RESUMO
A new analytical method for the determination of 22 perfluoroalkylated (carboxylic and sulfonic) acids in water samples is presented. The method's objective was to achieve the simultaneous quantification of compounds with different chain lengths (from C1 to C18). To this end, 500 mL of water were extracted with Oasis WAX solid-phase extraction cartridges and eluted with 3 mL of 5% ammonia in methanol. After evaporation to dryness, extracts were reconstituted in methanol:ultrapure water (1:1) and analyzed by mixed-mode liquid chromatography-tandem mass spectrometry (MMLC-MS/MS) using a weak anion exchange/reversed-phase column. The method provided good results, with limits of quantification lower than 1 ng/L in river water for most of compounds, except the two perfluorocarboxylic acids with the longest alkyl chain (>C14) and trifluoroacetic acid, for which a blank contamination problem was observed. The method proved good trueness and precision in both ultrapure and river water (R ≥ 81%, RSD ≤ 15%). After validation, the method was applied to the analysis of nine water samples where nine perfluoroalkylated acids were quantified. Seven of them were ultrashort- (C1-C4) and short-chain (C4-C8) perfluoroalkylated acids, pointing out the importance of developing methods capable to target such substances for further monitoring.
RESUMO
The present work reports on the assessment of luminescent probes derived from citric acid (CA) and ß-aminothiols (namely, l-cysteine (Cys) and cysteamine) for instrumental and smartphone-based fluorimetric sensing purposes. Remarkably, the evaluated luminescent probes derived from natural compounds showed pH-dependent dual excitation/dual emission features. Both fluorophores hold promise for the ratiometric fluorimetric sensing of pH, being especially convenient for the smartphone-based sensing of pH via ratiometric analysis by proper selection of B and G color channels. Time dependent density functional theory (TDDFT) calculations allowed to substantiate the pH dependent structure-property relationship and to unveil the critical role of the CA derived carboxyl group, these findings contributing to the fundamental knowledge on these systems for the rational design of new fluorophores and in establishing fluorescence sensing mechanisms of CA-derived systems. Besides, paper-based devices modified with CA-Cys were implemented in a three-phase separation approach for sensitive and selective ammonia sensing, yielding a remarkable enrichment factor of 389 and a limit of detection of 37 µM under optimal conditions. The proposed approach was successfully applied to the determination of ammonia nitrogen and extractable ammonium in water samples and marine sediments, respectively.