Pallavi Singhal

Green, Water-Dispersible Photoluminescent On–Off–On Probe for Selective Detection of Fluoride Ions

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 Eu3+ has been designed. We have synthesized water-soluble carboxylic acid-functionalized CQDs and monitored their interaction with Eu3+. Luminescence quenching in the CQD emission was observed (switch-off) on adding Eu3+ 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 Eu3+ and aggregation of CQDs are responsible for the luminescence quenching. ζ-Potential and X-ray photoelectron spectroscopy studies confirm Eu3+ binding with the COOH groups on CQD surface. Interestingly, luminescence regains after the addition of fluoride ions to the CQDs/Eu3+ system (switch-on). This has been assigned to the removal of Eu3+ from the CQD surface due to the formation of EuF3 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 Eu3+ 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.

Hot-Hole Extraction from Quantum Dot to Molecular Adsorbate

Ultrafast thermalized and hot-hole-transfer processes have been investigated in CdSe quantum dot (QD)/catechol composite systems in which hole transfer from photoexcited QDs to the catechols is thermodynamically favorable. A series of catechol derivatives were selected with different electron-donating and -withdrawing groups, and the effect of these groups on hole transfer and charge recombination (CR) dynamics has been investigated. The hole-transfer time was determined using the fluorescence upconversion technique and found to be 2-10 ps depending on the molecular structure of the catechol derivatives. The hot-hole-transfer process was followed after monitoring 2S luminescence of CdSe QDs. Interestingly, hot-hole extraction was observed only in the CdSe/3-methoxycatechol (3-OCH3) composite system owing to the higher electron-donating property of the 3-methoxy group. To confirm the extraction of the hot hole and to monitor the CR reaction in CdSe QD/catechol composite systems, ultrafast transient absorption studies have been carried out. Ultrafast transient-absorption studies show that the bleach recovery kinetics of CdSe QD at the 2S excitonic position is much faster in the presence of 3-OCH3. This faster bleach recovery at the 2S position in CdSe/3-OCH3 suggests hot-hole transfer from CdSe QD to 3-OCH3. CR dynamics in CdSe QD/catechol composite systems was followed by monitoring the excitonic bleach at the 1S position and was found to decrease with free energy of the CR reaction.

Electron-Transfer-Mediated Uranium Detection Using Quasi-Type II Core–Shell Quantum Dots: Insight into Mechanistic Pathways

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.

Metal–Ligand Complex-Induced Ultrafast Charge-Carrier Relaxation and Charge-Transfer Dynamics in CdX (X=S, Se, Te) Quantum Dots Sensitized with Nitrocatechol

The present work describes the effect of interfacial complex formation on charge carrier dynamics in CdX (X=S, Se, Te) quantum dots (QDs) sensitized nitro catechol (NCAT). To compare experiments were also carried out with catechol (CAT) where no such complexation was observed. Time-resolved emission studies suggest faster charge separation in CdS(Se)/NCAT system as compared to CdS(Se)/CAT although change in Gibbs free energy for hole transfer is less in former as compared to later. This suggests that complex formation favours charge separation. Similar studies were also carried out in CdTe/NCAT system where hole transfer process was not viable thermodynamically but due to complex formation charge separation was observed. Femtosecond transient absorption studies have been carried out to monitor charge carrier dynamics in early time scale. Transient studies show faster electron cooling in QDs/NCAT system as compared to pure QDs and has been assigned to the complex formation on QDs surface. Interestingly charge recombination dynamics is much faster in QDs/NCAT system as compared to pure QDs which can be attributed to the stronger coupling between QDs and NCAT. Our results suggest a strong metal-ligand complex formation on QDs surface that controls charge carrier dynamics in QDs/molecular adsorbate system and to the best of our knowledge it has never been reported.