Multiple headspace solid-phase microextraction of 2-cyclopentyl-cyclopentanone in polyamide 6.6: possibilities and limitations in the headspace analysis of solid hydrogen-bonding matrices.

The interactions between a polar analyte, 2-cyclopentyl-cyclopentanone, and a solid polar matrix, polyamide 6.6, during multiple headspace solid-phase microextraction (MHS-SPME) were studied. Strong hydrogen bonding between the analyte and the matrix was observed and shown to cause slow migration and adsorption of the analyte. These matrix effects led to erroneous quantitation despite the use of multiple headspace extraction. Addition of water disrupted the hydrogen bonding between the analyte and the matrix and a valid quantitation was achieved. The addition of water also increased the sensitivity and allowed the identification of 2,5-bis(cyclopentyl)-1-cyclopentanone. The amount of 2-cyclopentyl-cyclopentanone in five different polyamide 6.6 samples was measured using the developed multiple headspace solid-phase microextraction method with water-displacer. The measured concentrations were in the range of 1.44-15.61 microg/g. These concentrations were up to 30% higher than the concentrations measured after microwave-assisted extraction (MAE), which indicates incomplete recovery by MAE. The use of water as a displacer eliminated the matrix effects and complete recovery of the analyte was achieved by MHS-SPME.