Preparation Of Magnetic Solid Phase Extraction Adsorption Materials And Application In Biological Samples

In this thesis, magnetic octadecylsilane-polyacrylonitrile thin-films and bovine serum albumin?BSA? restricted access octadecyl- and phenyl- mixed functionalized magnetic silica nanoparticles?BSA-C18/Ph-Fe₃O₄@SiO₂ NPs? have been synthesized and employed as the miniaturized solid-phase extraction sorbents with the aid of magnetic separation techniques. The proposed sample pretreatment techniques were followed by the HPLC-UV or UHPLC-MS/MS detection for the analysis of some target analytes in different complex biological samples. The specific experiments steps are as follows:1. In this study, conventional thin-film microextraction?TFME? was endowed with magnetic by introducing superparamagnetic Fe₃O₄@SiO₂ nanoparticles into thin-films. Novel magnetic octadecylsilane?ODS?-polyacrylonitrile?PAN? thin-films were prepared by spraying, and used for the microextraction of quetiapine and clozapine in plasma and urine samples, followed by the detection of HPLC-UV. The influencing factors on the extraction efficiency of magnetic ODS-PAN TFME, including p H, extraction time, desorption solvent, desorption time, and ion strength were investigated systematically. Under the optimal conditions, both analytes showed good linearity over ranges of 0.070-9.000 ?g m L^-1 and 0.012-9.000 ?g m L^-1 in plasma and urine samples, respectively, with correlation coefficients?R2? above 0.9990. Limits of detection?LODs? for quetiapine in plasma and urine samples were 0.013 and 0.003 ?g m L^-1, respectively. LODs for clozapine in plasma and urine samples were 0.015 and 0.003 ?g m L^-1, respectively. The relative standard deviations?RSDs? for quetiapine and clozapine were less than 9.23%. After the validation, the protocol was successfully applied for the determination of quetiapine and clozapine in patients' plasma and urine samples with satisfactory recoveries between 99 to 110%. The proposed magnetic ODS-PAN TFME was very simple, fast and easy to handle. It showed high potential as a powerful pretreatment technology for routine therapeutic drug monitoring?TDM? in plasma and urine samples.2. In current study, a robust magnetic solid-phase extraction?MSPE? method based on bovine serum albumin?BSA? restricted access octadecyl- and phenyl-mixed-functionalized magnetic silica nanoparticles?BSA-C18/Ph-Fe₃O₄@SiO₂ NPs? as sorbent was developed for rapid extraction of venlafaxine, sertraline, diphenhydramine, fluoxetine and its metabolite norfluoxetine from fish muscle tissue followed by ultra-high performance liquid chromatography-tandem mass spectrometry?UHPLC-MS/MS?. The influencing factors?e.g. p H values, extraction time, elution solvent, elution volume and elution time? of MSPE were investigated systematically by the detection of HPLC-UV. Under the optimal conditions, by using paroxetine as the internal standard, the limits of quantification?LODs? of the target analytes were all estimated to be lower than 0.06 ng g^-1. The matrix effect of five target compounds was in the range of 95.07^-119.79%. Analytes-free fishes were exposed in drugs-contaminated water(containing 1 ng m L^-1 of venlafaxine, sertraline, diphenhydramine and fluoxetine) for 20 days. The contents of the four target drugs and the metabolite norfluoxetine in fish tissue were found to be distributed in the range of 1.54^-18.07 ng g^-1. Furthermore, the proposed method was applied in the six kinds of fish?blackhead fish, wuchang fish, carp, little yellow croake, diaozi fish and hairtail? in the loacal martet. It was found that venlafaxine and diphenhydramine were highly susceptible to the sample matrix. Norfluoxetine, fluoxetine and sertraline were successfully analysised in six kinds of fish with the recovery in the range of 88^-118%?except for sertraline in hairtail?. The experiment results indicated that the prepared BSA-C18/Ph-Fe₃O₄@SiO₂ NPs provided the potential of separation/preconcentration of the target pharmaceuticals, with the merits of strong magnetism, good reusability and biocompatibility.