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    Ultra-thin film sensors based on porphyrin-5-ylphosphonate diesters for selective and sensitive dual-channel optical detection of mercury(II) ions

    Year: 2021

    Journal: Dyes Pigment., Volume 186, FEB

    Authors: Ermakova, Elizaveta V.; Koroleva, Elena O.; Shokurov, Alexander V.; Arslanov, Vladimir V.; Bessmertnykh-Lemeune, Alla

    Organizations: Centre National de la Recherche Scientifique (CNRS); Russian Academy of Sciences (RAS); Russian Foundation for Basic Research [17-53-16018, 18-33-00339]

    Keywords: Porphyrin; Solid thin-film sensor; Mercury(II) detection; Langmuir monolayer; Langmuir-Schaefer film; Dual-channel optical sensor

    Reusable dual-channel optical sensors for Hg2+ ions were prepared by Langmuir-Schaefer (LS) method from amphiphilic (trans-A2)BC-type porphyrins functionalized at meso-positions of the tetrapyrrolic macrocycle by sterically demanding diethoxyphosphoryl and mesityl groups as well as electron donating RO, RS or RNH substituents (R = n-C8H17). These three novel amphiphilic porphyrin derivatives were synthesized in good yields and their floating films at the air-water interface were investigated. In these monolayers, porphyrin molecules display a slipped stack-of-card orientation, but their strong pi stacking is prohibited by bulky diethoxyphosphoryl and mesityl groups. The heteroatom substituent plays a key role in the molecular organization of the monolayers because it can participate in intermolecular hydrogen bonding, which influences the monolayer structure. Sensing properties of the porphyrins organized in Langmuir monolayers differ from those in the solution environment. Selective spectrophotometric detection of Hg2+ ions by these floating films is observed because interfering Cu2+, Zn2+, Cd2+, and Pb2+ ions are coordinated to donor centers located at the periphery of the macrocycle. Transfer of these floating films onto a polyvinyl chloride surface by LS technique affords perforated multilayer films with a tight molecular coverage of the solid support. The effect of the heteroatoms on the organization of these films was demonstrated by scanning electron microscopy (SEM) and electrochemical impedance spectroscopy (EIS). Both absorption and emission studies provide a strong evidence that chromophore-chromophore interactions are rather weak in these LS films. Binding of mercury(II) ions by the films and the regeneration of the sensors were explored visually and using reflection absorbance and fluorescence spectroscopies and then confirmed by X-ray fluorescence analysis. Detection limit of these selective and reusable dual-channel (absorbance and fluorescence) thin-film sensors is about 10(-8) M (2 ppb), that corresponds to the action level for Hg2+ ions in drinking water recommended by the U.S. Environmental Protection Agency (EPA).
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