In the present work, the impact of dilution and filtration of biological samples (plasma and urine) using ultra-centrifugal filters were analytically assessed as pretreatment steps before the electromembrane extraction. Pseudoephedrine, lidocaine, propranolol, and ketoconazole were chosen as the basic model drugs. They were analyzed by using high-performance liquid chromatography coupled with an ultraviolet-visible detector after the extraction process. In this way, the type of filter and sample dilution order were evaluated in addition to the method's figures of merit. Hence, purification of the biological samples via ultra-centrifugal filters results in a successful electromembrane extraction procedure in the presence of high applied voltages (≥300 V). It brings notable augmentation in the extraction recoveries. As a result, a reduction in the amount of electrical current of the extraction system (17.0-30.0 µA for plasma and 23.0-33.0 µA for urine) and acceptable repeatability (4.6-12.9%) were observed. In the water, linearity was attained between 25.0 and 1000.0 ng/mL; besides, limits of quantification were in the range of 10.0-25.0 ng/mL, and limits of detection were between 3.0 and 7.5 ng/mL.
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