A combined experimental and DFT study on the complexation of Mg<Superscript>2+</Superscript> with beauvericin

From extraction experiments and γ-activity measurements, the extraction constant corresponding to the equilibrium Mg²⁺(aq) + 1·Sr²⁺(nb) ⇆ 1·Mg²⁺(nb) + Sr²⁺(aq) taking place in the two-phase water–nitrobenzene system (1 = beauvericin; aq = aqueous phase, nb = nitrobenzene phase) was evaluated as log K _ex (Mg²⁺, 1·Sr²⁺) = 0.0 ± 0.1. Further, the stability constant of the 1·Mg²⁺ complex in nitrobenzene saturated with water was calculated for a temperature of 25 °C as log β_nb (1·Mg²⁺) = 9.1 ± 0.2. By using quantum mechanical DFT calculations, the most probable structures of the non-hydrated 1·Mg²⁺ and hydrated 1·Mg²⁺·3H₂O complex species were predicted.     

Extraction of Ba<Superscript>2+</Superscript>, Pb<Superscript>2+</Superscript> and Cd<Superscript>2+</Superscript> into nitrobenzene by using strontium dicarbollylcobaltate in the presence of tetramethyl <Emphasis Type="Italic">p-tert</Emphasis>-butylcalix[4]arene tetraketone

From extraction experiments and γ-activity measurements, the exchange extraction constants corresponding to the general equilibrium M²⁺(aq)+SrL²⁺(nb)⇔ML²⁺(nb)+Sr²⁺(aq) taking place in the two-phase water-nitrobenzene system (M²⁺ = Ba²⁺, Pb²⁺, Cd²⁺; L = tetramethyl p-tert-butylcalix[4]arene tetraketone; aq = aqueous phase, nb = nitrobenzene phase) were evaluated. Moreover, the stability constants of the ML²⁺ complexes in water saturated nitrobenzene were calculated; they were found to increase in the order Ba²⁺<Cd²⁺<Pb²⁺.     

A Combined Experimental and Theoretical Study on the Complexation of Ag<Superscript>+</Superscript> with a Hexaarylbenzene-Based Receptor

From extraction experiments and γ-activity measurements, the exchange extraction constant corresponding to the equilibrium Ag⁺(aq) + 1⋅Cs⁺(nb) ⇆ 1⋅Ag⁺(nb) + Cs⁺(aq) taking part in the two-phase water–nitrobenzene system (where 1 = hexaarylbenzene-based receptor; aq = aqueous phase, nb = nitrobenzene phase) was evaluated to be log ₁₀ K _ex(Ag⁺, 1⋅Cs⁺) = −1.0±0.1. Further, the stability constant of the hexaarylbenzene-based receptor⋅Ag⁺ complex (abbreviation 1⋅Ag⁺) in nitrobenzene saturated with water, was calculated at a temperature of 25 °C: log ₁₀ β _nb(1⋅Ag⁺) = 5.5±0.2. By using quantum mechanical DFT calculations, the most probable structure of the 1⋅Ag⁺ complex species was solved. In this complex having C₃ symmetry, the cation Ag⁺ synergistically interacts with the polar ethereal oxygen fence and with the central hydrophobic benzene ring via cation–π interaction.     

Experimental evidences for some unusual divalent cation complexes of valinomycin

From extraction experiments and γ-activity measurements, the exchange extraction constants corresponding to the general equilibrium M ²⁺ (aq) + 1 · Sr²⁺ (nb) ⇄ 1 · M ²⁺ (nb) + Sr²⁺ (aq) taking place in the two-phase water-nitrobenzene system (M ²⁺ = Cu²⁺, Zn²⁺, Cd²⁺, Pb²⁺, UO₂ ²⁺, Fe²⁺, Co²⁺, and Ni²⁺; 1 = valinomycin; aq = aqueous phase, nb = nitrobenzene phase) were evaluated. Moreover, the stability constants of the 1 · M ²⁺ complexes in water saturated nitrobenzene were calculated; they were found to increase in the order Fe²⁺ < Cd²⁺, Co²⁺ < Ni²⁺ < UO₂ ²⁺, Zn²⁺ < Cu²⁺ < Pb²⁺.     

