In the present work we report a non-aqueous electrophoresis method (NACE) for the separation and determination of eight tricyclic antidepressants (TCAs) in human serum. Separation is carried out in 1 M acetic acid, 50 mM ammonium acetate and 10 mM SDS in ACN. Standards and samples were prepared in 0.8 M acetic acid in ACN and introduced by electrokinetic injection. The interactions between TCAs and acetate ions were studied and deduced from comparison of both the actual experimental and theoretical mobility. The establishment of calibration curves in the presence or absence of serum matrix, between 20 and 200 ng/mL, together with the determination of most important analytical parameters and a study of robustness were performed. Validation of the CE method was carried out with serum samples spiked with the analytes. The NACE determination method offers better resolution and higher sensitivity than the determination of TCAs in aqueous media.
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