Detection of Nitroaromatics by Pyrene-Labeled Starch Nanoparticles

Starch nanoparticles (SNPs) were hydrophobically modified by using 1-pyrenebutyric acid (PyBA) with degrees of substitution (DS) between 0.0006 and 0.11. Fluorescence quenching studies were conducted on the pyrene-labeled starch nanoparticles (Py-SNPs) in dimethyl sulfoxide (DMSO) and water with nitromethane (NM), 4-mononitrotoluene (MNT), 2,6-dinitrotoluene (DNT), and 2,4,6-trinitrotoluene (TNT) to assess the mode of quenching of the pyrene labels in the two solvents. In DMSO where pyrene, starch, and the quenchers were soluble, a decrease in fluorescence signal was the result of dynamic encounters between the excited pyrene labels and the nitrated quenchers. In water where starch could be dispersed but pyrene and the nitroaromatic compounds (NACs) were sparingly soluble, quenching took place through the binding of NACs to pyrene aggregates. Py(11)-SNPs (Py-SNPs with a DS of 0.11)-coated filter papers (Py-CFPs) were prepared as fluorescence sensors. The fluorescence emitted by Py-CFPs was quenched to 25% of its original value within 10 ± 2, 72 ± 20, and 23 ± 4 s upon exposure to vapors of MNT, DNT, and TNT, respectively. When known amounts of NACs were deposited onto Py-CFPs, their limit of detection (LOD) when the fluorescence decreased by more than 3 standard deviations (3σ) from its original value equaled 9.2 ± 0.8, 3.3 ± 0.5, and 0.20 ± 0.02 ng/mm² for MNT, DNT, and TNT, respectively. These response times and LODs were among the best values reported to date in the scientific literature for fluorescence sensors. The selectivity of the Py-CFPs toward NACs was also investigated by comparing their response to the presence of non-nitrated aromatics, amines, and aromatic ketones. Quenching was only observed with the latter family of chemicals tested, but with much lower efficiency compared to TNT, thus reflecting some level of selectivity toward this specific NAC.