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Dr. Sandra Ast Tobias Fischer Holger Müller Dr. Wulfhard Mickler Mathias Schwichtenberg Dr. Knut Rurack Prof. Dr. Hans‐Jürgen Holdt 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(9):2990-3005
In a systematic approach we synthesized a new series of fluorescent probes incorporating donor–acceptor (D‐A) substituted 1,2,3‐triazoles as conjugative π‐linkers between the alkali metal ion receptor N‐phenylaza‐[18]crown‐6 and different fluorophoric groups with different electron‐acceptor properties (4‐naphthalimide, meso‐phenyl‐BODIPY and 9‐anthracene) and investigated their performance in organic and aqueous environments (physiological conditions). In the charge‐transfer (CT) type probes 1 , 2 and 7 , the fluorescence is almost completely quenched by intramolecular CT (ICT) processes involving charge‐separated states. In the presence of Na+ and K+ ICT is interrupted, which resulted in a lighting‐up of the fluorescence in acetonitrile. Among the investigated fluoroionophores, compound 7 , which contains a 9‐anthracenyl moiety as the electron‐accepting fluorophore, is the only probe which retains light‐up features in water and works as a highly K+/Na+‐selective probe under simulated physiological conditions. Virtually decoupled BODIPY‐based 6 and photoinduced electron transfer (PET) type probes 3 – 5 , where the 10‐substituted anthracen‐9‐yl fluorophores are connected to the 1,2,3‐triazole through a methylene spacer, show strong ion‐induced fluorescence enhancement in acetonitrile, but not under physiological conditions. Electrochemical studies and theoretical calculations were used to assess and support the underlying mechanisms for the new ICT and PET 1,2,3‐triazole fluoroionophores. 相似文献
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Novel allyl‐acrylate quaternary ammonium salts were synthesized using two different methods. In the first (method 1), N,N‐dimethyl‐N‐2‐(ethoxycarbonyl)allyl allylammonium bromide and N,N‐dimethyl‐N‐2‐(tert‐butoxycarbonyl)allyl allylammonium bromide were formed by reacting tertiary amines with allyl bromide. The second (method 2) involved reacting N,N‐dialkyl‐N‐allylamine with either ethyl α‐chloromethyl acrylate (ECMA) or tert‐butyl α‐bromomethyl acrylate (TBBMA). The monomers obtained with the method 2 were N,N‐diethyl‐N‐2‐(ethoxycarbonyl)allyl allylammonium chloride, N,N‐diethyl‐N‐2‐(tert‐butoxycarbonyl)allyl allylammonium bromide, and N,N‐piperidyl‐N‐2‐(ethoxycarbonyl)allyl allylammonium chloride. Higher purity monomers were obtained with the method 2. Solution polymerizations with 2,2′‐azobis(2‐amidinopropane) dihydrochloride (V‐50) in water at 60–70°C gave soluble cyclopolymers which showed polyelectrolyte behavior in pure water. Intrinsic viscosities measured in 0.09M NaCl ranged from 0.45 to 2.45 dL/g. 1H‐ and 13C‐NMR spectra indicated high cyclization efficiencies. The ester groups of the tert‐butyl polymer were hydrolyzed completely in acid to give a polymer with zwitterionic character. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 901–907, 1999 相似文献