Sorptive tape-spray tandem mass spectrometry using aluminum foil coated with mixed-mode microparticles.

Direct mass spectrometry (MS) is an exciting strategy in bioanalysis, enabling rapid decision-making in different scenarios. Its application is usually hindered by matrix effects and the typically low concentration of the target compounds in the biofluids. In this sense, combining a previous sample preparation step minimizes or removes these shortcomings. This article describes sorptive tape-spray tandem mass spectrometry (STS-MS/MS) based on mixed-mode particles as a strategy to combine sample preparation and MS analysis in a single device. The technique uses a sorptive tape (ST) consisting of mixed-mode polymeric microparticles (combining ionic exchange and hydrophobic interactions) coated over aluminum foil in a spatial controlled way. The tapes act as the sorptive phases to isolate the analytes from the sample matrix and substrates for STS-MS/MS. The performance of the technique has been evaluated by developing a method to determine codeine in saliva as proof of concept. The affordability of the STs elements allows the preparation of many individual phases at low cost so that several samples can be extracted simultaneously, thus increasing the sample throughput. The extraction variables were optimized following a multivariate approach. Working under the optimum conditions, the limit of detection was 0.3 µg L-1, while the intraday precision, calculated as relative standard deviation (RSD) at three concentration levels, was better than 9.4 %. The accuracy, expressed as relative recovery, was in the range of 78-98 %. The method was also applied to the analysis of real samples. Despite being a powerful strategy, the direct combination of microextraction to MS is not always affordable in all laboratories. For this reason, the STs were also combined with commercial liquid chromatography-MS working under the direct infusion mode to demonstrate the usefulness of the ST in classical extraction workflows.

Mixed-mode cationic exchange sorptive tapes combined with direct infusion mass spectrometry for determining opioids in saliva samples.

This article describes the synthesis of mixed-mode cationic exchange (MCX) tapes as sorptive phases in bioanalysis, and it faces the determination of methadone and tramadol in saliva as the model analytical problem. The tapes are synthesized using aluminum foil as substrate, which is subsequently covered with double-sided adhesive tape where the MCX particles (ca. 1.4 ± 0.2 mg) finally adhere. MCX particles allow the extraction of the analytes at the physiological pH, where both drugs are positively charged, minimizing the potential co-extraction of endogenous matrix compounds. The extraction conditions were studied considering the main variables (e.g. ionic strength, extraction time, sample dilution). Under the optimum conditions and using direct infusion mass spectrometry as the instrumental technique, detection limits as low as 3.3 µg·L-1 were obtained. The precision calculated at three different levels, and expressed as relative standard deviation, was better than 3.8%. The accuracy, expressed as relative recoveries, ranged from 83 to 113%. The method was finally applied to determine tramadol in saliva samples from patients under medical treatment. This approach opens the door to easily preparing sorptive tapes based on commercial (or ad-hoc synthesized) sorbent particles.