Robotic-assisted dynamic large drop microextraction.

By proper design of an innovative extraction device, a lab-made multipurpose autosampler was exploited in the automated performance of the dynamic large drops based microextraction. The pluses of this new analytical strategy were demonstrated in the determination of sulfonamides and fluoroquinolones in surface water samples, by direct immersion single drop microextraction (SDME) and liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) analysis. Operational autosampler features and critical experimental factors influencing SDME, including the extraction mode (static or dynamic), extraction, stirring rate, salt addition, drop size, number of cycles and drop exposition time, were comprehensively investigated using both univariate and multivariate optimization. The lab-made autosampler allowed to performance challenging dynamic and static large drop based SDMEs in an automated and effortless way and with minimal requirements of hardware and software. Large stable drops provided high surface area, enhancing the phase ratio and in consequence increasing the analytes uptake. The best extraction efficiencies were obtained as a result of the synergic interaction between the use of large drops and the automated dynamic mode of extraction. The developed method proved to be a reliable, sensitive, and robust analytical tool, with intraday RSDs ranging between 4.0 and 7.6% (n = 6), and interday RSDs between 4.8 and 9.3% (n = 6), and, LOD and LOQ in the range of 15-50 and 35-100 ng L, respectively.