This study describes an extraction method based on silylated extraction vessel-dispersive liquid-liquid microextraction (SEV-DLLME) for preconcentration of some triazole pesticides (penconazole, hexaconazole, tebuconazole, diniconazole, triticonazole, and difenconazole) from aqueous samples. For this purpose, the interior surface of funnel-shaped extraction vessel is activated by concentrated NaOH and HCl solutions, silylated by trimethylchlorosilane (TMCS) and used in extraction of the analytes from a relatively high volume of aqueous sample. The adsorbed analytes are desorbed by methanol, which acts as a dispersive solvent in the following DLLME method. In the first step, the effects of different factors i.e., concentrations of NaOH, HCl, and silylated agent and their contact times were studied using central composite design (CCD) and response surface method. Extraction time, extraction solvent (chloroform) volume, dispersive solvent (methanol) volume, centrifugation rate and time, and salting-out effect in DLLME procedure were optimized in the same way using CCD, in the second step. High enrichment factors (EFs) (more than 1,000 in most cases) and low detection limits (at sub lg L -1 level) are attainable by using gas chromatography-flame ionization detection. The repeatability and reproducibility of the proposed method are good and the relative standard deviations (RSD %) for six repeated experiments (C = 100 lg L -1 of each pesticide) are less than 7.25%. Finally, the method was successfully applied in determination of analytes in some aqueous samples such as wastewater, well water, and some fruit juice samples.

The ‘self-activation’ of host molecules via the incorporation of a guest has received considerable attention in supramolecular catalysis. Here, we demonstrate how HgCl2 effects the tosylation rate of tolanophanes (1a–c: n=2−4) with different alkyl chain lengths. Among these substrates, 1a has the highest strain in sp carbons and, therefore, is active even without assistance of HgCl2. In contrast, 1c is inert and needs to be activated in the presence of HgCl2. Therefore, the averaged reaction rate is in the following order: 1c>1b>1a, confirming the role of the supramolecular cavity of 1 over the strain of alkyne bonds. Ab initio calculations are consistent with the experimentally derived reactivity, supporting our size-fitting hypothesis. In contrast, acyclic analogues showed lower activity in the presence of HgCl2 to confirm the effect of the ring cavity. To gain more information, the HgCl2 complexation of 1b was examined by using 1H NMR and UV-vis spectroscopies. All products 5 are new and well characterized. The hydration of isomeric mixtures of 5b,c gave the corresponding single products 4b,c.