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It has to be stressed that solubilisation of C4-NS4 and C12-NS4 in water/TritonX-100 is a result of their inclusion in micelles. TritonX-100 was used at a concentration of 10-2M, which, based on the cmc (critical micelle concentration) of this surfactant (2 × 10 -4M[3], and on its AN (100-140[32, means an average micelle concentration of ∼10-4M. As the three ligands were studied in this medium at a concentration of 10-3M. an average of-10 ligand molecules are included in each micelle, at least for C4-NS4 and C12-NS4, which can reasonably be considered as fully micellised. As regards C1-NS4, besides its solubility in pure water, its calculated protonation constant indicates that it is not included in the micellar core see discussion in the same section, The water/surfactant solution contained 0.05M NaNO3 as the background electrolyte. On the other hand, the diox
-
3 as the background electrolyte. On the other hand, the dioxane/water mixture used contains sufficient organic solvent to allow solubilisation of the three ligands and sufficient water to allow the measurement of pH with standard pH meters. Mixtures of water with dioxane as the organic component are frequently used when pH-metric or potentiometric titrations are to be carried out on molecular systems that are insoluble in pure water. The choice of dioxane instead of other organic and water-miscible solvents (e.g., acetonitrile or ethanol) derives from the particular stability of dioxane even at the extremes of the pH interval examined (pH 2-12). which allows data from the potentiometric titrations to be collected that are reliable and not affected by noise or errors even at the beginning and end of a titration experiment.
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33846027752
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From Figure 1 it can be seen that the residual fluorescence in the presence of unprotonated C12-NS4 is not negligible, but ∼40% of the full emission found in the presence of the protonated ligand. Significant residual fluorescence (20-40, for TritonX-100/pyrene/ quencher systems in the presence of different lipophilic quenching molecules (refs, 15] and [16, has already been reported by us. To interpret this behaviour, the oblate ellipsoid shape assumed by TritonX-100 micelles has to be considered as well as the consequent selective compartmentalisation of both the fluorophore and the quencher, which results in significant lowering of the effective collisions between them. In this regard, it also has to be mentioned that the choice of pyrene is not casual: we also tested naphthalene, anthracene and dansyl amide as the fluorophore, obtaining, in the presence of C12-NS4 or other quencher i.e, free micellised R-NS4 molecules and micellised [C12-NS4Hg] 2
-
2+ complexes) a higher residual fluorescence, that is. less intense signal variation in the sensing process.
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1H NMR spectra are consistent with the formulated structures.
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1H NMR spectra are consistent with the formulated structures.
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