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Browsing Material embargado by Author "Aliaga Miranda, Margarita Elly"

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    Supramolecular Control on the Reactivity of New Quinolin-2(1h)-one derivatives Induced by Micellar systems
    (2025) Quintero Faúndez, Guillermo Esteban; Aliaga Miranda, Margarita Elly; Espinosa Bustos, Christian Marcelo; Pontificia Universidad Católica de Chile. Facultad de Química y de Farmacia
    Six new quinolin-2(1H)-one derivatives (E)-6-methoxy-1-methyl-3-(2-(3-methyl-4-nitroisoxazol-5-yl)vinyl)quinolin-2(1H)-one (MQI), 7-(diethylamino)quinolin-2(1H)-one-3-carbaldehyde (DQD1), 7-(diethylamino)-1-methylquinolin-2(1H)-one-3-carbaldehyde (DQD2), (E)-7-(diethylamino)-3-(3-(3-(4-nitrophenyl)-3-oxoprop-1-en-1-yl)-1-methylquinolin-2(1H)-one (DQD3), (E)-7-(diethylamino)-3-(3-(4-fluorophenyl)-3-oxoprop 1-en-1-yl)-1-methylquinolin-2(1H)-one (DQCh) and (E) 7(Diethylamino)-1-methyl-3-(2-(3-methyl-4-nitroisoxazol-5-yl)vinyl)quinolin-2(1H)-one (DQI) were synthesized and evaluated as colorimetric and fluorescent probes for bisulfite (HSO3) in aqueous micellar solutions. The compound MQI, designed as a Michael acceptor, showed low water solubility but significantly enhanced reactivity toward HSO3 in aqueous cationic micellar solution of cetyltrimethylammonium bromide (CTABr), with rate constants up to 200-fold higher than in zwitterionic systems, such as 3-(N,N-dimethyltetradecylammonium) propanesulfonate (SB3-14). On the other hand, DQD1-3, DQCh, and DQI were developed to improve the fluorescence response of quinoline-2(1H)-one ring. Notably, DQI displayed rare inverse solvatofluorochromism, dependent on solvent polarity, making it only the second reported case of this behavior in organic dyes to date. While DQD3 did not exhibit the appropriate photophysical or reactivity criteria due to the presence of both E/Z isomers, the other derivatives demonstrated the presence of only the E isomer (valid for DQCh and DQI), promising behavior in micellar systems, with binding constants (Ks) in the range of 103−106 M−1. Photophysical studies in water and micellar environments revealed that DQCh had the highest fluorescence quantum yield (𝜙𝑓) and excellent selectivity for HSO3 over other anions and biothiols. Complementarily, DQCh was testedin real sample analysis (white wine samples) with good results, also DFT calculations confirmed the adequate reactivity of the double-bound C-C ,-unsatured. On the other hand, DQI showed a low fluorescence and exhibited fast and selective “turn-off” responses to HSO3 and hypochlorite (ClO). Its reaction was supported by NMR analysis of Michael adduct formation. Overall, this study introduces new quinolin-2(1H)-one-based platforms for selective HSO3 −and/or ClO− sensing, highlighting the importance of aqueous micellar medium in tuning chemical reactivity and fluorescence properties. The findings contribute to developing functional probes for environmental and food analysis in an aqueous micellar solution, avoiding toxic organic solvents.