Tetracationic porphyrin (TMPyP) molecules were incorporated into an optically transparent TiO2 thin film, prepared by Glancing Angle Physical Vapour Deposition (GAPVD), by simple infiltration (at pH 6.4). The preparation of optically transparent TMPyP/TiO2 composite thin films provides a method for the integration of the porphyrin molecules into photonic devices for direct monitoring of gases. Previously, UV-visible and fluorescence spectral techniques have been used to study the reversible protonation of TMPyP in aqueous solution. The optical spectrum of TMPyP shows an intense Soret band at 423 nm with a 22 nm red shift upon protonation by HCl. The experimental conditions for monitoring the concentration of HCl gas by absorption spectroscopy have been optimized. The maximum absorbance change was observed at the Soret band wavelength. A selected temperature of 80 °C and a 300 s recovery period were found to be the optimum operating parameters (response time t50 = 16.8 ± 0.7 s). The composite with smaller surface concentration of TMPyP (¿ = 0.3 × 10-9 mol cm -2) presented the best detection limit (0.1 ppm). The response of the composite sensor was highly stable for several months. © 2010 Elsevier B.V.Peer Reviewe

Open porous and transparent microcolumnar structures of TiO₂ prepared by physical vapour deposition in glancing angle configuration (GLAD-PVD) have been used as host matrices for two different fluorescent cationic porphyrins, 5-(N-methyl 4-pyridyl)-10,15,20-triphenyl porphine chloride (MMPyP) and meso-tetra (N-methyl 4-pyridyl) porphine tetrachloride (TMPyP). The porphyrins have been anchored by electrostatic interactions to the microcolumns by self-assembly through the dip-coating method. These porphyrin/TiO₂ composites have been used as gas sensors for ammonia and amines through previous protonation of the porphyrin with HCl followed by subsequent exposure to the basic analyte. UV–vis absorption, emission, and time-resolved spectroscopies have been used to confirm the protonation–deprotonation of the two porphyrins and to follow their spectral changes in the presence of the analytes. The monocationic porphyrin has been found to be more sensible (up to 10 times) than its tetracationic counterpart. This result has been attributed to the different anchoring arrangements of the two porphyrins to the TiO₂ surface and their different states of aggregation within the film. Finally, there was an observed decrease of the emission fluorescence intensity in consecutive cycles of exposure and recovery due to the formation of ammonium chloride inside the film.