Sampling reliability, spatial resolution, spatial precision, and extraction efficiency in droplet-based liquid microjunction surface sampling.

Droplet-based liquid extraction approaches for spatially resolved surface sampling coupled with high-performance liquid chromatography/mass spectrometry (HPLC/MS) provide the ability to deal with complex sample matrices and to identify isomeric compounds not distinguishable by MS methods alone. Improvements in sampling reliability, spatial resolution, spatial precision and extraction efficiency are required to further the analytical utility of such sampling systems. An autosampler capable of droplet-based liquid extraction was coupled with an HPLC/MS system. Visual inspection of the junction formation between the probe and a glass surface allowed evaluation of the liquid junction formation reliability, spatial location and size as a function of variable parameters such as solvent composition, probe-to-surface distance and droplet volume during solvent dispense and aspiration. Quantitative analysis of a component from a model surface using a weak extraction solvent was used to evaluate the effect of extraction time and number of extraction cycles on analyte extraction efficiency. Reliable junction formation, independent of other variable parameters, was realized simply by maintaining a maximum distance of 0.4 mm between the probe and the sample surface. The smallest liquid junction diameter (1.6 mm) was observed when using a 1 μL dispensed volume and 90% aqueous extraction solvent with either methanol or acetonitrile. Good sampling precision was always achieved using an extraction solvent with at least 50% methanol or acetonitrile by volume. Quantitative sampling of rhodamine B from a magenta Sharpie ink surface using a weak extraction solvent showed that extraction efficiency could be improved by increasing the extraction time or the number of extraction cycles. A platform employing a commercially available autosampler coupled to HPLC/MS was developed and successfully applied to investigate the effect of different sampling parameters on the reliability, spatial resolution, spatial precision and extraction efficiency of the liquid junction surface sampling process. This article is a U.S. Government work and is in the public domain in the USA.