In this research, coupling of hollow fiber based liquid–liquid–liquid microextraction (HF-LLLME) method and ESI-IMS was used for the first time for preconcentration and determination of analytes in biological samples including urine and plasma. In hollow fiber based liquid–liquid–liquid microextraction, a layer of organic phase is impregnated into the pores of a 1.3 cm long porous hollow fiber, while the lumen of the hollow fiber was filled with CH 3 COOH (0.5 M) solution as an acceptor solution that was connected directly to the needle of a microsyringe.The fiber was then immersed into 3 ml of a basic aqueous sample. Effective parameters on HF-LLLME such as solvent type, pH of donor phase, acidity of acceptor phase, sample stirring rate, salt addition, extraction temperature and extraction time were studied. The best extraction efficienciy was achieved utilizing a 1.3 cm porous hollow fiber immobilized with n-octanol, 3 mL donor phase sample at pH 9.0 without NaCl addition, 0.50 M CH 3 COOH solution as acceptor phase, 900 rpm stirring rate and 25 min extraction time at room temperature. The analytes were extracted quantitatively from the sample solution into the acceptor solution with an enrichment factor 104. Due to its low cost, the hollow-fiber extraction device was disposed after a single extraction that eliminated the possibility of carry over effects. The limit of detection and relative standard deviation of the method were 2 ng/mL and 5.3%, respectively. In the second work, simultaneous analysis of two antidepressants drugs including trimipramine and desipramine by LLLME-ESI-IMS in biological samples (urine and plasma) was perform. The best extraction efficiencies was achieved using dodecane as a solvent, 0.020 M NaOH solution as donor phase, 0.10 M CH 3 COOH solution as acceptor phase, 860 rpm stirring rate, 20 min extraction time, 45?C sample temperature and 0.05 g/ml NaCl addition to sample. The limit of detection was 1 ng/mL and the relative standard deviation of the method was in the range of 5.3-5.4 %.
