Equilibrium Constants for the Formation of Ammine Complexes with Certain Metallic Ions<sup>1</sup>

Carlson, G. Anders; McReynolds, James P.; Verhoek, Frank H.

doi:10.1021/ja01224a036

Cited by 102 publications

(36 citation statements)

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“…However, the logarithmic protonation constant for C1‐NS4 measured in water is log K =7.0, a value very similar to that observed in water/TritonX‐100. This leads to two conclusions: 1) this ligand is included only to a negligible extent in the TritonX‐100 micelles or it interacts with micelles in the more external, highly hydrated mantle and 2) the nitrogen atom of the tertiary [16]aneNS4 framework has an intrinsically low basicity, probably related to its particularly hindered nature 24. Moreover, the protonation data found in the dioxane/water medium (Table 1) are almost identical for the three ligands.…”

Section: Resultsmentioning

confidence: 88%

Fluorescent Sensors for Hg²⁺ in Micelles: A New Approach that Transforms an ON–OFF into an OFF–ON Response as a Function of the Lipophilicity of the Receptor

Pallavicini

Fernandez

Foti

et al. 2006

Chemistry A European J

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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 TritonX‐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‐NS4) chain. The 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 7.07.0 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 C3–C4.

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Section: Resultsmentioning

confidence: 88%

Fluorescent Sensors for Hg²⁺ in Micelles: A New Approach that Transforms an ON–OFF into an OFF–ON Response as a Function of the Lipophilicity of the Receptor

Pallavicini

Fernandez

Foti

et al. 2006

Chemistry A European J

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“…Based on the Eq. (2), β1 and β2 were 2.24×10 7 and 5.01×10 13 , respectively. So the stability constants of binary Cu-SeMet complex were 2.24×10 7 (K1) and 2.24×10 6 (K2), respectively.…”

Section: Stability Constant Of Binary Cu-semet Complexmentioning

confidence: 95%

“…In the literature [8] , the stability constant of complex was determined by the method of electrochemistry [6][7][9][10][11][12] , spectroscopy [13][14][15][16][17] , and capillary electrophoresis [18][19][20][21] . Capillary electrophoresis is convenient, time-saving, and online analysis compared to the other two methods.…”

Section: Vol26mentioning

confidence: 99%

Interaction between Selenomethionine and Copper Ions

Wang¹,

暨南大学化学系²,

Bai³

et al. 2010

Acta Physico-Chimica Sinica

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有 4 个峰(峰 I, II, III, IV). 扫描电位从 600 mV 到-600 mV 时, Cu(II)-(SeMet)2 配合物在 14 mV 时被还原为 Cu(I)-SeMet 配合物; Cu(I)-SeMet 配合物在-194 mV 被还原为 Cu(0)和 SeMet. 由-600 mV 回扫时, 还原产物被逐次氧化为 Cu(I)-SeMet 配合物(128 mV)和 Cu(II)-(SeMet)2配合物(271 mV). 同时发现 Cu(I)-SeMet 配合物在电位-100 mV 至 200 mV 间是稳定的, Cu(I)的氧化还原过程被观察到. 此外, 采用毛细管电泳法测得二元 Cu-SeMet 配合物的稳定常数(K1和 K2)分别为 2.24×10 7 和 2.24×10 6. 最后, 推测 Cu-SeMet 配合物的结构为: 在 pH 3.9 时, 铜离子通过 Cu-Se 和 Cu-OCO 键与 SeMet 发生配位作用; 在生理条件时, 铜离子通过 Cu-N 和 Cu-OCO 键与 SeMet 发生配位作用.

