A solid-phase microextraction coating of sol-gel-derived perhydroxy cucurbit[6]uril and its application on to the determination of polycyclic aromatic hydrocarbon

A novel solid-phase microextraction coating that contains perhydroxy cucurbit[6]uril((OH)(12)Q[6]) was prepared by a sol-gel method. (OH)(12)Q[6] was used as a starting coating material with hydroxy-terminated poly(dimethylsiloxane) (OH-PDMS) to bond chemically to a fused-silica substrate using 3-(2-cyclooxypropoxyl)propyltrimethoxysilane as cross-linking agent; hydrolysis and polycondensation reactions then led to the formation of a (OH)(12)Q[6]/PDMS-coating. The coating has a high thermal stability (360 degrees C), long lifetime and can withstand organic and inorganic solvent rinsing because of the chemical binding between the coating and silica substrate. Its performance was tested by headspace (HS) solid-phase microextraction fiber coupled with gas chromatography to determine polycyclic aromatic hydrocarbon (PAHs) compounds in water samples. The (OH)(12)Q[6]/PDMS-coated fiber exhibited higher enrichment factors from fourfold for naphthalene to tenfold for pyrene compared with commercial PDMS fiber, and the enrichment factors increased with the number of condensed PAH rings. The strong adsorption affinity is believed to be attributed to hydrogen bonding and C-H center dot center dot center dot pi interactions between PAHs and (OH)(12)Q[6], according to the results of quantum chemical calculations. In the PAH analysis, the (OH)(12)Q[6]-coated fiber showed a good repeatability (< 4.7%) and reproducibility between fibers (<9.4%), low detection limits (0.03-0.15 mu g L-1), and a wide linearity (0.1-1000 mu gL(-1)) under optimized conditions. This method was used for the simultaneous determination of seven PAHs with satisfactory recoveries of 90.56%-107.4% for Huaxi river water samples and 90.23%-109.5% for local wastewater samples, respectively. (C) 2016 Elsevier B.V. All rights reserved.