Highly selective and effective solid phase microextraction of benzoic acid esters using ionic liquid functionalized multiwalled carbon nanotubes-doped polyaniline coating

• A novel MWCNT@IL/PANI fiber was prepared by electrochemical method.
• It showed high thermal stability.
• It exhibited high selectivity and extraction efficiency toward target analytes.

The present work reports the electrochemical fabrication of an ionic liquid functionalized multiwalled carbon nanotubes–polyaniline (MWCNT@IL/PANI) nanocomposite coating and its application in the headspace-solid phase microextraction (HS-SPME) and gas chromatography (GC) determination of benzoic acid esters (i.e., methyl benzoate, ethyl benzoate, propyl benzoate and butyl benzoate). The MWCNTs was firstly functionalized with amine-terminated IL (MWCNT@IL) through chemical reduction, and then was doped in PANI during the electropolymerization of aniline. The resulting coating was characterized by infrared spectroscopy, field emission scanning electron microscopy and thermo gravimetry. It showed net-like structure and had high thermal stability (up to 330 °C). Furthermore, it presented high selectivity for the four benzoic acid esters and thus suited for their HS-SPME–GC determination. Results showed that under optimized extraction conditions, the detection limits were less than 6.1 ng L−1 (S/N = 3) and the linear detection ranges were 0.012–50 μg L−1 (R ≥ 0.9957) for these analytes. The relative standard deviations (RSDs) were lower than 6.4% for five successive measurements with one fiber, and the RSDs for fiber-to-fiber were 4.4–9.6% (n = 5). The developed method was successfully applied to the determination of these benzoic acid esters in perfume samples.