3D-Printed Microflow Injection Analysis Platform for Online Magnetic Nanoparticle Sorptive Extraction of Antimicrobials in Biological Specimens as a Front End to Liquid Chromatographic Assays.

In this work, the concept of 3D-printed microflow injection (3D-μFI) embodying a dedicated multifunctional 3D-printed stator onto a rotary microvalve along with a mesofluidic sample preparation platform is proposed for the first time. A transparent 3D-printed stereolithographic mesofluidic chip device accommodating polyaniline (PANI) decorated magnetic nanoparticles (32.5 ± 3.8 mg) is harnessed to in-line sorptive microextraction as a front end to liquid chromatography with peak focusing. As a proof-of-concept application, the 3D-μFI assembly was resorted to matrix cleanup and automatic programmable-flow determination of organic emerging contaminants (4-hydroxybenzoate analogues and triclosan as antimicrobial model analytes) in human saliva and urine samples. By using a sample volume of 1.0 mL with a loading flow rate of 200 μL min-1, an eluent volume of 120 μL at 80 μL min-1, and online HPLC injection of 300 μL of the mixture of eluate and Milli-Q water (in a 1:2 ratio) to prevent band broadening effects of the most polar analytes, the limits of detection (3σ criterion) ranged from 1.1 to 4.5 ng mL-1 for methylparaben (MP), ethylparaben (EP), propylparaben (PrP), phenylparaben (PhP), butylparaben (BP), and triclosan (TCS). Enhancement factors of 16-25 were obtained for the target analytes. Spike recoveries ranged from 84 to 117% for both saliva and urine samples. The online 3D-μFI hyphenated method is synchronized with the chromatographic separation and features a chip lifetime of more than 20 injections with minimal losses of moderately nonpolar compounds on the walls of the mesofluidic device.