CHEM2915 Seminar Series Research Paper Summary

By: Amanda Yung (SID 460321833)

Reference:

A novel colorimetric and fluorescent probe for detecting fluoride anions: from water and toothpaste
samples. Yu, M., Xu, J., Peng, C., Li, Z., Liu, C. Wei, L. Tetrahedron, 2016, 72, 273-278.

Aims and product of paper

Fluoride ions are necessary as a trace element in the human body, but excessively large fluoride ion
concentrations in the body can lead to a plethora of health issues. These health issues typically result
from the ingestion of water containing high fluoride ion levels. Thus, it is important to monitor
fluoride ion concentrations in water bodies. However, existing fluoride detection methods require
training and specialized equipment, making them inaccessible. Hence, this study aimed to develop a
fluorescent probe to detect fluoride ions quantitatively and easily, and test its ability to detect
fluoride ions in tap water and toothpaste samples.

The fluorescent probe developed is a 1,8-napthalimide-based derivative, and the structure of the
probe is shown in Fig. 1.

Fig. 1: Chemical structure of fluorescent probe developed.

The probe has a high fluorescence quantum yield and can detect fluoride ions from not only organic
sources (tetrabutylammonium fluoride (TBAF)), similar to previous fluoride-binding fluorescent
probes, but also fluoride ions from inorganic sources (NaF). This allows the probe to be used in
testing water samples, as water samples from the environment typically contain inorganic fluoride
ions. The probe also has a low detection limit of 1.8 M F-, making it sensitive to and thus suitable
for the detection of fluoride ions. Most importantly, in the presence of increasing concentrations of
fluoride ions, the probe gradually changes colour from yellow to cyan and its fluorescence intensity
decreases. These changes can be detected by the naked eye, making the probe easy to use in
fluoride detection, and allowing the fluoride ion concentration to be quantitatively measured.
Hence, the probe developed is highly suitable to address the aims of the study.
A figure from the study

Figure 2 shows the emission and absorption spectra of the fluorescent probe (1.0 x 10-5 M in DMSO)
obtained from UV-vis and fluorescence titration experiments. In the former, the absorbance of the
probe at different wavelengths was measured in the presence of various amounts of fluoride ions. In
the fluorescence titration experiments, the probe was excited at 460 nm in the presence of various
amounts of fluoride ions, and the intensity of the fluorescence over a range of wavelengths was
measured. The absorption spectrum (left) shows that as increasing amounts of fluoride ions were
added, the probe had decreasing absorption at 459 nm and increasing absorption at 605 nm and 640
nm, resulting in a colour change from yellow to cyan. The emission spectrum (right) indicates that
the fluorescence intensity decreased as increasing amounts of fluoride ions were added.

Fig. 2: Absorption (left) and emission spectrum (right) of the fluorescent probe (1.0 x 10-5 M in
DMSO) with different amounts of TBAF (1.0 x 10-2 M in water) added, excited at 460 nm (from Yu et
al., 2016).

Conclusions and other investigations

This study successfully developed a fluorescent probe that exhibits a large, visible change in the
presence of fluoride ions. The probe is both sensitive and specific to fluoride ions, and was
successful in detecting fluoride ion levels in tap water and toothpaste samples. It appears to be
highly suitable for use in detection of fluoride ion concentrations in healthcare or environmental
studies.

A possible application of the probe may be to track the movement of fluoride ions in bodies of water
and locate the source. By taking water samples at different points along a body of flowing water and
testing the fluoride ion concentration in each sample, one could check if the fluoride ions were
caused by chemical waste or leakages, which could potentially be detrimental to the environment.

In addition, fluoride salts are also used in biological assays as phosphatase inhibitors. In such assays,
the fluorescent probe could be added to measure the free fluoride ion concentration in the assay. If
a known amount of fluoride ions was added, one would be able to then indirectly measure the
number of fluoride ions bound, and thus the concentration of phosphatases or level of phosphatase
activity.