Polydopamine inner wall-coated hypodermic needle as microextraction device and electrospray emitter for the direct analysis of illicit drugs in oral fluid by ambient mass spectrometry.

In this article, polydopamine inner wall-coated hypodermic needles (PDA-HNs) are evaluated as both microextraction devices and electrospray ionization (ESI) emitters for determining selected illicit drugs (methamphetamine, cocaine, and methadone) in oral fluid samples. The PDA film, located in the inner wall of the needle, allows the extraction of the analytes at alkaline pH, where their hydrophobic character is promoted. The extracted analytes are finally eluted in a methanol/formic acid mixture that also acts as ESI solution. For this purpose, a dedicated interface based on the connection of a PEEK tube with the needle hub is proposed. This assembly allows delivering the ESI solution by the infusion syringe pump of the mass spectrometer, providing an efficient ESI on the tip of the needle. The double use of the PDA-HNs as microextraction devices and ESI emitters permits the determination of the target analytes with limits of detection and precision (expressed as relative standard deviation) values better than 2.4 µg/L and 17.6%, respectively. The accuracy was evaluated by analyzing independent spiked oral fluid samples, obtaining good results.

Polydopamine coated hypodermic needles as a microextraction device for the determination of tricyclic antidepressants in oral fluid by direct infusion MS/MS.

In-needle microextraction consists of the confinement of the sorbent, by coating or packing, inside a metallic needle. The size of the needles reduces the eluent requirements providing an efficient preconcentration of the analytes. In this work, hypodermic needles coated with polydopamine (PDA) are presented as microextraction devices to isolate six tricyclic antidepressants from oral fluid samples. The coating consists of the in-surface polymerization of dopamine at pH 8.5 and mild conditions (room temperature and water as solvent). The PDA coating over the stainless-steel surface confers the needles with a high extraction ability towards the target analytes. After the extraction, the eluates were analyzed by direct infusion MS spectrometry, working in multiple reaction monitoring (MRM) mode, which provided a sample throughput of 30 samples per hour. The variables affecting the synthesis (number of coating cycles, the concentration of dopamine, and needle surface pre-treatment) and the extraction (sample salinity, sample loading cycles, and the number of elution strokes) were studied in depth. Under the optimum conditions, a matrix-matched calibration model was built. The limits of quantification are between 2 and 5 ng mL-1 with linear ranges up to 1000 ng mL-1 for all analytes. The precision, expressed as relative standard deviation (RSD), is better than 10% for all analytes. Accuracy was calculated as recovery, and the obtained values are between 84% and 107%. A single-blind assay was also performed to evaluate the suitability of the method for real application.