ABSTRACT
Carbon dot (CD)-based fluorimetric sensors have attracted immense attention for the detection of metal ions. Among the available works in this direction, more than 70% of the studies reported the detection of Fe3+ through luminescence quenching. Ferric ions are significant species from environmental and biological point of view. Excited-state electron transfer from carbon dots to ferric ions is suggested as the reason for the luminescence quenching. However, to date, no solid proof was provided to demonstrate this electron transfer process. Herein, N-doped blue luminescent carbon dots prepared via hydrothermal carbonization are used to demonstrate the exact mechanism operating in the above-mentioned detection strategy. The carbon dots possessed an average size of 4.9 nm, and exhibited good aqueous solubility as well as an excitation wavelength-dependent emission. Fe3+-mediated luminescence quenching was quantitatively achieved at the micromolar level, with a detection limit of 1.426 µM. The CD-mediated reduction of ferric ions is confirmed by spectral analysis. Fe3+-induced luminescence quenching was partially restored in the presence of ascorbic acid, enabling the sub-micromolar level monitoring of this analyte, with the lowest detection amount of 276 nM. Turnbull's blue method is adopted for confirming the reducing role of ascorbic acid, which eventually increased the luminescence of the system, evoking a turn-on response.
ABSTRACT
This article reveals the first ever prospective application of Graphene-Rhodamine array (GRH) as a colorimetric and fluorimetric sensor for Hg(2+) ions. The duality of Graphene to undergo π-π and dispersive interactions with Rhodamine as well as to act as a selective adsorbent for Hg(2+) is conceptualized in this study. These interactions lead to decrease in absorbance of the dye in the presence of graphene, which is restored when kept in contact with Hg(2+) ions. The feasibility of the mechanism has been proved using EDTA as the coordinating ligand. It is noteworthy that all the optical variations occurred in the visible scale of the electromagnetic spectrum. The GRH array exhibited higher sensitivity toward the target ion with a limit of detection of 2 ppb. A perfect linear variation of absorbance at 554 nm with Hg(2+) concentration was observed in 0-1000 nM range, enabling the use of the system as a quantitative sensor for the test ion. The commendable selectivity of the array toward Hg(2+) ion has been investigated by observing the optical response in the presence of other environmentally relevant metal ions. A reversible turn off and turn on INHIBIT logic gate has been proposed which extends the scope of the designed array for the development of automated chemical systems. The fluorescence resonance energy transfer (FRET) ability of graphene paves the backbone for the fluorimetric detection. Fluorimetric strategy yielded a much lower limit of detection of 380 ppt using this probe, which makes a significant advance in trace detection of Hg(2+) ions.
