On-line coupling of in-tube boronate affinity solid phase microextraction with high performance liquid chromatography-electrospray ionization tandem mass spectrometry for the determination of cis-diol biomolecules.

Boronate affinity solid phase microextraction (BA-SPME) is a new format appeared recently with great potential for specific extraction of cis-diol-containing compounds. Unlike conventional SPME, BA-SPME relies on covalent interactions and thereby features with specific selectivity, eliminated matrix effect and manipulable capture/release. However, only on-fiber BA-SPME and its off-line combination with high performance liquid chromatography (HPLC) have been reported so far. In this study, we report on-line coupling of in-tube BA-SPME with HPLC-electrospray ionization tandem mass spectroscopy (in-tube BA-SPME-HPLC-ESI-MS/MS) for the specific and sensitive determination of cis-diol-containing biomolecules. A boronate affinity extraction phase was prepared onto the inner surface of the capillary by copolymerization of vinylphenylboronic acid (VPBA) and ethylene glycol dimethacrylate (EDMA). The extraction conditions were optimized by choosing appropriate extraction/desorption solutions and extraction time. The extraction capacity, linear range, reproducibility and life-time were investigated. The developed method was successfully applied for the determination of dopamine in urine samples. Since many cis-diol-containing compounds are of great biological importance, the in-tube BA-SPME-HPLC method can be a promising tool.