Rapid and sensitive tapered-capillary microextraction combined to on-line sample stacking-capillary electrophoresis for extraction and quantification of two beta-blockers in human urine.

A tapered-capillary microextraction (tCap-μEx) combining with field-amplified stacking (FASI) method for CE analysis was developed. The tCap-μEx method is based on the construction of a micro solid phase extraction (SPE) column by narrowing the end of a silica capillary from 530µm (inner diameter) to 20µm, enabling the packing of 45µm sorbent particles without a frit. Various parameters that may affect the microextraction and FASI-CE analysis have been investigated and optimized. This study shows that microextraction exhibits advantages of small sample and sorbent volumes (less than 200μL sample and 2μL sorbent) and fast extraction time of 6min. The method was successfully applied for efficient determination of atenolol and metoprolol in human urine samples, with recovery of 93.7-105.5% and RSD (n=3) lower than 8.5%. Twenty-one-fold and nineteen-fold average enhancement of detection sensitivity was achieved for atenolol and metoprolol, respectively, versus the CE method without tCap-μEx and FASI. The method is environmentally friendly and allows reuse of the sorbent at least 8 times without an obvious loss in performance. The results indicate that the proposed method could be potentially applied in a wide range of doping control, clinical, forensic toxicology, food analysis and environmental analyses.