Carboxyl hybrid monolithic column in-tube solid-phase microextraction coupled with UPLC-QTRAP MS/MS for the determination of amphetamine-type stimulants

A carboxyl functionalized organic-inorganic hybrid monolithic column (TMOS-co-CES) was applied as in-tube solid-phase microextraction (SPME) sorbent combining with ultra-performance liquid chromatography-triple quadrupole/linear ion trap mass spectrometer for separation and analyzation of seven typical amphetamine-type stimulants (ATSs), including amphetamine (AM), methamphetamine (MAM), cathinone, methcathinone, 3,4-methylenedioxyamphetamine, 3,4-methylenedioxymethamphetamine and 3,4-methylenedioxyethylamphetamine. The application potential of TMOS-co-CES material to ATSs was preliminarily confirmed by computational simulation by using cathinone as a representative. The influences of various SPME parameters and analytical performance were investigated systematically. As matched with the results of computational simulation, TMOS-co-CES column could capture ATSs under milder near neutral pH condition with high extraction efficiency basing on the adsorption mechanism explained as a mixed mode of electrostatic and hydrophobic interactions. Seven target trace ATSs in spiked sewage, pond water and urine could be rapidly and conveniently separated and enriched by the proposed TMOS-co-CES in-tube SPME method under the optimized conditions with good accuracy, repeatability and resistance to matrix interference. Moreover, AM and MAM had been successfully detected in real urines of suspected drug abusers by TMOS-co-CES in-tube SPME method, which indicated that the proposed method had good application feasibility for drug monitoring. The mild extraction condition and ideal method performance further made the TMOS-co-CES in-tube SPME method more potential in applications for forensic analysis and drug abuse.