Challenges in the identification process of phenidate analogues in LC-ESI-MS/MS analysis: Information enhancement by derivatization with isobutyl chloroformate.

A new analytical technique for the structural elucidation of four representative phenidate analogues possessing a secondary amine residue, which leads to a major/single amine-representative fragment/product ion at m/z 84 both in their GC-EI-MS and LC-ESI-MS/MS spectra, making their identification ambiguous, was developed. The method is based on "in vial" chemical derivatization with isobutyl chloroformate in both aqueous and organic solutions, followed by liquid chromatography-electrospray ionization mass spectrometry (LC-ESI-MS/MS). The resulting carbamate derivatives promote rich fragmentation patterns with full coverage of all substructures of the molecule, enabling detailed structural elucidation and unambiguous identification of the original compounds at low ng/mL levels.