Ratiometric luminescence detection of H2O2 in food samples using a terbium coordination polymer sensitized with 3-carboxyphenylboronic acid.

A ratiometric luminescent probe was fabricated using adenosine monophosphate (AMP) as a bridging ligand and 3-carboxyphenylboronic acid (3-CPBA) as the sensitizer and functional ligand that allowed the probe to recognize hydrogen peroxide (H2O2). The probe was labeled AMP-Tb/3-CPBA. Adding H2O2 caused the nonluminescent 3-CPBA to be converted into 3-hydroxybenzoic acid, which strongly luminesces at 401 nm. This meant that adding H2O2 decreased the AMP-Tb/3-CPBA luminescence intensity at 544 nm and caused luminescence at 401 nm. The 401 and 544 nm luminescence intensity ratio (I401/I544) was strongly associated with the H2O2 concentration between 0.1 and 60.0 µM, and the detection limit was 0.23 µM. Dual emission reverse-change ratio luminescence sensing using the probe allowed environmental effects to be excluded and the assay to be very selective. We believe that the results pave the way for the development of new functionalized lanthanide coordination polymers for use in luminescence assays.

Detecting phosphate using lysine-sensitized terbium coordination polymer nanoparticles as ratiometric luminescence probes.

Probes for detecting phosphate ions (Pi) are required for environmental monitoring and to protect human health. Here, novel ratiometric luminescent lanthanide coordination polymer nanoparticles (CPNs) were successfully prepared and used to selectively and sensitively detect Pi. The nanoparticles were prepared from adenosine monophosphate (AMP) and Tb3+, and lysine (Lys) was used as a sensitizer (through the antenna effect) to switch on Tb3+ luminescence at 488 and 544 nm while Lys luminescence at 375 nm was quenched because of energy transfer from Lys to Tb3+. The complex involved is here labeled AMP-Tb/Lys. Pi destroyed the AMP-Tb/Lys CPNs and therefore decreased the AMP-Tb/Lys luminescence intensity at 544 nm and increased the luminescence intensity at 375 nm at an excitation wavelength of 290 nm, meaning ratiometric luminescence detection was possible. The ratio between the luminescence intensities at 544 and 375 nm (I544/I375) was strongly associated with the Pi concentration between 0.1 and 6.0 µM, and the detection limit was 0.08 µM. The dual-emission reverse-change ratio luminescence sensing method can exclude environmental effects, so the proposed assay was found to be very selective. The method was successfully used to detect Pi in real water samples, and acceptable recoveries were found, suggesting that the method could be used in practice to detect Pi in water samples.

Ratiometric fluorescence nanoprobe based on carbon dots and terephthalic acid for determining Fe2+ in environmental samples.

A ratiometric fluorescent nanoprobe using carbon dots (CDs) and involving oxidation of terephthalic acid (TPA) induced by hydroxyl radicals (·OH) was developed for sensitively and selectively determining Fe2+ ions. When Fe2+ ions are added to the TPA@CDs/H2O2 system, ·OH produced through the Fenton reaction oxidizes the non-fluorescent TPA to give 2-hydroxyl terephthalic acid, which fluoresces at 423 nm when excited at 286 nm. The ·OH and Fe3+ produced quench CD fluorescence at 326 nm. The 2-hydroxyl terephthalic acid to CD fluorescence intensity ratio linearly increased as the Fe2+ concentration increased in the range 0.5-50 µM, and the detection limit was 0.25 µM. The new assay is very selective because it involves dual-emission reverse change ratio fluorescence sensing, which can exclude matrix effects. The new nanoprobe was used to determine Fe2+ concentrations in real water samples, and the recoveries were found to be acceptable. Schematic of the ratiometric fluorometric method for determining Fe2+ based on CDs and TPA.