In this work, a novel quick, easy, cheap, effective, rugged, and safe technique with hydrophobic natural deep eutectic solvent as both extractant and analyte protectant was developed and combined with gas chromatography–tandem mass spectrometry to analyze pyrethroid residues in tomatoes. Eight hydrophobic natural deep eutectic solvents were first evaluated as analyte protectants and those with decanoic acid or lactic acid as hydrogen bond donor were demonstrated to be effective in compensating for the matrix effects of pyrethroids in the gas chromatography system. Hence, they were added to solvent standards for correcting the quantitation errors instead of matrix‐matched calibration standards. Then the abilities of these acid‐based deep eutectic solvents to extract pyrethriods from tomatoes were evaluated. Results showed the recoveries of all pyrethroids reached to over 80% with only 5 mL menthol:decanoic acid (1:1) used, and good phase separation was easily achieved without the addition of inorganic salt in the extraction step, indicating hydrophobic natural deep eutectic solvent could be a green substitute for acetonitrile in the quick, easy, cheap, effective, rugged, and safe extraction. Compared with the conventional method, the proposed protocol improved the recoveries, reduced the matrix effects, and simplified the extraction step, demonstrating to be an effective, fast, and green method.

A dispersive liquid–liquid extraction based on Pickering emulsion stabilized with ferroferric oxide grafted nitrogen‐doped graphitized carbon black has been developed to simultaneously determine seven aldehydes in environmental water samples, in combination with pentafluorobenzyl hydroxylamine precolumn derivatization gas chromatography–tandem mass spectrometry. The nitrogen‐doped graphitized carbon was prepared from dicyandiamide waste residue with a simple acid wash process. The effects of magnetic emulsifier amount, extraction time, solution pH, and oil/water volume ratio on the formation of magnetically responsive Pickering emulsion and the extraction efficiency of the proposed dispersive liquid–liquid extraction were also investigated. Under the optimized conditions, satisfactory linearities were obtained for all aldehydes with correlation coefficients larger than 0.9984. The limits of detection and quantitation of seven aldehydes were in the range of 17.3–30.1 ng/L and 54.3–103.4 ng/L, respectively, with intra‐ and interday relative standard deviations less than 8.6%. The mean recoveries at three spiked levels ranged from 70.0 to 101.4%. With the Pickering emulsion as a “minimized extractor”, the extraction was accomplished within 5 min. After extraction, the magnetic disperser could be recovered for reuse at least five times by an external magnetic field. The proposed method was demonstrated to be feasible, simple, and economic for the trace analysis of the aldehydes in environmental water samples.

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Rationale Exploring the formation mechanism of the exceptional adducts of alkoxides with Ru(II)–arene cations in alkyl alcohol solution using electrospray ionization mass spectrometry (ESI‐MS) is crucial for further understanding the physicochemical properties of Ru(II)–arene complexes in solution. Methods All mass spectra were collected with an AB SCIEX TripleTOF 5600+ mass spectrometer in positive mode. Theoretical calculations were carried out using the density functional theory method at the B3LYP level with a hybrid basis set consisting of 6‐31G(d,p) and LanL2DZ in the Gaussian 03 program. Results When ruthenated [15]paracyclophanes (Ru‐[15]PCPs) and Ru(II)–arene dimers were dissolved in alkyl alcohol solvents, the adducts of alkoxides with Ru(II)–arene cations were observed under positive ion mode ESI‐MS, which resulted from the coordination of alkyl alcohol molecules with the Ru(II)–arene cations followed by the deprotonation of O‐H bonds of the coordinated alcohols. Furthermore, the number of alkoxides binding to Ru‐[15]PCPs was regulated by the number of ruthenium atoms. Attributed to good solubility and small steric hindrance, the signal intensity of the adducts of methoxides with Ru(II)–arene cations was the strongest among the three alkyl alcohols used in this study. Conclusions The characteristic adducts of alkoxides with Ru(II)–arene cations were pervasively present in positive ion mode ESI‐MS of nine Ru(II)–arene complexes dissolved in alkyl alcohol solvents. Taking into consideration the solubility and signal response, methanol is the most suitable solvent for the ESI‐MS experiments with Ru(II)–arene complexes among the solvents studied, where almost only the diagnostic adducts of methoxides with Ru(II)–arene cations are present.