A new approach to the use of micelles in the fluorescent sensing of metal cations is proposed and applied to the case of Hg2+. We demonstrate how it is possible to transform a system from an ON-OFF to an OFF-ON sensor by changing the length of the chain used to lipophilise a ligand that resides inside Triton X-100 micelles together with pyrene as the fluorophore. Three tetrathia-monoaza macrocyclic ligands have been synthesised with the same ring but functionalised on the nitrogen atom with a methyl (C1-NS4), an n-butyl (C4-NS4) or an n-dodecyl (C12-N54) chain. ne three ligands have been fully characterised in water containing TritonX-100 micelles by means of potentiometric titrations and their apparent protonation and complexation constants with Hg2+ were determined. On the basis of the distribution diagrams obtained, the more lipophilic C12-NS4 has been developed as an ON-OFF fluorescent sensor for mercury: working at pH < 4, in the absence of Hg2+ the ligand is inside the micelles, protonated and non-quenching, while on addition of mercury the [C12-NS4Hg](2+) complex forms which remains inside the micelles and is quenching. On the other hand, the ligand of intermediate chain length, C4-NS4, can be used to obtain an OFF-ON sensor at 7.0 < pH < 9.5. In the absence of added metal at pH > 7.0 the ligand is unprotonated, it stays inside the micelles and is quenching, while addition of Hg2+ in the 7.0-9.5 pH range results in the formation of [C4-NS4Hg](2+), which is hydrophilic enough to leave the micelles and to be released into the bulk solution where it is no longer capable of quenching pyrene fluorescence. Additional studies on C1-NS4, C3-NS4 and C8-NS4 indicate that the optimal chain length to observe this OFF-ON behaviour is C-3-C-4
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Titolo: | Fluorescent Sensors for Hg2+ in Micelles: A Ne w Approach that Transforms an ON-OFF into an OFF-ON Response as a Function of the Lipophilicity of the Receptor. |
Autori: | |
Data di pubblicazione: | 2007 |
Rivista: | |
Abstract: | A new approach to the use of micelles in the fluorescent sensing of metal cations is proposed and applied to the case of Hg2+. We demonstrate how it is possible to transform a system from an ON-OFF to an OFF-ON sensor by changing the length of the chain used to lipophilise a ligand that resides inside Triton X-100 micelles together with pyrene as the fluorophore. Three tetrathia-monoaza macrocyclic ligands have been synthesised with the same ring but functionalised on the nitrogen atom with a methyl (C1-NS4), an n-butyl (C4-NS4) or an n-dodecyl (C12-N54) chain. ne three ligands have been fully characterised in water containing TritonX-100 micelles by means of potentiometric titrations and their apparent protonation and complexation constants with Hg2+ were determined. On the basis of the distribution diagrams obtained, the more lipophilic C12-NS4 has been developed as an ON-OFF fluorescent sensor for mercury: working at pH < 4, in the absence of Hg2+ the ligand is inside the micelles, protonated and non-quenching, while on addition of mercury the [C12-NS4Hg](2+) complex forms which remains inside the micelles and is quenching. On the other hand, the ligand of intermediate chain length, C4-NS4, can be used to obtain an OFF-ON sensor at 7.0 < pH < 9.5. In the absence of added metal at pH > 7.0 the ligand is unprotonated, it stays inside the micelles and is quenching, while addition of Hg2+ in the 7.0-9.5 pH range results in the formation of [C4-NS4Hg](2+), which is hydrophilic enough to leave the micelles and to be released into the bulk solution where it is no longer capable of quenching pyrene fluorescence. Additional studies on C1-NS4, C3-NS4 and C8-NS4 indicate that the optimal chain length to observe this OFF-ON behaviour is C-3-C-4 |
Handle: | http://hdl.handle.net/11571/34851 |
Appare nelle tipologie: | 1.1 Articolo in rivista |