Heteroatom-Doped Carbon Quantum Dots and Polymer Composite as Dual-Mode Nanoprobe for Fluorometric and Colorimetric Determination of Picric Acid

High Resolution Image Download MS PowerPoint Slide Oxygen- and nitrogen-heteroatom-doped, water-dispersible, and bright blue-fluorescent carbon dots (ON–CDs) were prepared for the selective and sensitive determination of 2,4,6-trinitrophenol (picric acid, PA). ON–CDs with 49.7% quantum yield were one-pot manufactured by the reflux method using citric acid, d -glucose, and ethylenediamine precursors. The surface morphology of ON–CDs was determined by scanning transmission electron microscopy, high-resolution transmission electron microscopy, dynamic light scattering, Raman, infrared, and X-ray photoelectron spectroscopy techniques, and their photophysical properties were estimated by fluorescence spectroscopy, UV–vis spectroscopy, fluorescence lifetime measurement, and 3D-fluorescence excitation–emission matrix analysis. ON–CDs at an average particle size of 3.0 nm had excitation/emission wavelengths of 355 and 455 nm, respectively. With the dominant inner-filter effect- and hydrogen-bonding interaction-based static fluorescence quenching phenomena supported by ground-state charge-transfer complexation (CTC), the fluorescence of ON–CDs was selectively quenched with PA in the presence of various types of explosives (i.e., 2,4,6-trinitrotoluene, tetryl, 1,3,5-trinitroperhydro–1,3,5-triazine, 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane, pentaerythritol tetranitrate, 3-nitro-1,2,4-triazole-5-one, and TATP-hydrolyzed H 2 O 2 ). The analytical results showed that the emission intensity varied linearly with a correlation coefficient of 0.9987 over a PA concentration range from 1.0 × 10 –9 to 11.0 × 10 –9 M. As a result of ground-state interaction (H-bonding and CTC) of ON–CDs with PA, an orange-colored complex was formed different from the characteristic yellow color of PA in an aqueous medium, allowing naked-eye detection of PA. The detection limits for PA with ON–CDs were 12.5 × 10 –12 M (12.5 pM) by emission measurement and 9.0 × 10 –10 M (0.9 nM) by absorption measurement. In the presence of synthetic explosive mixtures, common soil cations/anions, and camouflage materials, PA was recovered in the range of 95.2 and 102.5%. The developed method was statistically validated against a reference liquid chromatography coupled to tandem mass spectrometry method applied to PA-contaminated soil. In addition, a poly(vinyl alcohol)-based polymer composite film {PF(ON–CDs)} was prepared by incorporating ON–CDs, enabling the smartphone-assisted fluorometric detection of PA.