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 pKa 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.
ABSTRACT
This work presents a study on the influence of eight different ionic liquids (ILs) in the composition of dry membranes used for gaseous CO2 optical sensing. The presence of CO2 causes a displacement of a colorimetric pH indicator toward its acid form that increases the emission intensity of the luminophore by an inner filter process. The influence of ILs in the membrane on the stability and dynamic behavior-usually the main drawbacks of these sensors-of the membranes is studied. The characterization of the different membranes prepared was carried out and the discussion of the results is presented. In all cases, the response and recovery times improved considerably, with the best case being response times of only 10 s and recovery times of 48 s, compared to response and recovery times of 41 and 100 s, respectively, for membranes without IL. The useful life of the detection membranes is also considerably longer than that of membranes that do not include IL, at least 292 days in the best case. The sensing membrane without luminophore and only containing the pH indicator is proposed for the color-based measurement of CO2 using a digital camera for possible use in food-packaging technology. Graphical abstract á .
ABSTRACT
A study of different alternatives to improve the stability and lifetime of sensors for the determination of gaseous CO2 has been performed. It includes the characterization of different sensing membranes, a discussion of the results obtained and possibilities for the future. The solid sensor membrane for gaseous CO2 based on changes in the luminiscence of a luminophore immobilized on O2-insensitive film, concurrent with the displacement of a pH indicator, has some drawbacks, such as the loss of efficiency over time and the need to maintain the sensor in special atmospheric conditions. As a solution to these drawbacks, two alternatives were tested, the first alternative was replacing the newly proposed tetraoctyl ammonium hydroxide (TOAOH ) phase transfer agent with other basic agents that did not undergo a Hoffman degradation reaction, and the second alternative was the use of hydrophilic polymers that could retain water needed for CO2 sensing more efficiently. The different membranes tested indicated that the use of tetramethyl ammonium (TMAOH) instead of TOAOH as the phase transfer agent produced better results regarding stability and sensitivity. In addition, replacing the membrane polymer with hydrophilic polymers improved the sensing characteristics in terms of response time and stability over hydrophobic polymers. With a detection limit of 0.006%, the response time is 19s and the recovery time is 100s. The lifetime of the sensing membranes, which do not need to be held in any special atmosphere other than darkness, is longer than at least 300 days for membranes with TMAOH in hydrophilic polymer and 515 days for membranes with TMAOH in ethyl cellulose.
