Abstract
Pharmaceutical compounds are small, invisible, and biologically powerful molecules that, due to widespread production and consumption, have become part of the environment, causing long-term adverse effects on biota even at low doses. Advances in sensitive and reliable analytical methods have made their detection possible in complex environmental matrices such as wastewater. Given the large number of synthesized pharmaceuticals with various therapeutic purposes, the occurrence of a synergistic effect is to be expected, interfering with their analysis. Therefore, the challenging analysis is often improved through the application of different sample preparation techniques. This paper includes the development of an SPE-HPLC-DAD method for the determination of eleven pharmaceuticals from water samples. To achieve better recoveries for the specified pharmaceutical (sulfamethoxazole) and possibly other components of the mixture, a sulfamethoxazole-imprinted polymer (MIP-SMETOX) was prepared and used in combination with a commercial sorbent (Oasis HLB) for MIP-SPE-HPLC-DAD. After optimization of the extraction conditions, both methods were validated. The LOD was 0.1 to 0.5 µg/L for SPE-HPLC-DAD and 0.1 to 0.25 µg/L for MIP-SPE-HPLC-DAD, depending on the pharmaceuticals. The matrix effect is different (77-196%) for both methods. A decrease in the signal for sulfamethoxazole (77%) was observed with SPE-HPLC-DAD, while MIP-SMETOX as a sorbent is not suitable for procaine (196%), and this is also the highest matrix effect. To extend the data obtained, additional in silico methods were used to gain deeper insights into the nature and strength of the binding interactions. Both methods (with and without MIP) confirmed their purpose by determining various validation performance features, and the final goal of the developed methods was tested using complex wastewater. The MIP-SMETOX produced justified its production, as the MIP-SPE-HPLC-DAD method is generally slightly better than the method using only a commercial sorbent.