A ‘sandwich’ structure for highly sensitive detection of TNT based on surface-enhanced Raman scattering

Ultra-sensitive detection of 2,4,6-trinitrotoluene (TNT) plays an important role in society security and human health. The Raman probe molecule p-aminothiophenol (PATP) can interact with TNT in three ways to form a TNT-PATP complex. In this paper, a ‘sandwich’ structure was developed to detect TNT with high sensitivity. Au nano-pillar arrays (AuNPAs) substrates modified by low-concentration PATP through Au–S bonds were acted as capture probe for TNT. Meanwhile, Ag nano-particles (AgNPs) modified by PATP at higher concentration were employed as tags for surface-enhanced Raman scattering (SERS). The formation of the TNT-PATP complex is not only the means by which AuNPAs substrates recognize and capture TNT, but also links the SERS tags to TNT, forming an AuNPAs-TNT-AgNPs ‘sandwich’ structure. The Raman signal of PATP was greatly enhanced mainly because novel ‘hot spots’ formed between the AuNPAs and AgNPs of the ‘sandwich’ structure. The Raman signal of PATP was further amplified by the chemical enhancement effect induced by the TNT-PATP complex formation. Based on this mechanism, the limit of detection (LOD) of TNT was determined from the Raman signal of PATP. The LOD reached 10−9 mg/mL (4.4 × 10−12 M), much lower than that suggested by the US Environmental Protection Agency (88 nM). Moreover, TNT was selectively detected over several TNT analogues 2,4-dinitrotoluene (DNT), p-nitrotoluene (NT) and hexogen (RDX). Finally, the ‘sandwich’ structure was successfully applied to TNT detection in environmental water and sand.