Detection of 2,4-Dinitrotoluene (DNT) as a Model System for Nitroaromatic Compounds via Molecularly Imprinted Short-Alkyl-Chain SAMs

Abstract

A 2-D molecularly imprinted monolayer (2-D MIM) approach was used to prepare a simple and robust sensor for nitroaromatic compounds with 2,4-dinitrotoluene (DNT) as the model compound, which is a precursor and analog for explosive 2,4,6-trinitrotoluene (TNT). In contrast to studies utilizing long-chain hexadecylmercaptan self-assembled monolayers (SAM)s for sensing, a shorter-chain alkylthiol (i.e., butanethiol SAM) was utilized for DNT detection. The role of the chain length of the coadsorbed alkylthiol was emphasized with a matched template during solution adsorption. Semiempirical PM3 quantum calculations were used to determine the molecular conformation and complexation of the adsorbates. A switching mechanism was invoked on the basis of the ability of the template analyte to alter the packing arrangement of the alkylthiol SAMs near defect sites as influenced by the DNT–ethanol solvent complex. A 2-D MIM was formed on the Au surface electrode of a quartz crystal microbalance (QCM), which was then used to sense various concentrations of the analyte. Interestingly, the 2-D MIM QCM also enabled the selective detection of DNT even in a mixed solution of competing molecules, demonstrating the selectivity figure of merit. Likewise, electrochemical impedance spectroscopy (EIS) data at different concentrations of DNT confirmed the 2-D MIM effectiveness for sensing based on the interfacial conformation and electron-transport properties of the imprinted butanethiol SAM.