3D-printed stereolithographic fluidic devices for automatic nonsupported microelectromembrane extraction and clean-up...

There is a quest of novel functional and reliable platforms for enhancing the efficiency of microextraction approaches in troublesome matrices, such as industrial wastewaters. 3D printing has been proven superb in the analytical field to act as the springboard of microscale extraction approaches.

In this work, low-force stereolithography (SL) was exploited for 3D printing and prototyping bespoke fluidic devices for accommodating nonsupported microelectromembrane extraction (μEME). The analytical performance of 3D-printed μEME devices with distinct cross-sections, including square, circle, and obround, and various channel dimensions was explored against that of commonly used circular polytetrafluoroethylene (PTFE) tubing in flow injection systems. A computer-controlled millifluidic system was harnessed for the (i) automatic liquid-handling of minute volumes of donor, acceptor, and organic phases at the low μL level that spanned from 3 to 44 μL in this work, (ii) formation of three-phase μEME, (iii) in-line extraction, (iv) flow-through optical detection of the acceptor phase, and (v) solvent removal and regeneration of the μEME device and fluidic lines. Using methylene blue (MB) as a model analyte, experimental results evinced that the 3D-printed channels with an obround cross-section (2.5 mm × 2.5 mm) were the most efficient in terms of absolute extraction recovery (59%), as compared to PTFE tubing of 2.5 mm inner diameter (27%). This is attributed to the distinctive convex interface of the organic phase (1-octanol), with a more pronounced laminar pattern, in 3D-printed SL methacrylate-based fluidic channels against that of PTFE tubing on account of the enhanced 1-octanol wettability and lower contact angles for the 3D-printed devices. The devices with obround channels were leveraged for the automatic μEME and in-line clean-up of MB in high matrix textile dyeing wastewater samples with relative recoveries ≥81%, RSD% ≤ 17.1% and LOD of 1.3 mg L^-1. The 3D-printed nonsupported μEME device was proven superb for the analysis of wastewater samples with an elevated ionic strength (0.7 mol L^-1 NaCl, 5000 mg L^-1 Na₂CO₃, and 0.013 mol L^-1 NaOH) with recorded electric currents below 12 μA.

The coupling of 3D printing with nonsupported μEME in automatic flow-based systems is herein proposed for the first time and demonstrated for the clean-up of troublesome samples, such as wastewaters.