Single drop microextraction as a concentrating probe for rapid screening of low molecular weight drugs from human urine in atmospheric‐pressure matrix‐assisted laser desorption/ionization mass spectrometry

Abstract

The present work reports the development of a new analytical procedure for simple and rapid screening of low molecular weight drugs (<500 Da) from human urine samples by atmospheric-pressure matrix-assisted laser desorption/ionization mass spectrometry (AP-MALDI-MS) combined with single drop microextraction (SDME). The success of the proposed method is due to the use of methyltrioctylammonium chloride (MTOAC) as additive to avoid the noise arising from the matrix ions (alpha-cyano-4-hydroxycinnamic acid (CHCA)). SDME also aided in alleviating the interferences arising from other matrix ions present in the urine samples prior to AP-MALDI-MS analysis. Factors affecting the extraction efficiency of drugs, such as selection of solvent, stirring speed, extraction time, exposure volume of extraction phase and salt addition, have been optimized. The optimum molar ratio of CHCA/MTOAC that gave the minimum background noise of CHCA ions was 700:1. The limit of detection (LOD) and relative standard deviation (RSD) of the method were in the ranges 0.3-1.6 microM and 7.8-11.4%, respectively. The SDME method was compared with liquid-liquid extraction (LLE) and hollow fiber liquid-phase microextraction (HF-LPME) to evaluate the compatibility of the present method in the extraction of drugs from urine samples. The role of MTOAC as matrix ion signal suppressor and SDME as analyte-separating device in the rapid screening of low molecular weight drugs from human urine samples using AP-MALDI/MS has been reported.