High throughput determination of free biogenic monoamines and their metabolites in urine using thin-film solid phase microextraction

UPLC-MS/MS methods are the gold standard for routine, high-throughput measurements of biogenic monoamines for the diagnosis of catecholamine-producing tumors. However, this cannot be achieved without employing efficient sample pretreatment methods. Therefore, two pretreatment methods, thin-film solid phase microextraction (TF-SPME) and packed fibers solid phase extraction (PFSPE), were developed and evaluated for the analysis of biogenic monoamines and their metabolites in urine. A hydrophilic-lipophilic balance (HLB) coating was chosen for the thin-film blade format SPME method and compared with a Polycrown ether (PCE) composite nanofiber used as an adsorbent for the PFSPE method. Under optimal conditions, the absolute extraction recovery and relative matrix effect of the newly developed TF-SPME method were determined to be 35.7–74.8% and 0.47–3.63%, respectively. The linearity was 0.25–500 ng mL −1 for norepinephrine, epinephrine, dopamine, normetanephrine 3-methoxytyramine, serotonin, histamine, and 0.1–500 ng mL −1 for metanephrine. The intra-and inter-assay coefficients of variation were 0.7–8.7%, and the respective accuracies were calculated to be 90.8–104.7% and 89.5–104.5% for TF-SPME. Compared with the PFSPE method, the TF-SPME method had a higher extraction efficiency, lower matrix effects and a wider linear range for eight target substances, which ensured higher accuracy of simultaneous detection of all compounds of interest. Therefore, the proposed TF-SPME method can be employed for the high throughput screening for neuroendocrine tumors in a routine clinical setting and other relative research by simultaneous quantitation of urine eight biological monoamines in a single run. • TF-SPME facilitates high throughput determination of urinary monoamines biomarkers. • A HLB coating was developed and optimized for the thin-film blade format SPME method. • TF-SPME method is compared with some existing methods showing superior performance. • The first time SPME method has demonstrated low LOD values for monoamines analysis.