RT Journal Article T1 Wide range luminescence lifetime-based pH sensing with covalently immobilized multi-protonatable Ru(II) complexes A1 Knöbl, Ya Jie A1 Bedoya, Maximino A1 Farquharson, Alexander A1 Courtney, Patrick A1 Orellana Moraleda, Guillermo AB To overcome the limitations of optical pH sensors, the response of which is just ca. one pH unit around the pKa value of the indicator dye and capitalize on the advantages of red-luminescent Ru(II) complexes for optical sensing, multi-pKa members of this family are proposed. Bipyridine ligands bearing protonatable groups (amines and carboxylates) are the basis to design and prepare the indicator dyes. Their photophysical properties and response to pH changes were investigated in the pH 3.5 − 9.0 range. The complex [Ru(DCB)2DEAMB], where DCB and DEAMB stand for 2,2’-bipyridine-4,4’-dicarboxylate and 4,4’-(N,N-diethylaminomethyl)-2,2’-bipyridine, respectively, shows a reversible monotonic change of its emission wavelength maximum (648 – 634 nm), luminescence intensity (1.40x) and lifetime (335 – 429 ns) in solution with increasing pH. This complex and two similar ones were covalently tethered to commercial TentaGel® M Br polymer microbeads for luminescence phase shift fiberoptic pH measurements. The immobilized [Ru(DCB)2DEAMB] displays the widest pH sensitivity over pH 3.5 to pH 8.5. The stability of this sensor was satisfactory when cycling between pH 3.5 and 8.5 for five days as well as under a three-day cycle between each pH unit. Changes of the buffer type, buffer concentration and osmolarity did not significantly influence the sensor response; however, large variations of dissolved oxygen and, naturally, temperature would require correction by the corresponding sensors. The novel, robust luminescent pH sensor has been tested in phase-sensitive mode for cell cultures monitoring in commercial bioreactors, but its response would also be suitable for in situ monitoring of natural waters. PB Elsevier YR 2024 FD 2024-11-19 LK https://hdl.handle.net/20.500.14352/112771 UL https://hdl.handle.net/20.500.14352/112771 LA eng NO Ya Jie Knöbl, Maximino Bedoya, Alexander Farquharson, Patrick Courtney, Guillermo Orellana, Wide range luminescence lifetime-based pH sensing with covalently immobilized multi-protonatable Ru(II) complexes, Sensors and Actuators B: Chemical, Volume 425, 2025, 136960, ISSN 0925-4005, https://doi.org/10.1016/j.snb.2024.136960. (https://www.sciencedirect.com/science/article/pii/S0925400524016903) NO Universidad Complutense de Madrid DS Docta Complutense RD 17 abr 2025