Chromo-Fluorogenic Detection of Nerve-Agent Mimics Using Triggered Cyclization Reactions in Push-Pull Dyes <<>>
Written by Ana M. Costero, Margarita Parra, Salvador Gil, Raúl Gotor, Pedro M. E. Mancini, Ramón Martínez-Máñez, Félix Sancenón, Santiago Royo on May 28, 2010 – 1:16 am -A genus of azo and stilbene derivatives (1-9) are synthesized, and their chromo-fluorogenic behavior in the personality of nerve-agent simulants, diethylchlorophosphate (DCP), diisopropylfluorophosphate (DFP), and diethylcyanophosphate (DCNP) in acetonitrile and opposing decipherment of water/acetonitrile (3:1 v/v) buffered at pH 5.6 with MES, is investigated. The set compounds restrict 2-(2-N,N-dimethylaminophenyl)ethanol or 2-[(2-N,N-dimethylamino)phenoxy]ethanol reactive groups, which are divide of the conjugated [pi]-system of the dyes and are masterful to come apart acylation reactions with phosphonate substrates followed by a quick intramolecular N-alkylation. The nerve-agent mimic-triggered cyclization resistance transforms a dimethylamino collection into a quaternary ammonium, inducing a change-over of the electronic properties of the delocalized systems that results in a hypsochromic market of the absorption strip of the dyes. Nearly the same reactivity studies are also carried out with other "non-toxic" organophosphorus compounds, but no changes in the UV/Vis spectra were observed. The emission bearing of the reagents in acetonitrile and water-acetonitrile 3:1 v/v mixtures is also intentional in the attendance of nerve-agent simulants and other organophosphorous derivatives. The reactivity internuncio 1-9 and DCP, DCNP, or DFP in buffered water-acetonitrile 3:1 v/v solutions lower than drunk pseudo first-order kinetic conditions, using an superabundance of the corresponding simulant, are forced in ukase to condition the kind constants (k) and the half-life times (t1/2=ln2/k) for the reprisal. The detection limits in water/acetonitrile 3:1 v/v are also distinct for 1-9 and DCP, DCNP, and DFP. Finally, the chromogenic detection of nerve vehicle simulants both in revelation and in gas work in are tested using silica gel containing adsorbed compounds 1, 2, 3, 4, or 5 with choice results <<>>
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