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“…To There is another way to dissolve the [AgWea] + complex, used by Carlson et al [11] for a Potentiometrie determination of the equilibrium constants K1 and K2: By adding the same stoichiometric amount of a strong acid (HN03) and further ethylamine, the pH of the sample is lowered, but the concentration of free ea is not changed, as the equilibrium of the reaction H + + ea^eaH + is shifted nearly quantitatively to the right site, because of the large equilibrium constant k = 10 10 " 8 1/mol (see [11]). …”

Section: Selective Solvation Of the Ag + -Ion By H20 And Ethylaminementioning

confidence: 99%

¹⁰⁹Ag NMR-Studies of the Selective Solvation of the Ag⁺ -Ion in Water-Ethylamine-Mixtures and of the Coordination of Halide-Anions to the Silver-Ethylamine Solvate Complexes

Kronenbitter

Schweizer

Schwenk

1980

Zeitschrift Für Naturforschung A

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109 Ag chemical shift measurements of 0.02 up to 3 molar solutions of AgNOa, AgCl, and AgBr in solvent mixtures of H2O (W) and ethylamine (ea) were performed. The extremely long relaxation times T\ and T2 were determined with new techniques.The Ag + -ion in solvent mixtures of W and ea shows a strongly selective solvation by ea. The 109 Ag chemical shift of the solvate complex [Ag ea2] + surrounded solely by W is 62 = (335 ± 2) ppm (referred to the Ag+-ion in W). A further solvation in addition to the inner solvation sphere was determined; this solvation is not or only weakly selective. There is a rapid chemical exchange; the lifetime of the inner solvation sphere is long compared with the Larmor period, whereas the solvation outside this sphere is changed in times shorter than the Larmor period.In contrast to the N03~-anion, the halide anions Cl~ and Br~ are partly coordinated to the [Ag ea2] + complex. The equilibrium constants for this coordination were determined as well as the chemical shifts of the [Ag ea2• Cl] and the [Ag ea2• Br] complexes. The bromine ion is coordinated for shorter times than the Larmor period, whereas the time of the coordination of the chlorine ion may be comparable to the Larmor period or shorter.

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Equilibrium Constants for the Formation of Ammine Complexes with Certain Metallic Ions¹

Cited by 102 publications

References 0 publications

Fluorescent Sensors for Hg²⁺ in Micelles: A New Approach that Transforms an ON–OFF into an OFF–ON Response as a Function of the Lipophilicity of the Receptor

Fluorescent Sensors for Hg²⁺ in Micelles: A New Approach that Transforms an ON–OFF into an OFF–ON Response as a Function of the Lipophilicity of the Receptor

Interaction between Selenomethionine and Copper Ions

¹⁰⁹Ag NMR-Studies of the Selective Solvation of the Ag⁺ -Ion in Water-Ethylamine-Mixtures and of the Coordination of Halide-Anions to the Silver-Ethylamine Solvate Complexes

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Equilibrium Constants for the Formation of Ammine Complexes with Certain Metallic Ions1

Cited by 102 publications

References 0 publications

Fluorescent Sensors for Hg2+ in Micelles: A New Approach that Transforms an ON–OFF into an OFF–ON Response as a Function of the Lipophilicity of the Receptor

Fluorescent Sensors for Hg2+ in Micelles: A New Approach that Transforms an ON–OFF into an OFF–ON Response as a Function of the Lipophilicity of the Receptor

Interaction between Selenomethionine and Copper Ions

109Ag NMR-Studies of the Selective Solvation of the Ag+ -Ion in Water-Ethylamine-Mixtures and of the Coordination of Halide-Anions to the Silver-Ethylamine Solvate Complexes

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Product

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Equilibrium Constants for the Formation of Ammine Complexes with Certain Metallic Ions¹

Fluorescent Sensors for Hg²⁺ in Micelles: A New Approach that Transforms an ON–OFF into an OFF–ON Response as a Function of the Lipophilicity of the Receptor

Fluorescent Sensors for Hg²⁺ in Micelles: A New Approach that Transforms an ON–OFF into an OFF–ON Response as a Function of the Lipophilicity of the Receptor

¹⁰⁹Ag NMR-Studies of the Selective Solvation of the Ag⁺ -Ion in Water-Ethylamine-Mixtures and of the Coordination of Halide-Anions to the Silver-Ethylamine Solvate Complexes