A hollow-fiber liquid-phase microextraction(HF-LPME) method has been developed for the purification and preconcentration of biogenic polyamines and their precursor amino acids in human saliva.Putrescine(Put),cadaverine(Cad),spermidine(Spe),ornithine(Orn),lysine(Lys),and arginine(Arg)were determined by the CE-LIF detection after microextraction.Several factors that affect extraction efficiency,separation,and detection were investigated.Under the optimum conditions,six analytes could achieve baseline separation within 30 min,exhibiting a linear calibration at three orders of magnitude(r^2 > 0.998);the obtained enrichment factors of HF-LPME were between 19(for Orn) and 218(for Cad),and the LODs were in the range of 0.0072-0.26 nmol/L.The proposed HF-LPME/CE-LIF method has been successfully applied for the sensitive analyses of the real-world saliva samples collected from healthy volunteers and different patients with oral diseases,providing a potential method for primary non-invasive diagnosis of some oral diseases.
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