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4 - 6.1% and 5.2 - 9.0% for repeatability and reproducibility, respectively (6.9 - 9.7% and 14.1 - 14.6% for spermidine). Successful determination of the studied polyamines and their N-acetylated forms was performed on the saliva of 17 volunteers.In this study, a special orthogonal separation method, named as dual-tautomerism separation (DTS), was developed for the purification of tautomeric compounds from complex matrixes. In DTS, isomers of these compounds are individually collected and asymmetrically transformed to the mixtures of is