Experimental evidences for some unusual divalent cation complexes of valinomycin

From extraction experiments and γ-activity measurements, the exchange extraction constants corresponding to the general equilibrium M ²⁺ (aq) + 1 · Sr²⁺ (nb) ⇄ 1 · M ²⁺ (nb) + Sr²⁺ (aq) taking place in the two-phase water-nitrobenzene system (M ²⁺ = Cu²⁺, Zn²⁺, Cd²⁺, Pb²⁺, UO₂ ²⁺, Fe²⁺, Co²⁺, and Ni²⁺; 1 = valinomycin; aq = aqueous phase, nb = nitrobenzene phase) were evaluated. Moreover, the stability constants of the 1 · M ²⁺ complexes in water saturated nitrobenzene were calculated; they were found to increase in the order Fe²⁺ < Cd²⁺, Co²⁺ < Ni²⁺ < UO₂ ²⁺, Zn²⁺ < Cu²⁺ < Pb²⁺. Correspondence: Emanuel Makrlík, Faculty of Applied Sciences, University of West Bohemia, Pilsen, Czech Republic.     

Experimental Evidence for a Valinomycin – Proton Complex

Summary. From extraction experiments and γ-activity measurements, the extraction constant corresponding to the equilibrium H⁺ (aq) + NaL⁺ (nb) = HL⁺ (nb) + Na⁺ (aq) taking place in the two-phase water-nitrobenzene system (L = valinomycin, aq = aqueous phase, nb = nitrobenzene phase) was evaluated as log K_ex (H⁺, NaL⁺) = −1.1 ± 0.1. Further, the stability constant of the valinomycin-proton complex in nitrobenzene saturated with water was calculated as log β_nb(HL⁺) = 5.3 ± 0.1. Finally, the stability constants of complexes of some univalent cations with valinomycin were summarized and discussed.     

Experimental Evidence for a Calix[4]arene-Proton Complex

From extraction experiments and γ-activity measurements, the extraction constant corresponding to the equilibrium H⁺(aq) + 1 ·Na⁺(nb) ⇆ 1 ·H⁺(nb) + Na⁺(aq) taking place in the two-phase water-nitrobenzene system (1 = p-tert-butylcalix[4]arene-tetrakis(N, N-diethylacetamide); aq = aqueous phase, nb = nitrobenzene phase) was evaluated as log K _ex(H⁺, 1 ·Na⁺) = −1.4 ± 0.1. Further, the stability constant of the p-tert-butylcalix[4]arene-tetrakis(N,N-diethylacetamide)-H⁺ complex in water saturated nitrobenzene was calculated for a temperature of 25°C as log β_nb(1 · H⁺) = 8.1 ± 0.1.     

Experimental Evidence for a Calix[4]arene-Proton Complex

Summary. From extraction experiments and γ-activity measurements, the extraction constant corresponding to the equilibrium H⁺(aq) + 1 ·Na⁺(nb) ⇆ 1 ·H⁺(nb) + Na⁺(aq) taking place in the two-phase water-nitrobenzene system (1 = p-tert-butylcalix[4]arene-tetrakis(N, N-diethylacetamide); aq = aqueous phase, nb = nitrobenzene phase) was evaluated as log K _ex(H⁺, 1 ·Na⁺) = −1.4 ± 0.1. Further, the stability constant of the p-tert-butylcalix[4]arene-tetrakis(N,N-diethylacetamide)-H⁺ complex in water saturated nitrobenzene was calculated for a temperature of 25°C as log β_nb(1 · H⁺) = 8.1 ± 0.1.     

Stability of the valinomycin - strontium complex in water saturated nitrobenzene

Summary From extraction experiments and<span style='font-size:12.0pt;font-family:Symbol; mso-bidi-font-family:Symbol'>g-activity measurements, the extraction constant corresponding to the equilibrium Ba²⁺(aq)+SrL²⁺(nb)?BaL²⁺(nb)+Sr²⁺(aq) taking place in the two-phase water-nitrobenzene system (L= valinomycin; aq= aqueous phase,</o:p>nb= nitrobenzene phase) was evaluated as logK_ex(Ba²⁺, SrL²⁺)=1.3. Furthermore, the stability constant of the valinomycin-strontium complex in nitrobenzene saturated with water was calculated for a temperature of 25 °C: logb_nb(SrL²⁺)=5.4.     

