A fully automatic millifluidic sensing platform coupling in-line nonsupported microelectromembrane extraction (μ-EME) with electrochemical detection (ECD) is herein proposed for the first time. Exploiting the features of the second generation of flow analysis, termed sequential injection (SI), the smart integration of SI and μ-EME-ECD enables (i) the repeatable formation of microvolumes of phases for the extraction step in a membrane-less (nonsupported) arrangement, (ii) diverting the acceptor plug to the ECD sensing device, (iii) in-line pH adjustment before the detection step, and (iv) washing of the platform for efficient removal of remnants of wetting film solvent, all entirely unsupervised. The real-life applicability of the miniaturized sensing system is studied for in-line sample cleanup and ECD of diclofenac as a model analyte after μ-EME of urine as a complex biological sample. A comprehensive study of the merits and the limitations of μ-EME solvents on ECD is presented. Under the optimal experimental conditions using 14 μL of unprocessed urine as the donor, 14 μL of 1-nonanol as the organic phase, and 14 μL of 25 mM NaOH as the acceptor in a 2.4 mm ID PTFE tubing, an extraction voltage of 250 V, and an extraction time of 10 min, an absolute (mass) extraction recovery of 48% of diclofenac in urine is obtained. The proposed flow-through system is proven to efficiently remove the interfering effect of predominantly occurring organic species in human urine on ECD with RSD% less than 8.6%.

CLECEM group Department of Analytical Chemistry University of Valencia C Doctor Moliner 50 Burjassot Valencia46100 Spain

Department of Chemistry Faculty of Science Chulalongkorn University Bangkok10330 Thailand

FI TRACE Group Department of Chemistry Faculty of Science University of the Balearic Islands Carretera de Valldemossa km 7 5 Palma de Mallorca Illes BalearsE 07122 Spain

Institute of Analytical Chemistry of the Czech Academy of Sciences Veveří 97 BrnoCZ 60200 Czech Republic

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