Considering the high toxicity and widespread availability of fluoride ions in different environmental matrices, it is imperative to design a probe for its detection. In view of this, a selective fluorescent on-off-on probe based on carbon quantum dots (CQDs) and Eu has been designed. We have synthesized water-soluble carboxylic acid-functionalized CQDs and monitored their interaction with Eu. Luminescence quenching in the CQD emission was observed (switch-off) on adding Eu ions. We investigate the reason for this luminescence quenching using time-resolved emission and high-resolution transmission electron microscopy (HRTEM) studies and observed that both electron transfer from CQDs to Eu and aggregation of CQDs are responsible for the luminescence quenching. ζ-Potential and X-ray photoelectron spectroscopy studies confirm Eu binding with the COOH groups on CQD surface. Interestingly, luminescence regains after the addition of fluoride ions to the CQDs/Eu system (switch-on). This has been assigned to the removal of Eu from the CQD surface due to the formation of EuF and is confirmed by X-ray diffraction and HRTEM measurements. The sensitivity of the probe was tested by carrying out experiments with other competing ions and was found to be selective for fluoride ions. Experiments with variable concentrations of fluoride ions suggest that the working range of the probe is 1-25 ppm. The probe has been successfully tested for the detection of fluoride ions in a toothpaste sample and the results were compared to those of ion chromatography. To the best of our knowledge, this is the first report based on CQDs and Eu for the detection of fluoride ions, wherein a clear mechanism of the detection has been demonstrated, which, in turn, will help to develop better detection methods. The suggested probe is green, economical, rapid, efficient, and, most importantly, selective and can be used for the detection of fluoride ions in real environmental samples.

Uranium is one of the most toxic and important elements present in the environment, and because of its high toxicity, ultra-trace-level detection is of utmost importance. Many methods were reported earlier for this purpose, but each has its own limitations such as high cost, sophisticated instrumentation, sample processing, and so forth. Herein we have demonstrated an alternate method that is much simpler and can be used for the ultra-trace-level detection of uranium. We have synthesized 3-mercaptopropionic acid (MPA)-capped CdSe/CdS core-shell quantum dots (CSQDs) and used its photoluminescence properties to detect uranium in solution. Steady-state emission studies suggest the luminescence quenching of CSQDs in the presence of uranium. Redox levels of CSQDs and uranium suggests that the electron-transfer process from photoexcited CSQDs to uranium is a thermodynamically viable process, which has subsequently been confirmed by time-resolved studies. A Stern-Volmer plot of CSQDs with uranium suggests that the detection limit of this method is 74.5 ppb. The method has an advantage over other reported methods for being simple and low cost and requiring a small amout of sample processing. To the best of our knowledge, we are reporting for the first time uranium detection using quasi-type II CSQDs and proposing the mechanistic path through luminescence spectroscopy, which in turn helps us to design an efficient detection method.

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The selective separation of uranyl ions from an aqueous solution is one of the most important criteria for sustainable nuclear energy production. We report herein a known, but unexplored extractant, tetraalkyl urea, which shows supreme selectivity for uranium in the presence of interfering thorium and other lanthanide ions from a nitric acid medium. The structural characterization of the uranyl complex (UO2X2·2L, where X = NO3(-), Cl(-) and Br(-)) by IR, NMR and single crystal X-ray diffraction provides insight into the strong interaction between the uranyl ion and the ligand. The origin of this supreme selectivity for uranyl ions is further supported by electronic structure calculations. Uranyl binding with the extractant is thermodynamically more favourable when compared to thorium and the selectivity is achieved through a combination of electronic and steric effects.

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