Interaction of the divalent lead cation with cyclosporin A: an experimental and theoretical study

On the basis of extraction experiments and γ-activity measurements, the extraction constant corresponding to the equilibrium Pb²⁺(aq) + 1·Sr²⁺(nb) ? 1·Pb²⁺(nb) + Sr²⁺(aq) occurring in the two-phase water–nitrobenzene system (1 = cyclosporin A; aq = aqueous phase, nb = nitrobenzene phase) was evaluated as log K _ex (Pb²⁺, 1·Sr²⁺) = 0.1 ± 0.1. Further, the stability constant of the 1·Pb²⁺ complex in nitrobenzene saturated with water was calculated for a temperature of 25 °C: log β _nb (1·Pb²⁺) = 9.2 ± 0.2. Finally, applying quantum chemical DFT calculations, the most probable structure of the proven 1·Pb²⁺ cationic complex species was derived. In the resulting complex, the “central” cation Pb²⁺ is bound by four bonding interactions to the corresponding four oxygen atoms of the parent cyclosporin A ligand. The interaction energy, E(int), of the considered 1·Pb²⁺ complex was found to be ?1016.3 kJ/mol, confirming also the formation of this complex.

     

Solvent extraction of lead using a nitrobenzene solution of strontium dicarbollylcobaltate in the presence of polyethylene glycol PEG 400

Summary From extraction experiments and γ-activity measurements, the extraction constant corresponding to the equilibrium Pb²⁺(aq)+SrL²⁺ (nb)↔PbL²⁺ (nb)+Sr²⁺ (aq) taking place in the two-phase water-nitrobenzene system (L=PEG 400; aq = aqueous phase, nb = nitrobenzene phase) was evaluated as logK_ex(Pb²⁺, SrL²⁺)=2.0±0.1. Further, the stability constant of the PEG 400 - lead complex in nitrobenzene saturated with water was calculated for a temperature of 25 °C: log β_nb(PbL²⁺)=12.9±0.1.     

Experimental and theoretical study on the complexation of Ca2+ with beauvericin

From extraction experiments and γ-activity measurements, the exchange extraction constant corresponding to the equilibrium Ca²⁺(aq) + 1·Sr²⁺(nb) ? 1·Ca²⁺(nb) + Sr²⁺(aq) taking place in the two-phase water–nitrobenzene system (1 = beauvericin; aq = aqueous phase, nb = nitrobenzene phase) was evaluated as log K _ex(Ca²⁺, 1·Sr²⁺) = 1.1 ± 0.1. Further, the stability constant of the 1·Ca²⁺ complex in nitrobenzene saturated with water was calculated for a temperature of 25 °C: log β _nb(1·Ca²⁺) = 10.1 ± 0.2. Finally, by using quantum mechanical density functional level of theory calculations, the most probable structures of the non-hydrated 1·Ca²⁺ and hydrated 1·Ca²⁺·H₂O complex species were predicted.     

Extraction of lithium with nitrobenzene solution of strontium bis-1,2-dicarbollylcobaltate in the presence of 15-crown-5

From extraction experiments and γ-activity measurements, the extraction constant corresponding to the equilibrium 2Li⁺(aq)+SrL₂ ²⁺(nb) 2LiL⁺(nb)+Sr²⁺(aq) taking place in the two-phase water-nitrobenzene system (L=15-crown-5; aq=aqueous phase, nb=nitrobenzene phase) was evaluated as logK _ex (2Li⁺;SrL₂ ²⁺)=−3.7. Further, the stability constant of the 15-crown-5—lithium complex in nitrobenzene saturated with water was calculated: log β_nh(LiL⁺)=7.0.     

Distribution of Strontium in the System Water — Ca(NO3)2 — Nitrobenzene — Strontium Dicarbollylcobaltate — 18-crown-6

From several strontium distribution experiments with ⁸⁵Sr tracer, the extraction constant corresponding to the equilibrium Ca²⁺(aq)+SrL²⁺(nb) CaL²⁺(nb)+Sr²⁺ (aq) in the two-phase water-nitrobenzene system (L = 18-crown-6; aq = aqueous phase, nb = nitrobenzene phase) was tentatively evaluated as log K _ex (Ca²⁺,SrL²⁺) = –1.9±0.1. Furthermore, the stability constant of the calcium — 18-crown-6 complex in nitrobenzene saturated with water was calculated for a temperature of 25 °C: log _nb(Cal²⁺) = 10.1±0.1.     

