Ultrasensitive Surface Plasmon Resonance Detection of Trinitrotoluene by a Bis-aniline-Cross-Linked Au Nanoparticles Composite

Abstract

A bis-aniline-cross-linked Au nanoparticles (NPs) composite is electropolymerized on Au surfaces. The association of trinitrotoluene, TNT, to the bis-aniline bridging units via pi-donor-acceptor interactions allows the amplified detection of TNT by following the surface plasmon resonance (SPR) reflectance changes as a result of the coupling between the localized plasmon of the AuNPs and the surface plasmon wave associated with the gold surface. The detection limit for analyzing TNT by this method is approximately 10 pM. The electropolymerization of the bis-aniline-cross-linked AuNPs composite in the presence of picric acid results in a molecular-imprinted matrix for the enhanced binding of TNT. The imprinted AuNPs composite enabled the sensing of TNT with a detection limit that corresponded to 10 fM. Analysis of the SPR reflectance changes in the presence of different concentrations of TNT revealed a two-step calibration curve that included the ultrasensitive detection of TNT by the imprinted sites in the composite, KassI. for the association of TNT to the imprinted sites, 6.4 x 10(12) M-1, followed by a less sensitive detection of TNT by the nonimprinted pi-donor bis-aniline sites (KNIass. = 3.9 x 10(9) M-1). The imprinted AuNPs composite reveals impressive selectivity. The structural and functional features of the bis-aniline-cross-linked AuNPs composites were characterized by different methods including ellipsometry, AFM, and electrochemical means. The dielectric properties of the AuNPs composite in the presence of different concentrations of TNT were evaluated by the theoretical fitting of the respective experimental SPR curves. The ultrasensitive detection of the TNT by the AuNPs composite was attributed to the changes of the dielectric properties of the composite, as a result of the formation of the pi-donor-acceptor complexes between TNT and the bis-aniline units. These changes in the dielectric properties lead to a change in the conductivity of the AuNPs matrix.