In recent years, different geometrical configurations of SPME have been directly coupled to mass spectrometry, resulting in benefits such as diminishing matrix effects, improvement of detection limits, and considerable enhancement of analysis throughput. Although SPME fibers have been used for years, their potential for quantitative analysis when directly combined with mass spectrometry has not been explored to its full extent. In this study, we present the direct coupling of biocompatible-SPME (Bio-SPME) fibers to mass spectrometry via nano-ESI emitters as a powerful tool for fast quantitative analysis of target analytes in biofluids. Total sample preparation time does not exceed 2 min and, by selecting an appropriate fiber length and sample vessel, sample volumes ranging between 10 and 1500 μL can be used. Despite the short extraction time of the technique, limits of detection in the sub-nanogram per millilitre with good accuracy (≥ 90 %) and linearity (R2>0.999) were attained for all the studied probes...

A new SPME device was developed and applied for quick solventless extraction/enrichment of small molecules from complex matrices. Subsequently, the device was coupled as a transmission mode substrate to DART resulting in limits of detection in the low pg mL⁻¹ level in less than 3 minutes with reproducibility below 5% RSD.