Ionic liquid-mediated sol-gel coatings for capillary microextraction

Ionic liquid (IL)-mediated sol-gel hybrid organic-inorganic materials present enormous potential for effective use in analytical microextraction. This opportunity, however, has not yet been explored. One obstacle to materializing this prospect arises from high viscosity of ILs significantly slowing down sol-gel reactions. In this work, we developed a method that overcomes this hurdle and provides IL-mediated advanced sol-gel materials for capillary microextraction (CME). We examined two different ILs: (a) a phosphonium-based IL, trihexyltetradecylphosphonium tetrafluoroborate, and (b) a pyridinium-based ionic liquid, N-butyl-4-methylpyridinium tetrafluoroborate. These ILs were evaluated in conjunction with two types of hydroxy-terminated polymers: (a) two Si-OH terminated polymers (PDMS and BMPO), and (b) two C-OH terminated polymers (PEG and polyTHF) that differ in their sol-gel reactivity. Scanning electron microscopy results demonstrate that ILs can serve as porogenic agents in sol-gel reactions. The IL-mediated sol-gel coatings prepared with silanol-terminated polymers provided up to 28 times higher extractions in off-line CME-GC compared to analogous sol-gel coatings prepared without any IL in the sol solution. Contrary to this, the IL-mediated sol-gel coatings prepared with C-OH terminated polymers provided lower extraction efficiencies compared to their IL-free counterparts. These observations were explained by (a) lower sol-gel reactivity of C-OH groups in PEG and polyTHF compared to Si-OH groups in PDMS and in hydrolyzed alkoxysilane precursors and (b) extremely high viscosity of ionic liquids. This study shows that IL-generated porous morphology alone is not enough to provide effective extraction media: careful choice of the organic polymer and the precursor with close sol-gel reactivity must be made to ensure effective chemical bonding of the organic polymer to the created sol-gel material to be able to provide the desired sorbent characteristics. Additionally, IL-mediated sol-gel PDMS coatings provided run-to-run RSD values of 4.2-5.0% and detection limits ranging from 3.2 ng/L to 17.4 ng/L. PDMS sol-gels prepared without ILs provided RSD values of 2.8-14.1%, and detection limits ranging from 4.9 ng/L to 487.0 ng/L.