RESUMO
By attaching the1-pyreneiodide ancillary ligand to the surface of polyvinylpyrrolidone-stabilized gold (Au:PVP) cluster or the cetyltrimethyl ammonium bromide-stabilized gold (Au:CTAB) nanorod, a new class of luminescent mixed ligand-stabilized gold nanostructures is synthesized. This postsynthetic surface modification method followed by us is a comparatively easier and hassle-free technique to acquire surface-active luminescent "functional nanomaterials". Careful analyses of transmission electron microscopy images revealed that the sizes of these Au-clusters or Au-nanorods remain unchanged without any noticeable aggregation in the medium. Owing to the formation of an excimer within the neighboring pyrenes mounted on the surface of core nanostructures (i.e., Au:PVP nanocluster and Au:CTAB nanorod), the resulting pyrene-grafted nanocomposites exhibit strong emission characteristics. The strong excimer emission is significantly quenched in the presence of electron-deficient chemical inputs, and this phenomenon can be used for analytical purposes. Using these luminescent Au-nanomaterials, we demonstrate a selective detection and sensing of trace-level nitroaromatic explosives (e.g., trinitrotoluene, trinitrophenol (TNP), dinitrotoluene, 4-nitrotoluene, etc.). It was observed that the Py-Au:PVP nanocluster is equally effective for explosive detection in both solution and solid phases with the limit of detection up to 10 nanomolar. A high Stern-Volmer constant of up to 3.88 × 106 M-1 was seen in the case of TNP in anhydrous methanol at 298 K. The deactivation pathway operating within the Py-Au:PVP nanocluster and the analytes is thought to be a result of a predominating static quenching process, where a nonfluorescent D-A supramolecular adduct is formed in the medium. Py-Au:PVP has also been successfully used to develop latent fingerprints from nonporous surfaces under an exposure of 365 nm UV light. The results suggest that these new composite materials could behave as potential "functional nanomaterials", which might be a promising alternative for on-the-spot detection of explosive traces as well as for easy visualization of latent fingerprints.
RESUMO
Two luminescent cyclometalated Pt(II)-complexes, 1â¢Pt and 2â¢Pt, respectively, were synthesized by using unsymmetrical Câ§Nâ§N ligands having different alkyl substituents. These π-electron-rich complexes are used for sensing various electron deficient nitroaromatic explosives, e.g., 4-nitrotoluene (NT), 2,4-dinitrotoluene (DNT), 2,4,6-trinitrotoluene (TNT), and 2,4,6-trinitrophenol (TNP), in aqueous, nonaqueous, as well as in the solid state as a paper strip with maximum detection limit of ca. 10-9 M. It was demonstrated that the sparingly soluble 2â¢Pt complex becomes water-soluble in the presence of all kinds of surfactants, viz., cationic (e.g., cetyltrimethylammonium bromide, CTAB), anionic (e.g., sodium dodecyl sulfate, SDS), and neutral (e.g., Triton X-100). This may be due to the incorporation of its long lyophilic tail group (-C12H25) inside the micellar core, exposing planar Pt(II)Câ§Nâ§N headgroup to the aqueous bulk phase. It was also observed that the extent of solubility of these Pt(II)-complexes in micellar media strongly depends on the length of the existing alkyl chain. For instance, the presence of longer dodecyl chain makes 2â¢Pt complex ca. 1000-fold more soluble than the complex 1â¢Pt, which contains a shorter propyl chain. Their sensing behavior essentially arises by the quenching of Pt(II)-based intense luminescence due to the supramolecular charge transfer (CT) process originating from Pt(II)Câ§Nâ§N-antenna to the electron deficient nitroaromatic explosives. Our present work shows that the micellar adducts formed by highly luminophoric material and surfactant molecules could effectively detect such explosives in aqueous medium with better sensitivity compared to what were observed in other media.
