In-Tube Solid-Phase Microextraction and Liquid Chromatography Using a Monolithic Column for the Selective Determination of Residual Ethylenediamine in Industrial Cationic Polymers

The selective determination of the diamine ethylenediamine (EDA) in the presence of a higher amount of residual dimethylamine in cationic polymers has been developed. The strategy uses both a solution derivatization with a selective agent of primary amines such as o-phthaldialdehyde-N-acetyl-L-cysteine (OPA-NAC) and an in-tube solid-phase microextraction (IT-SPME) coupled to liquid chromatography (LC). A 70 cm long, 0.32 mm internal diameter, and 3 mu m thick commercially available capillary column coated with 95% polydimethylsiloxane and 5% polydiphenylsiloxane was employed to replace the injection loop of a Rheodyne injection valve. A volume of 1 mL of derivatized sample was passed through the capillary, and 100 mu L of water was later used for cleaning and filling the capillary. After, the injection was effected and the desorption of the derivative from the capillary was carried out in the dynamic mode using the mobile phase. Chromatographic separation was performed in less than 2 min using a monolithic silica column Onyx (100 mm x 3.0 mm i.d.) under isocratic conditions. The effect of several parameters affecting derivatization and IT-SPME was investigated. The quantification of EDA was realized over the range of 0.07-2 mu g/mL with adequate linearity, accuracy, and reproducibility, and the limit of detection was 20 ng/mL The method is rapid and low in cost, and sample handling and organic solvent consumption have been minimized. Its application to polymeric cationic surfactants used in water treatment allowed the selective quantification of residual EDA at low microgram per milliliter levels of concentration without off-line preconcentration.