Ambient molecular imaging by laser ablation atmospheric pressure chemical ionization mass spectrometry

RATIONALE The functions and properties of compounds are not only specified by their chemical structures, but also by their location inside a sample. Mass spectrometry is a powerful tool for imaging, whereby the kind of sample and compound depend on the used sampling and ionization methods. The developed laser ablation mass spectrometry method delivers high resolution images of small molecules in native samples. METHODS A UV laser ablation (LA) system was combined with an atmospheric pressure chemical ionization (APCI) mass spectrometer. The spatially resolved sampling was performed by focusing the 213 nm laser beam onto a sample. The fine aerosol generated by the ns pulsed laser irradiation was then transported to the APCI mass spectrometer by a nitrogen stream. In the APCI source, post‐ionization was accomplished by a corona discharge. The resulting ions were detected with an orbitrap mass spectrometer. RESULTS The properties of the novel LA‐APCI‐MS setup are demonstrated by spatially resolved analysis of several samples including tablets, TLC plates and dried droplets. The target compounds are detected with high spatial and mass resolution. For higher molecular weight compounds like thyroxine, fragmentation was observed, whereas small molecules like caffeine stayed intact. CONCLUSIONS LA‐APCI‐MS is introduced as an ambient molecular mass spectral imaging method for molecules with high resolution in space and mass. The combination of two independent instruments offers flexible ion source and mass analyzer exchange and therefore LA‐APCI‐MS opens up new possibilities for molecular imaging under ambient conditions. Copyright © 2013 John Wiley & Sons, Ltd.