Novel Fluorescence Guanidine Molecules for Selective Sulfate Anion Detection in Water Complex Samples over a Wide pH Range

Quantitative analysis of sulfate anions in water still remains an important challenge for the society. Among all the methodologies, the most successful one is based on optical supramolecular receptors because the presence of small concentrations of sulfate anion modifies the photophysical properties of the receptor. In this case, fluorescence anion sensors have been designed by the incorporation of guanidine motifs into fluorenyl cores. The photophysical behaviors of the new mono- (M) and bis-guanidine (B) derivatives were studied through pH dependence, solvent effects, and ion sensing on steady-state spectra and time-resolved fluorescence spectroscopy. In more detail, the results demonstrate that M is a highly selective and sensitive sulfate ion receptor in real water samples and, even more importantly, its function remains unchanged at different ranges of pH. The reason behind this resides on the fluorescence quenching produced by an internal charge-transfer process when the sulfate anion is complexed with M. It is worth noting that the global and partial affinity constants (1010 M-2 and 105 M-1, respectively) of complex formation are far above from the current sulfate sensors in water (104 M-1) which give an LOD of 0.10 μM in water with an analytical range of 2.5-10 μM. On the other hand, although it would seem, at first sight, that the B derivate will be the most promising one, the possibility of having two simultaneous protonation states reduces the complex formation and, therefore, its sensitivity to sulfate anions. The results presented here offer the possibility of using a new molecule in water environments, which opens the door to infinite applications such as the detection of trace amounts of sulfate ions in food or water.