A versatile millifluidic 3D-printed inverted Y-shaped unit (3D-YSU) was prototyped to ameliorate the concentration capability of nonsupported microelectromembrane extraction (μ-EME), exploiting optosensing detection for real-time monitoring of the enriched acceptor phase (AP). Continuous forward-flow and stop-and-go flow modes of the donor phase (DP) were implemented via an automatic programmable-flow system to disrupt the electrical double layer generated at the DP/organic phase (OP) interface while replenishing the potentially depleted layers of analyte in DP. To further improve the enrichment factor (EF), the organic holding section of the OP/AP channel was bifurcated to increase the interfacial contact area between the DP and the OP. Exploiting the synergistic assets of (i) the continuous forward-flow of DP (1050 μL), (ii) the unique 3D-printed cone-shaped pentagon cross-sectional geometry of the OP/AP channel, (iii) the bifurcation of the OP that creates an inverted Y-shape configuration, and (iv) the in situ optosensing of the AP, a ca. 24 EF was obtained for a 20 min extraction using methylene blue (MB) as a model analyte. The 3D-YSU was leveraged for the unsupervised μ-EME and the determination of MB in textile dye and urban wastewater samples, with relative recoveries ≥88%. This is the first work toward analyte preconcentration in μ-EME with in situ optosensing of the resulting extracts using 3D-printed millifluidic platforms.

CLECEM Group Department of Analytical Chemistry University of Valencia C Doctor Moliner 50 46100 Burjassot Valencia Spain

Department of Chemistry Institute of Analytical Chemistry University of Natural Resources and Life Sciences Vienna Muthgasse 18 1190 Vienna Austria

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

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

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