Rapid quantification of 2,4-dichlorophenol in river water samples using molecularly imprinted polymers coupled to ambient plasma mass spectrometry

Rapid quantification of environmental pollutants is important for water quality control and environmental monitoring. In this work, we report the development of molecularly imprinted polymers (MIPs) obtained from poly(methyl vinyl ether-alt-maleic acid) polymer. The synthesized materials were used for selective pre -concentration of 2,4-dichlorophenol, a priority pollutant which creates a threat to public health. The structure of poly(methyl vinyl ether-alt-maleic acid) was functionalized with 4-aminomethylpyridine (4-AMP) to incorporate pyridine groups presumably responsible for increased affinity towards 2,4-dichlorophenol. The synthesis was performed with different degree (10%, 20% and 30%) of 4-AMP functionalization to investigate the influence of pyridine group content on the final MIPs properties. The molecular imprinting process was conducted by ami-dation of polymers' anhydride groups with diethylenetriamine. Moreover, the experimental data indicated that maximum adsorption capacity was observed for the highest 4-AMP functionalization degree. Similarly, MIPs with the highest 4-AMP content proved to possess the highest selectivity towards the analyte. Finally, the functionalized MIPs were used to quantify 2,4-dichlorophenol by their direct introduction into a specially designed ambient mass spectrometry setup. The detection limits were improved significantly over the ones measured for pure analyte solution. The proposed analytical technique was used to quantify 2,4-dichlorophenol in river water and wastewater samples. Good recovery results were obtained, which proves that the method can be used for analysis of complex real-life samples.