D₂O plays important roles in a variety of fields (such as the nuclear industry and bioorganic analysis), and thus its isotopic purity (H₂O contents) is highly concerned. Due to its highly similar physical properties to H₂O and large excess amounts of H₂O over D₂O, it is challenging to distinguish D₂O from H₂O. On the basis of the characteristic NIR-II phosphorescence of singlet oxygen (¹O₂), and the fact that H₂O is a more efficient quencher for ¹O₂ than D₂O, here, we proposed to simply use the 1275 nm emission of ¹O₂ for the analysis of the isotopic purity of D₂O. In normal cases (a xenon lamp for excitation), such steady-state emission is extremely weak for valid analytical applications, we thus employed laser excitation for intensification. To this goal, a series of photosensitizers were screened, and eventually polythiophene PT10 was selected with high singlet oxygen quantum yield (Φ_Δ = 0.51), high H₂O/D₂O contrast, and excellent photostability. Upon excitation with a 445 nm laser, a limit of detection (LOD, 3σ) of 0.1% for H₂O in D₂O was achieved. The accuracy of the proposed method was verified by the analysis of the isotopic purity of several D₂O samples (with randomly added H₂O). More interestingly, the hygroscopicity of D₂O was sensitively monitored with the proposed probe in a real-time manner; the results of which are important for strengthening the care of D₂O storage and the importance of humidity control during related investigations. Besides D₂O isotopic purity evaluation, this work also indicated the potential usefulness of the NIR-II emission of singlet oxygen in future analytical detection.

Qin Yang

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