Preparation and characterization of dummy-template molecularly imprinted polymers as potential sorbents for the recognition of selected polybrominated diphenyl ethers.

The main aim of this work was to conduct the preliminary/basic research concerning the preparation process of a new dummy molecularly imprinted polymer (DMIP) materials. Developed DMIPs were proposed as a sorption material in solid-phase extraction (SPE) technique for recognition of selected low mass polybrominated diphenyl ethers (PBDEs) - PBDE-47 and PBDE-99. Four new DMIPs were synthesized employing bulky polymerization technique by application of structural analogue of low mass PBDEs - 4,4'-Dihydroxydiphenyl ether, as a dummy template. The DMIPs and corresponding non-imprinted polymers were prepared using different functional monomers: methacrylic acid; methyl methacrylate and different porogen agents: acetonitrile and tetrahydrofuran. The polymerization reaction was thermally initiated with 1,1'-azobis (cyclohexanecarbonitryle). Ethylene glycol dimethacrylate was applied as a cross-linker. To optimize geometries and to calculate energies of the respective template-monomer complexes, the computational molecular modeling method was employed. The particles morphology and physicochemical characteristics of developed DMIPs and their equivalent NIPs were performed using nitrogen sorption porosimetry, scanning electron microscopy, and Fourier transform infrared spectroscopy. The sorption capacities of prepared DMIPs and corresponding NIPs were studied using standard binding test. The adsorption capability studies give a possibility to assess the imprinting factor (IF) values, which were in the range from 1.1 to 4.0, depending on the DMIP type. The recovery values of PBDE-47 and PBDE-99 from prepared organic solutions were in the range from 43 to 92%, depending on the studied DMIP. Performed basic laboratory studies give a possibility to select the optimal DMIP material which might be applied in the environmental samples preparation process as a potential sorbent for the recognition of low mass PBDEs.