Simultaneous determination of polyamines in human nail as 4-(N,N-dimethylaminosulfonyl)-7-fluoro-2,1,3-benzoxadiazole derivatives by nano-flow chip LC coupled with quadrupole time-of-flight tandem mass spectrometry.

Background: Polyamines are active biogenic amines which play an important role in cell growth and proliferation and the synthesis of proteins and nucleosides. In recently studies, rapid tumor growth has been associated with markedly altered polyamine biosynthesis and accumulation. Therefore, the accurate detection and identification of all the polyamines simultaneously in a single analysis is becoming more and more important for the study of their biochemical roles.

Methods: The development of a simultaneous determination method for 9 polyamines in human nails was attempted by the combination of nano-flow chip LC and quadrupole time-of-flight tandem mass spectrometry (Q-TOF-MS/MS). The proposed method was for the determination in the nails of healthy persons and cancer patients.

Results: The derivatives of the polyamines in human nail were completely separated by a gradient of an 18 min duration wash program using a reversed-phase chip column. The polyamine derivatives were then introduced into the Q-TOF-MS/MS instrument and sensitively detected in the ESI(+) mode. Polyamine concentration was different based on the gender, i.e., PUT and SPD is higher in men than in women in the healthy persons. Additionally, in the lung cancer patients group, as compared with the healthy persons, concentrations of PUT, N¹-actPUT, and SPM were significantly increased.

Conclusions: We here present a novel sensitive, simple method for the simultaneous determination of polyamines in human nails. Furthermore, we show that polyamines (ORN, DAP, CAD, N¹-actPUT, N⁸-actSPD, N¹-actSPM) were detected from the human nails. Human nails may may serve as the noninvasive bio sample for diagnosis of the chronic disease.