Background-Free Fluorescence-Decay-Time Sensing and Imaging of pH with Highly Photostable Diazaoxotriangulenium Dyes.

Novel fluorescent diazaoxatriangulenium (DAOTA) pH indicators for lifetime-based self-referenced pH sensing are reported. The DAOTA dyes were decorated with phenolic-receptor groups inducing fluorescence quenching via a photoinduced-electron-transfer mechanism. Electron-withdrawing chlorine substituents ensure response in the most relevant pH range (apparent p Ka' values of ∼5 and 7.5 for the p, p-dichlorophenol- and p-chlorophenol-substituted dyes, respectively). The dyes feature long fluorescence lifetimes (17-20 ns), high quantum yields (∼60%), and high photostabilities. Planar optodes are prepared upon immobilization of the dyes into polyurethane hydrogel D4. Apart from the response in the fluorescence intensity, the optodes show pH-dependent lifetime behavior, which makes them suitable for studying 2D pH distributions with the help of fluorescence-lifetime-imaging techniques. The lifetime response is particularly pronounced for the sensors with high dye concentrations (0.5-1 wt % with respect to the polymer) and is attributed to the efficient homo-FRET mechanism.

Optical Oxygen Sensors Show Reversible Cross-Talk and/or Degradation in the Presence of Nitrogen Dioxide.

A variety of luminescent dyes including the most common indicators for optical oxygen sensors were investigated in regard to their stability and photophysical properties in the presence of nitrogen dioxide. The dyes were immobilized in polystyrene and subjected to NO2 concentrations from 40 to 5500 ppm. The majority of dyes show fast degradation of optical properties due to the reaction with NO2. The class of phosphorescent metalloporphyrins shows the highest resistance against nitrogen dioxide. Among them, palladium(II) and platinum(II) complexes of octasubstituted sulfonylated benzoporphyrins are identified as the most stable dyes with almost no decomposition in the presence of NO2. The phosphorescence of these dyes is reversibly quenched by nitrogen dioxide. Immobilized in various polymeric matrices, the sulfonylated Pt(II) benzoporphyrin demonstrates about one order of magnitude more efficient quenching by NO2 than by molecular oxygen. Our study demonstrates that virtually all commercially available and reported optical oxygen sensors are likely to show either irreversible decomposition in the presence of nitrogen dioxide or reversible luminescence quenching. They should be used with extreme caution if NO2 is present in relatively high concentrations or it may be generated from other species such as nitric oxide. As an important consequence of nearly anoxic systems, production of nitrogen dioxide or nitric oxide may be therefore erroneously interpreted as an increase in oxygen concentration.