3D printed fluidic platform with in-situ covalently immobilized polymer monolithic column for automatic solid-phase extraction.

In this work, 3D stereolithographic printing is proposed for the first time for the fabrication of fluidic devices aimed at in-situ covalent immobilization of polymer monolithic columns. Integration in advanced flow injection systems capitalized upon programmable flow was realized for fully automatic solid-phase extraction (SPE) and clean-up procedures as a 'front-end' to on-line liquid chromatography. The as-fabricated 3D-printed extraction column devices were designed to tolerate the pressure drop of forward-flow fluidic systems when handling large sample volumes as demonstrated by the determination of anti-microbial agents, plastic additives and monomers as models of emerging contaminants (4-hydroxybenzoic acid, methylparaben, phenylparaben, bisphenol A and triclosan). Decoration of the monolithic phase with gold nanoparticles (AuNPs) was proven most appropriate for the enrichment of phenolic-type target compounds. In particular, the absolute recoveries for the tested analytes ranged from 73 to 92% both in water and saliva samples. The 3D printed composite monolith showed remarkable analytical features in terms of loading capacity (2 mg g-1), breakthrough volume (10 mL), satisfactory batch-to-batch reproducibility (<9% RSD), and easy on-line coupling of the SPE device to HPLC systems. The fully automatic 3D-printed SPE-HPLC hyphenated system was also exploited for the on-line extraction, matrix clean-up and determination of triclosan in 200 μL of real saliva samples.