Extraction of bisphenols with functionalized magnetic nanoparticle

Objective: In this thesis, due to the trace or ultra-trace amounts of bisphenols in environmental water matrices, studies were carried out to develop robust, environmentally friendly, high selectivity and sensitivity, accurate and easy to use analytical methods. A new magnetic solid phase extraction (MSPE) method was developed for the extraction of bisphenol A (BPA) and bisphenol F (BPF) from environmental water samples. Fe3O4@SiO2@epoxy@amine magnetic nanoparticles were obtained by silanization of Fe3O4 magnetic nanoparticles and modification of the surface with polyetheramines. The synthesized magnetic nanoparticles are new and there is no information about their use in the literature before. Functionalized magnetic nanoparticles were intended to offer a new approach in the extraction of bisphenols due to their advantages in time, reagent and labour saving as well as high extraction efficiency. Material and Methods: As a solid phase material, Fe3O4 magnetic nanoparticles were coated with tetraethyl orthosilicate (TEOS) in the first stage (Fe3O4@SiO2). In the second stage, magnetic nanoparticles were functionalized with epoxy groups using 3-glycidoxypropyl trimethoxysilane (GPTMS). The surface of the obtained Fe3O4@SiO2@epoksi magnetic nanoparticles was modified by polymerization with polyetheramines (Fe3O4@SiO2@epoksi@amin). The developed MSPE (Magnetic Solid Phase Extraction) method was optimized by investigating parameters such as pH effect, extraction time, solvent selection, and solvent volume. Under optimum conditions, the analytical performance of the method was evaluated, and the method was applied to spring water, bottled water, wastewater, and Büyük Menderes River water samples. Results and Conclusion: The characterization studies of Fe3O4, Fe3O4@SiO2, Fe3O4@SiO2@epoksi, Fe3O4@SiO2@epoksi@amin magnetic nanoparticles were conducted using FTIR (Fourier Transform Infrared Spectroscopy) and SEM (Scanning Electron Microscopy). The method was developed by optimizing various extraction parameters such as the pH of the medium, extraction time, solvent selection, and solvent volume. In the pH study, it was not affected by pH. The optimum conditions were determined as extraction time 60 min, extraction solvent 50% ACN-50% MeOH (50% acetonitrile-50% methanol) mixture and solvent volume 0.5 mL. Under these conditions, Fe3O4@SiO2@epoxy@amine magnetic nanoparticles were added to environmental water samples containing BPA and BPF and analysed for BPA and BPF by high performance liquid chromatography (HPLC) to verify the applicability of the method. The analytical performance of the method was evaluated within the linear working range of 5 ng mL-1 to 100 ng mL-1 for BPA and BPF. Relative standard deviation values of 1.3% and 3.2% were obtained for BPA and BPF, respectively. The developed Magnetic Solid Phase Extraction (MSPE) method showed reproducibility in the extraction of BPA and BPF with limits of quantification (LOQ) of 0.061 ng L-1 and 0.173 ng L-1, respectively. For the analysis of endocrine disrupting chemicals such as BPA and BPF, recoveries in the range of 83.2% to 104.1% were obtained from tap water, plastic bottle water, waste water and Büyük Menderes River water samples. Fe3O4@SiO2@epoxy@amine magnetic nanoparticles were successfully applied for the extraction and enrichment of BPA and BPF.