Graphene-doped electrochemical copolymer coating of 2,2-bithiophene and 3-methylthiophene for the highly effective solid-phase microextraction of volatile benzene homologues.

We report the electrochemical fabrication of a poly(2,2-bithiophene-co-3-methylthiophene)-graphene composite coating and its application in the headspace solid-phase microextraction and gas chromatography determination of benzenes (i.e., bromobenzene, 4-bromotoluene, 2-nitrotoluene, 3-nitrotoluene and 1,2,4-trichlorobenzene). The coating was uniform and showed cauliflower-like microstructure. It had high thermal stability (up to 375°C) and could be used for at least 180 times of solid-phase microextraction without a decrease in extraction performance. Furthermore, it presented high extraction capacity for the benzenes due to the hydrophobic effect and π-π interaction between the analytes and the coating. Under optimized extraction conditions, good linearity (correlation coefficients higher than 0.9946), wide linear range (0.01-50 μg/L), and low limits of detection (5.25-12.5 ng/L) were achieved for these analytes. The relative standard deviation was lower than 5.7% for five successive measurements with one fiber, and the relative standard deviation for fiber-to-fiber was 4.9-6.8% (n = 5). The solid-phase microextraction and gas chromatography method was successfully applied for the determination of three real samples, and the recoveries for standards added were 89.6-106% for nail polish, 85.8-110% for hair dye, and 90-106.2% for correction fluid, respectively.