The ability of meso-tetra(pentafluorophenyl)porpholactone (T(F)PL) and its Pt(II) complex [meso-tetra(pentafluorophenyl)porpholactonato]Pt(II) (T(F)PLPt) to function as optical high pH sensors is described. Under strongly alkaline or high methoxide conditions, their UV-vis spectra undergo dramatic and reversible red-shifts. The dynamic range for the sensor T(F)PLPt in solution is from pH 11.5 to 13.2. Using (1)H, (19)F, and (13)C NMR, UV-vis and IR spectroscopy, mass spectrometry, and the use of model compounds, the molecular origin of this optical shift is deduced to be a nucleophilic attack of OH(-)/MeO(-) on the lactone carbonyl of the chromophore, representing a novel mechanism for porphyrin-based sensors. The sensing compound was solubilized with Cremophor EL for use in aqueous solutions and embedded in polymer matrixes for testing as optical fiber-based optodes and planar sheet optode materials.
Data on the variability of pH levels in cement-based materials is essential for a better understanding of the early aging of materials and the long-term performance of concrete structures. Current approaches for measuring pH levels in concrete are inadequate with respect to radiometric range and resolution and spatial granularity. We report on a methodology for mapping pH levels in concrete utilizing a halochromic porphyrin sensor molecule that allows a simple measurement of surface values of pH level using a commercial digital camera setup. As proof of concept, cement paste, mortar, and concrete samples were subject to accelerated carbonation and then evaluated for pH profiles at different ages of degradation. Comparative tests on the same specimens were also conducted using phenolphthalein as the pH indicator. Spatial distribution of pH level from pH 11.0 to 13.5 were mapped at various levels of carbonation.
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