Functionalization of Ag nanoparticles with the bis-acridinium lucigenin as a chemical assembler in the detection of persistent organic pollutants by surface-enhanced Raman scattering.

Organochlorine pesticide endosulfan has been detected for the first time by using surface-enhanced Raman scattering (SERS) at trace concentrations. The bis-acridinium dication lucigenine was successfully used as a molecular assembler in the functionalization of metal nanoparticles to facilitate the approach of the pesticide to the metal surface. From the SERS spectra valuable information about the interaction mechanism between the pesticide and lucigenin can be deduced. In fact, endosulfan undergoes an isomerization upon adsorption onto the metal, while the viologen undergoes a rotation of the acridinium planes to better accommodate the pesticide molecule. An interaction between the N atom of the central acridinium ring and the pesticide Cl-CC-Cl fragment is verified through a charge-transfer complex. The present study affords important information which can be applied to the design of chemical sensor systems of persistent organic pollutants based on the optical detection on functionalized metal nanoparticle.