A Novel ppb-Level Sensitive and Highly Selective Europium-Based Diketone Luminescent Sensor for the Quantitative Detection of Aluminum Ions in Water Samples

Abstract

A novel Eu(tta)3([4,4′-(t-bu)2-2,2′-bpy)] complex (tta-thenoyltrifluoroacetone), a ratiometric luminescent-based optical sensor for the quantitative determination of aluminum ion, is synthesized and characterized using XRD and 1H NMR. The XRD data reveal the slightly distorted octahedral structure. The complex displays a bright red emission at 613 nm in methanol which is characteristic of europium (III) complexes. Upon the addition of Al3+ ions, the red emission disappears, and a new blue emission at 398 nm emerges, manifesting the ratiometric nature of the complex. The turn-off of the red emission and turn-on of the blue emission are attributed to Eu-Al trans-metalation, as supported by Raman data that show the emergence of Al-O vibrations at 418, 495, and 608 cm−1 concomitant with the disappearance of Eu-O and Eu-N bond vibrations. Most aluminum sensors are known to suffer from interferences from other metals including Cu2+, Co2+, and Cd2+. However, the sensor reported here is tested for 11 common cations and shows no interference on sensitivity. To the best of our knowledge, this is the first known Eu-based luminescence sensor that successfully exhibited the ability to detect aluminum ions in ppb levels in aqueous environments. The calculated Al3+ binding constant is 2.496 × 103 ± 172. The complex shows a linear relationship in the range of 0–47.6 ppb (1.76 × 10−6 M) Al3+ and the limit of detection (LOD) is 4.79 ppb (1.77 × 10−7 M) in MeOH. ICP-OES is used for validation of the sensor complex in water and then it was used for quantitative detection of Al3+ ions in water as a real-life application. The complex can accurately detect Al3+ ions in the range of 4.97–24.9 ppb (1.84 × 10−7 M–9.2 × 10−7 M) with an LOD of 8.11 ppb (2.99 × 10−7 M). Considering that the aluminum ion serves no recognized function within the human body, its accumulation can lead to severe neurological disorders, including Parkinson’s and Alzheimer’s diseases. With the LOD value significantly lower than the WHO-recommended maximum permissible level of 200 ppb for aluminum in drinking water, even without high-power laser-aided signal enhancement, the sensor shows promise for detecting trace amounts of aluminum contamination in water. Therefore, it can significantly aid in the monitoring of even the smallest aluminum ion contamination in drinking water, industrial effluents, and natural water bodies.