A novel ion-imprinted polymer based on pyrrole as functional monomer for the voltammetric determination of Hg(II) in water samples

Abstract

A novel selective ion-imprinted polymer (IIP) was synthesized, characterized, and used as part of a carbon paste electrode (CPE) for the electrochemical analysis of Hg(II) in real water samples by differential pulse anodic stripping voltammetric (DPASV). Hg-IIP (mercury-ion imprinted polymer) was synthesized using pyrrole for the first time as a functional monomer, ethylene glycol dimethacrylate (EGDMA) as a cross-linker agent, and sodium persulfate as initiator. The CPE was modified with IIP (CPE-IIP) with a composite mixture of Hg-IIP (10%), graphite (90%), and 0.08 g of paraffin oil. A notable difference in the Hg(II) Iap (anodic peak current) between a CPE, CPE-IIP and CPE-NIP (non-imprinted polymer) was observed when optimizing the differential pulse anodic stripping voltammetry (DPASV) parameters by a Box-Behnken design. When analyzing a 50 µmol l−1 Hg(II) solution, the optimal conditions (step potential: 0.11 V, amplitude: 0.15 s, modulation time: 0.005 s, and interval time: 0.15 s) allowed an Iap of 144 µA with a %RSD < 10% for the CPE-IIP response, in comparison to the Iap of 1.47 µA obtained with the CPE-NIP, Iap confirming the existence and performance of the recognition cavities in the IIP. The proposed methodology presents a limit of detection (LOD) of 0.02 mg l−1 within a linear range of 0.09 mg l−1 to 20.05 mg l−1. The inter-day and intra-day precision were measured in two concentration levels (1 mg l−1 and 10 mg l−1) with %RSD < 10%. The developed methodology was successfully applied to determine Hg(II) in three spiked samples (10 mg l−1) of natural water sources without acid digestion, obtaining percentage recoveries close to 99.74%, which demonstrates that digestion treatment is not required for this kind of samples.