Preconcentration and Determination Of Fluoxetine and Norfluoxetine in Biological and Water Samples with β-cyclodextrin Multi-walled Carbon Nanotubes as a Suitable Hollow Fiber Solid phase Microextraction Sorbent and High Performance Liquid Chromatography

Abstract

‒A simple, selective and sensitive hollow fiber solid phase microextraction (SPME) combined with HPLC for the determination of fluoxetine (FLX) and norfluoxetine (NFLX) in human urine and real water samples has been developed and fully validated. Two solid phase microextraction sorbents, β-cyclodextrin functionalized multi-walled carbon nanotubes (βCD-MWCNTs) and acyl chloride functionalized MWCNTs, were synthesized and placed in the surface and pores of polypropylene hollow fiber by sol‒gel technique. In order to compare the analytical performance of βCD-MWCNTs as a new SPME sorbent with acyl chloride functionalized MWCNTs and MWCNTs, the hollow fiber device was directly immersed into the sample solution under a magnetic stirring. The βCD-MWCNTs are quite effective for extraction of fluoxetine and norfluoxetine. The extraction parameters such as pH of donor phase, donor phase volume, stirring rate, extraction time, type and volume of desorption solvent, and desorption time were thoroughly optimized. Under optimal conditions, the proposed method shows good linearity in the range of 1‒340 and 0.9‒360 ng/mL with a correlation coefficients of 0.9952 and 0.9967, low limits of detection of 0.4 and 0.3 ng/mL, and the high pre-concentration factors of 144 and 151 for determination of FLX and NFLX, respectively. Usage of proposed method for determination of FLX and NFLX in human urine and real water samples demonstrated a promising, simple, selective and sensitive sample preparation and determination method that can be applied in routine analysis.