Solvent extraction of magnesium, zinc and manganese into nitrobenzene by using strontium dicarbollylcobaltate in the presence of valinomycin

From extraction experiments and γ-activity measurements, the exchange extraction constants corresponding to the general equilibrium M²⁺(aq)+SrL²⁺(nb)⇔ML²⁺(nb)+Sr²⁺(aq) taking place in the two-phase water-nitrobenzene system (M²⁺ = Mg²⁺, Zn²⁺, Mn²⁺; L = valinomycin; aq = aqueous phase, nb = nitrobenzene phase) were evaluated. Further, the stability constants of the ML²⁺ complexes in water saturated nitrobenzene were calculated. They were found to increase in the order of Mg²⁺<Mn²⁺<Zn²⁺.     

Extraction of silver from water into nitrobenzene using sodium dicarbollylcobaltate in the presence of valinomycin

Summary From extraction experiments andg-activity measurements, the extraction constant corresponding to the Ag⁺(aq) + NaL⁺(nb)?AgL⁺(nb) + Na⁺(aq) equilibrium in the two-phase water-nitrobenzene system (L=valinomycin; aq=aqueous phase, nb=nitrobenzene phase) was evaluated as log K_ex(Ag⁺,NaL⁺)=-0.6±0.1. The stability constant of the valinomycin-silver complex in nitrobenzene saturated with water was calculated: log b_nb(AgL⁺)=4.6±0.1. The stability constants of complexes of some univalent cations with valinomycin were summarized and discussed.     

Extraction of lead from water into nitrobenzene by using strontium dicarbollylcobaltate in the presence of benzo-15-crown-5

Summary From extraction experiments andg-activity measurements, the extraction constant corresponding to the equilibrium Pb²⁺(aq)+SrL(nb)?PbL(nb)+Sr²⁺(aq)taking place in the two-phase water-nitrobenzene system (L = benzo-15-crown-5; aq = aqueous phase, nb = nitrobenzene phase) was evaluated aslog K_ex(Pb²⁺,SrL)=0.1±0.1. Further, the stability constant of the benzo-15-crown-5-lead complex in nitrobenzene saturated with water was calculated for a temperature of25 °C:log b_nb(PbL)=13.2±0.1.     

Extraction of lead with nitrobenzene solution of strontium bis-1,2-dicarbollylcobaltate in the presence of 15-crown-5

From extraction experiments and γ-activity measurements, the extraction constant corresponding to the equilibrium Pb²⁺(aq)+SrL₂ ²⁺(nb)⇆PbL₂ ²⁺(nb)+Sr²⁺(aq) taking place in the two-phase water-nitrobenzene system (L=15-crown-5; aq = aqueous phase, nb = nitrobenzene phase) was evaluated: logK _ex (Pb²⁺,SrL₂ ²⁺)=3.0. Further, the stability constant of the PbL₂ ²⁺ complex in nitrobenzene saturated with water was calculated: log β_nb(PbL ₂ ²⁺ )=17.8     

Extraction and theoretical study on the complexation of the strontium cation with beauvericin

From extraction experiments and γ-activity measurements, the extraction constant corresponding to the equilibrium Sr²⁺(aq) + 2A^?(aq) +1(nb) ? 1·Sr²⁺(nb) + 2A^?(nb) taking place in the two-phase water–nitrobenzene system (A^? = picrate, 1 = beauvericin; aq = aqueous phase, nb = nitrobenzene phase) was evaluated as log K _ex(1·Sr²⁺,2A^?) = ?0.6 ± 0.1. Further, the stability constant of the 1·Sr²⁺ complex in nitrobenzene saturated with water was calculated for a temperature of 25 °C: log β _nb(1·Sr²⁺) = 8.5 ± 0.1. Finally, by using quantum-mechanical DFT calculations, the most probable structure of the resulting cationic complex 1·Sr²⁺ was derived.     

Experimental and theoretical study on the complexation of the cesium cation with dibenzo-30-crown-10

From extraction experiments and γ-activity measurements, the extraction constant corresponding to the equilibrium Cs⁺ (aq) + A⁻ (aq) + 1(nb) \rightleftarrows \rightleftarrows 1·Cs⁺(nb) + A⁻(nb) taking place in the two-phase water–nitrobenzene system (A⁻ = picrate, 1 = dibenzo-30-crown-10; aq = aqueous phase, nb = nitrobenzene phase) was evaluated as log K _ex (1·Cs⁺, A⁻) = 4.0 ± 0.1. Further, the stability constant of the 1·Cs⁺ complex in nitrobenzene saturated with water was calculated for a temperature of 25 °C: log β _nb (1·Cs⁺) = 5.9 ± 0.1. Finally, by using quantum–mechanical DFT calculations, the most probable structure of the resulting cationic complex species 1·Cs⁺ was derived.