Cucurbit[7]uril as a matrix solid-phase dispersion for the extraction of quaternary ammonium pesticides from vegetables and their determination using HPLC-UV.

Cucurbit[7]uril (Q[7]) was first used as a dispersant sorbent material in a matrix solid-phase dispersion for the simultaneous extraction of four quaternary ammonium pesticides from vegetables before analysis using high-performance liquid chromatography with UV detection. Q[7] exhibited a better selectivity and adsorption capability for these compounds, which is due to its ability to bind selectively organic molecules into its hydrophobic cavity and to form stable host-guest inclusion complexes. Various parameters affecting the extraction were investigated and optimized, such as sorbent/sample mass ratio, grinding time, rinsing and eluting conditions. Under optimized conditions, the proposed method exhibited a linear response in the concentration range of 1-100 µg·kg-1, satisfactory recoveries for eight types of vegetable samples (>70%), and high repeatability (RSD < 9.0%). The limits of quantification were between 0.43 µg·kg-1 and 0.99 µg·kg-1, which is nearly 50 times lower than the maximum residue limits established by the European Council.

Specific recognition of cationic paraquat in environmental water and vegetable samples by molecularly imprinted stir-bar sorptive extraction based on monohydroxylcucurbit[7]uril-paraquat inclusion complex.

Molecularly imprinted stir-bar coatings were created based on a hydroxylcucurbit[7]uril-paraquat inclusion complex. The inclusion complex that contained paraquat (PQ) as a template and monohydroxylcucurbit[7]uril ((OH)Q[7]) as a monomer was preassembled mainly through cavity inclusion interaction of (OH)Q[7] to form a one-dimensional self-assembly structure. The inclusion complex was anchored chemically on the surface of a glass stir bar with hydroxy-terminated poly(dimethylsiloxane) by the sol-gel technique to obtain a molecularly imprinted polymer-coated stir bar (MIP-SB). The molecularly imprinted coating showed specific adsorption for cationic PQ in aqueous media. Other quaternary amine compounds with a similar structure that coexisted in the solution, such as ethyl-viologen, diquat, and difenzoquat, were almost not extracted by the prepared MIP-SB. The sorptive capacity of the MIP-SB for PQ was nearly four times that of the non-imprinted stir bar (NIP-SB). The recognition mechanism indicated that the selectivity and extraction capacity resulted mainly from the imprinted cavity in the polymer that was formed by a one-dimensional assembly structure consisting of the (OH)Q[7]-PQ inclusion complex. The imprinted cavity was complementary to the PQ in shape, size, and functionality. A method to determine PQ in environmental water and vegetable samples was developed by combining MIP-SB sorptive extraction with HPLC-UV. The linear range was from 100 to 10,000 ng L-1 with a 8.2 ng L-1 detection limit for water samples and 0.02-0.85 mg kg-1 with a 0.005 mg kg-1 detection limit for vegetable samples. The limit of detection for both samples was lower than the EU-established maximum residual levels and that of other previously reported methods. The average recoveries were 70.0-96.1% with a relative standard deviation ≤ 7.6%, which showed the successful application in real sample analysis. Molecularly imprinted stir-bar coatings were created based on a hydroxylcucurbit[7]uril-paraquat (PQ) inclusion complex, which showed a specific recognition toward cationic PQ. A method to determine PQ in environmental water and vegetable samples was established by combining MIP-SB sorptive extraction with HPLC-UV.