Environmental impact of molecularly imprinted polymers used as analyte sorbents in mass spectrometry

The molecularly imprinted polymers (MIPs) with the following herbicides used as templates 2,4-dichlorophenoxyacetic acid (2,4-D) or 4-chloro-2-methylphenoxy- acetic acid (MCPA) were synthesized by precipitation polymerization technique using 4-vinylpyridine (4-VP) as a functional monomer, ethylene glycol dimethacrylate (EGDMA) as a cross-linking agent, and 2,2'-azobisisobutyronitrile (AIBN) as an initiator in methanol solvent. For the flavonoid MIPs, rutin (Ru) and quercetin (Q) were used as templates and synthesized via a similar technique, utilizing acrylamide (AA) as a functional monomer. Analysis of binding in the molecularly imprinted and non-imprinted polymer (NIP) has proved that MIP shows a higher affinity towards the analytes, compared to NIP. MIP was used to determine analytes in water using the Flowing Atmospheric-Pressure Afterglow Mass Spectrometry (FAPA-MS) technique. In this approach, the method limit of detection (MLOD) of 2,4-D, MCPA, Ru, and Q in MIP was 4, 3, 10, and 5 μg in 1 g MIP, respectively. The release kinetics of the analytes from MIP and their stability in water was studied. The cultures of Tetradesmus obliquus (Turpin) M.J. Wynne and Daphnia magna Straus were used for in vivo toxicity studies revealing that only Ru-MIP and Q-MIP had negative effect on the living organisms used in the bioassays.