Effects of substituents on fluorometric detection of cyanide anions by indolium–coumarin dyads

Literature Information

Publication Date 2015-08-27
DOI 10.1039/C5CP03877D
Impact Factor 3.676
Authors

Masaya Nakamura, Takayuki Hirai


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Abstract

We synthesized an indolium–coumarin dyad (1) and its derivatives with –Cl (2), –N(CH3)2 (3), or –NO2 (4) substituent, and used them for fluorometric detection of cyanide anions (CN−) in aqueous media. All of the dyads exhibit fluorescence enhancement by CN−via a nucleophilic interaction of CN− with the indolium carbon atoms. Their fluorescence response and selectivity to CN−, however, depend strongly on the substituents. Ab initio calculation and kinetic analysis were performed to verify the behaviors. Substitution of electron-withdrawing groups (2 and 4) increases the electrophilicity of the indolium carbon. This decreases the activation enthalpy for the nucleophilic interaction with CN− and facilitates rapid CN− sensing. Compound 4 with very high electrophilicity, however, also promotes nucleophilic interaction with OH− in the solution, resulting in decreased CN− selectivity. As a result of this, the –Cl-substituted compound 2 containing the indolium carbon with appropriate electrophilicity facilitates rapid (within 1 min) and selective CN− detection.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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