoflower (FeO4@ZnO) nanoparticles in 1-octyl-2,3-dimethylimidazolium bis(trifluoromethanesulfonimide) was used as an extractant. After extraction, the nanofluid was magnetically collected by the addition of FeO4@ZnO nanoparticles without centrifugation. In DLLME, the joint use of an ionic liquid (IL)-based nanofluid and magnetic retrieval is unprecedented and makes this microextraction process rapid and effective. The main parameters affecting the extraction efficiency were optimized by an orthogonal experiment and a single-factor experiment using tea infusions. Under the optimal conditions, the recoveries of the analytes were between 83.0 and 104.4%, the limits of detection ranged from 0.44 to 1.0 μg L−1, and the intra-day precision and inter-day precision were both lower than 7.5%. The proposed method was successfully applied to the analysis of acaricides in four tea infusions, and the recoveries were between 79.2 and 93.1%, with RSDs of 0.4 to 5.8%. The developed method is promising as an environmentally friendly, convenient, and efficient sample preparation technique.

A novel liquid phase microextraction method based on the solidification of floated ionic liquids (SFIL-LPME) was developed to determine four phthalate esters (diethyl phthalate, diallyl phthalate, benzyl butyl phthalate, and dicyclohexyl phthalate) in environmental waters and bottle beverages and subsequently separate them using high-performance liquid chromatography. In this work, we customized a tributyldodecylphosphonium tetrafluoroborate ([P4 4 4 12][BF4]) ionic liquid (IL) to obtain a low density such that it can be solidified at a low temperature, and then used as an extraction solvent in liquid-phase microextraction based on the solidification of floated organic drops (SFO-LPME). This means that more potential ILs can be customized to broaden extraction solvents in SFO-LPME. To identify the significant factors that affect extraction efficiency, parameters such as the volume of [P4 4 4 12][BF4], the extraction time, the rotation speed, the extraction temperature and the ionic strength were optimized using a Plackett–Burman design. A central composite design was then used to optimize the identified significant factors to study the effect of interactions on the experiment. Under these optimized conditions, the extraction recoveries of the four phthalate esters in water samples ranged from 73.0 to 94.6% and in bottled beverage were from 70.2 to 101.3%, with relative standard deviations (RSDs) ranging from 0.6 to 8.2% and 0.6 to 7.8%. Good linearity for both water samples and bottled beverages were obtained in the range of 5–500 μg L−1, with correlation coefficients greater than 0.9993. The limits of detection for the four phthalate esters varied from 0.27 to 1.1 μg L−1 for water samples and 1.22 to 2.36 μg L−1 for bottled beverages. The two developed methods were then successfully applied to the determination of phthalate esters in environmental waters and bottled beverages.

A novel and simple ionic-liquid-mingled air-assisted liquid–liquid microextraction based on solidification of floating organic droplets combined with high performance liquid chromatography was developed for the determination of six benzoylureas (BUs) in water and honey samples. In this method, a mixture of low-density and low melting point extraction solvents and aqueous sample solutions was rapidly sucked up and injected several times using a glass syringe. The influence of the main factors on the efficiency of this procedure is studied. Under the optimal conditions, the enrichment factors (EFs) for BUs were acquired in the range of 144 to 187, limits of detection (LODs) were between 0.01 and 0.1 μg L−1 and limits of quantitation (LOQs) were changed in the range of 0.03 and 0.33 μg L−1. The obtained extraction recoveries ranged from 84.03% to 109.20% with intra-day lower than 4.5%, and inter-day precision lower than 6.5%. The method is successfully applied to determine the BUs in environmental water and honey samples with recoveries in the range of 78.57–109.72%, which proved the potential use of this method in real samples.