Amine-Capped ZnS−Mn2+ Nanocrystals for Fluorescence Detection of Trace TNT Explosive

Abstract

Mn²⁺-doped ZnS nanocrystals with an amine-capping layer have been synthesized and used for the fluorescence detection of ultratrace 2,4,6-trinitrotoluene (TNT) by quenching the strong orange Mn²⁺ photoluminescence. The organic amine-capped nanocrystals can bind TNT species from solution and atmosphere by the acid−base pairing interaction between electron-rich amino ligands and electron-deficient aromatic rings. The resultant TNT anions bound onto the amino monolayer can efficiently quench the Mn²⁺ photoluminescence through the electron transfer from the conductive band of ZnS to the lowest unoccupied molecular orbital (LUMO) of TNT anions. The amino ligands provide an amplified response to the binding events of nitroaromatic compounds by the 2- to ∼5-fold increase in quenching constants. Moreover, a large difference in quenching efficiency was observed for different types of nitroaromatic analytes, dependent on the affinity of nitro analytes to the amino monolayer and their electron-accepting abilities. The amine-capped nanocrystals can sensitively detect down to 1 nM TNT in solution or several parts-per-billion of TNT vapor in atmosphere. The ion-doped nanocrystal sensors reported here show a remarkable air/solution stability, high quantum yield, and strong analyte affinity and, therefore, are well-suited for detecting the ultratrace TNT and distinguishing different nitro compounds.