| Abstract: | Herein, electromembrane extraction was combined with ultraviolet spectrophotometry using a customized manifold for preconcentration and simultaneous determination of morphine, codeine, and papaverine in water and human urine samples. Absorption spectra of the extracts were recorded inside the lumen of the hollow fiber using two fiber optics connected to a miniature spectrophotometer. Partial least squares regression was applied to resolve the overlapped spectra of the analytes. Performance of the model was validated by an independent test set. Central composite design was applied to optimize the extraction parameters. The optimized extraction conditions are as follows; supporting liquid membrane: 2‐nitrophenyl octyl ether containing 15% v/v bis(2‐ethylhexyl) phosphate, applied voltage: 80 V, donor pH: 3.0, acceptor pH: 1.0, extraction time: 20 min. Finally, the optimized extraction method was validated for determination of the mentioned alkaloids in human urine samples. The method showed good linearity (R2 > 0.995) for all of the mentioned alkaloids. The limits of detection for morphine, codeine, and papaverine in diluted human urine were found to be 0.6, 1.1, and 0.6 ng/mL, respectively with acceptable relative standard deviations. Enrichment factors of 104, 108, and 102 were achieved for morphine, codeine, and papaverine, respectively. |
