Visualization of exhaled hydrogen sulphide on test paper with an ultrasensitive and time-gated luminescent probe

Luminescent chemosensors for hydrogen sulphide (H2S) are of great interest because of the close association of H2S with our health. However, current probes for H2S detection have problems such as low sensitivity/selectivity, poor aqueous-solubility or interference from background fluorescence. This study reports an ultrasensitive and time-gated “switch on” probe for detection of H2S, and its application in test paper for visualization of exhaled H2S. The complex probe is synthesized with a luminescent Tb3+ centre and three ligands of azido (–N3) substituted pyridine-2,6-dicarboxylic acid, giving the probe high hydrophilicity and relatively fast reaction dynamics with H2S because there are three –N3 groups in each molecule. The introduced –N3 group as a strong electron-withdrawing moiety effectively changes the energy level of ligand via intramolecular charge transfer (ICT), and thus breaks the energy transferring from ligand to lanthanide ion, resulting in quenching of Tb3+ luminescence. On addition of H2S, the –N3 group can be reduced to an amine group to break the process of ICT, and the luminescence of Tb3+ is recovered at a nanomolar sensitivity level. With a long lifetime of luminescence of Tb3+ centre (1.9 ms), use of a time-gated technique effectively eliminates the background fluorescence by delaying fluorescence collection for 0.1 ms. The test paper imprinted by the complex probe ink can visualize clearly the trace H2S gas exhaled by mice.