Simultaneous determination of polyamines and acetylpolyamines in human urine by capillary electrophoresis with fluorescence detection

There has been evidence linking elevated polyamines ( PA s) and acetylpolamines ( A c PA s) level and cancer. So the simultaneous analysis of these compounds has become important task for cancer diagnosis and antitumor drug monitoring. A simple, fast and inexpensive CZE ‐ LIF method has been developed for the determination of cadaverine ( CAD ), putrescine ( PUT ), spermine ( SPM ), spermidine ( SPD ), acetylspermine ( ASPM ), and acetylspermidine ( ASPD ) in human urine using 4‐chloro‐7‐nitro‐2,1,3‐benzooxadiazole as a fluorescent reagent. Labeling reaction conditions were systematically investigated and were found to be 20 mM borate buffer at pH 7.4, labeling reaction time, and temperature were 10 min and 70°C, respectively. Under these optimized conditions the four PA s, two A c PA s and the internal standard were separated in 6 min. An Exactive‐ MS with an ESI source was used for identification of the bis‐derivative of the ASPM . The method was validated in term of linearity, LOD s, repeatability, intra‐ and interday assays, recovery, and selectivity. The LOD s for CAD , PUT , SPM , SPD , ASPM , and ASPD were found to be 7.6, 10.0, 9.0, 8.8,7.8, and 3.3 nM, respectively. The method was successfully applied for the analysis of PA s and A c PA s in healthy human urine samples.