The Failure of Molecular Imprinting in Conducting Polymers: A Case Study of Imprinting Picric Acid on Polycarbazole

Abstract

The aims of this study were to investigate the potential of utilising molecularly imprinted polycarbazole layers to detect highly toxic picric acid (PA) and to provide information about their performance. Quantum chemical calculations showed that strong interactions occur between PA and carbazole (bond energy of approximately 31 kJ/mol), consistent with the theoretical requirements for effective molecular imprinting. The performance of the sensors, however, was found to be highly limited, with the observed imprinting factor values for polycarbazole (PCz) layers being 1.77 and 0.95 for layers deposited on Pt and glassy carbon (GC) electrodes, respectively. Moreover, the molecularly imprinted polymer (MIP) layers showed worse performance than unmodified Pt or GC electrodes, for which the lowest limit of detection (LOD) values were determined (LOD values of 0.09 mM and 0.26 mM, respectively, for bare Pt and MIP PCz/Pt, as well as values of 0.11 mM and 0.57 mM for bare GC and MIP PCz/GC). The MIP layers also showed limited selectivity and susceptibility to interfering agents. An initial hypothesis on the reasons for such performance was postulated based on the common properties of conjugated polymers.

Keywords

• molecularly imprinted polymer
• sensor
• picric acid
• 2,4,6-trinitrophenol
• detection
• polycarbazole