Electromembrane surrounded solid phase microextraction using electrochemically synthesized nanostructured polypyrrole fiber

• Electromembrane surrounded SPME using conductive polymers is carried out.
• The polypyrrole coating was prepared and utilized as both cathode and SPME sorbent.
• The developed method was applied for extraction of some antidepressant drugs.
• Effects of various parameters on extraction efficiency of analytes were optimized.
• The method was applied for analysis of analytes in different biological samples.

Electromembrane surrounded solid phase microextraction using conductive polymers as the sorbent is carried out for the first time for extraction of two antidepressants including amitriptyline (AMI) and doxepin (DOX), as model analytes. The polypyrrole coating was prepared and utilized as both cathode and SPME sorbent. Different variables such as the conditions for preparation of polypyrrole fiber, pH of the donor and the acceptor phases, applied voltage, and extraction time were optimized. Under the optimized conditions, figures of merit of the proposed method were investigated in human whole blood and urine samples. Intra- and inter-assay precisions ranged between 3.1–7.5% and 7.6–12.3%, respectively were obtained in different extraction media. Detection limits of 0.15 and 0.05 for AMI and 0.3 and 0.1 ng mL−1 for DOX were achieved in the urine and blood samples, respectively. Linearity of the method was studied up to 50.0 ng mL−1 for both analytes and coefficients of determination better than 0.9966 were achieved. Regardless of the high sample cleanup, which makes the proposed method suitable for analysis of drugs from complicated matrices, clean chromatograms were obtained. Finally, the proposed method was applied for analysis of AMI and DOX in different real samples and reasonable data were obtained.