NIR optical carbon dioxide gas sensor based on simple azaBODIPY pH indicators

Abstract

Two simple boron-dipyrromethene-type fluorophore (azaBODIPYs) dyes are synthesized and tested for the determination of CO₂ gas by an inner filter process. The indicators are noncovalently entrapped in suitable polymers according to their polarity, featuring absorption maxima at 620 nm and fluorescent emission maxima in the range 675–720 nm. Molar absorptivity and fluorescence quantum yield data were determined for these two synthesized azaBODIPYs. These indicators have high molar absorption coefficients of 7.1 × 10⁴ and 2.1 × 10⁴ M⁻¹ cm⁻¹ and quantum yields of 21 and 9%. The pK_a values of the indicators are determined from absorbance and fluorescence measurements with values of 7.9 and 8.5, depending on the positioning of the substitution pattern of the electron-donating functionalities. The two azaBODIPYs present excellent photostability, making them suitable for long duration measurements. These azaBODIPY dyes act as fluorescent pH indicators in a polymeric sensing membrane along with microcrystalline powder of chromium-doped gadolinium aluminium borate as the luminophore, a transfer phase agent (tetraoctyl or tetramethyl ammonium hydroxide) and a plasticizer or surfactant to improve membrane permeability to gaseous CO₂. The response time ranges from 42 to 60 s and recovery time from 103 to 120 s, with a detection limit of 0.04 and 0.57% CO₂. The store time of the sensing membranes is longer than 570 days in the best case, and it does not need to be kept in any special atmosphere other than darkness.