Transition Metal Ion-binding Properties of a 14-Membered N2O2S2- Macrobicyclic Ligand

The selective liquid–liquid extraction of various transition metal cations from the aqueous phase to the organic phase was carried out using a 14-membered N₂O₂S₂-macrobicycle. Metal picrates such as Pb²⁺, Co²⁺, Zn²⁺, Ni²⁺,Cu²⁺ and Cd²⁺ were used in this extraction studies. It was found that the ligand showed moderate selectivity towards Pb²⁺ only among the other metals. The extraction constant (log K _ex) was determined to be 13.8 for Pb²⁺ complex.     

Ion-pair extraction of transition metal cations from aqueous media using novel N2O2-macrocyclic crown ligands

Three new macrocyclic crown ether ligands containing nitrogen–oxygen donor atoms were designed and synthesized from 1,4-bis(2′-formylphenyl)-1,4-dioxabutane and 4-nitro-o-phenylenediamine. Ion-pair extraction of metal picrates such as Ag⁺, Hg²⁺, Cd²⁺, Zn²⁺, Cu²⁺, Ni²⁺, Mn²⁺, Co²⁺, and Pb²⁺ from aqueous phase to the organic phase was carried out using the novel ligands. The solvent effect over the metal picrate extractions was investigated at 25 ± 0.1 °C by using UV–visible spectrometry. The extractability and the values of the extraction constants (log K_ex) were determined for the extracted complexes.     

Liquid—liquid distribution behavior of ion-pairs of triphenylmethane dye cations and their analytical applications

The extraction of ion-pairs of monovalent anions (chloride, bromide, iodide, perchlorate, benzenesulfonate, naphthalenesulfonate and octanesulfonate ions) with pararosaniline, crystal violet, ethyl violet and methylene blue cations is described. The extraction constants (K_ex) for these ion-pairs between an aqueous phase and several organic phases (1,2-dichloroethane, chloroform, o-dichlorobenzene, chlorobenzene, benzene and toluene) were determined. The values of log K_ex for ion-pairs with ethyl violet were on average about 2.7 times larger than those of crystal violet, which were in turn about 6 times larger than those for pararosaniline. The order of the extractability of ion-pairs was 1,2-dichloroethane > chloroform > o-dichlorobenzene > chlorobenzene > benzene > toluene, and the differences of the log K_ex between two successive solvents averaged 0.4, 1.9, 2.1, 2.6 and 0.8, respectively. Ethyl violet and crystal violet are useful extraction-spectrophotometric reagents for iodide, perchlorate and alkyl or arylsulfonate ions.     

The synthesis and characterization of 22-membered diazapentathia macrocycles and investigation of their ion extraction capability from aqueous media

Two new macrocyclic ligands, (5) and (6), containing nitrogen–sulfur donor atoms were designed and synthesized in a multi-step reaction sequence. Ion extraction capability of macrocycles (5) and (6) were investigated involving solvent extraction of metal picrates such as Ag⁺, Hg²⁺, Cd²⁺, Zn²⁺, Cu²⁺, Ni²⁺, Mn²⁺, Co²⁺ and Pb²⁺ from aqueous phase to the organic phase. The metal picrate extractions were carried out at 25 ± 0.1 °C and extractions were measured by u.v.–visible spectrometry. The extractability and selectivity of the mentioned metal picrates were evaluated depending on the organic solvents used for extraction. The extraction constant (log K_ex) and the complex composition of each metal complex were determined using spectroscopic methods.     

Extraction Equilibria between Benzene and Water of Uni- and Bivalent Metal Picrates with Lariat 16-Crown-5: Effect of the Side Arms on the Extraction Ability and Selectivity

The overall extraction constants (K_ex) of uni- andbivalent metal picrates with 15-(2,5-dioxahexyl)-15-methyl-16-crown-5(L16C5) were determined between benzene and water at 25°C. TheK_ex values were analyzed into the constituent equilibriumconstants, i.e., the extraction constant of picric acid, the distributionconstant of the crown ether, the stability constant of the metalion–crown ether complex in water, and the ion-pair extraction constantof the complex cation with the picrate anion. The K_ex valuedecreases in the orders Ag⁺ > Na⁺ >Tl⁺ > K⁺ > Li⁺ andPb²⁺ > Ba²⁺ > Sr²⁺ for theuni- and bivalent metals, respectively, which are the same as those observedfor 16C5. The extraction selectivity was found to be governed by theselectivity of the ion-pair extraction of the L16C5–metal picratecomplex rather than by that of the complex formation in water. Theextraction ability of L16C5 is smaller for all the metals than that of 16C5,which is mostly attributed to the higher lipophilicity of L16C5. Differencesin the extraction selectivity between L16C5 and 16C5 were observed for thebivalent metals but little for the univalent metals. The side-arm effect onthe extraction selectivity was interpreted on the basis of the negativecorrelation between the effect on the complex stability constant in waterand that on the ion-pair extraction constant.     

Solvent extraction of strontium picrate from water into nitrobenzene in the presence of benzo-15-crown-5

From extraction experiments with 85Sr as a tracer, the extraction constant corresponding to the equilibrium Sr²⁺(aq) + 2A^- (aq) + 2L (nb) Û SrL₂ ^,2+ (nb) 2A^- (nb) in the two-phase water-nitrobenzene system (A^- = picrate, L = benzo-15-crown-5; aq = aqueous phase, nb = nitrobenzene phase) was evaluated as log K _ex     

Extraction behavior of strontium from nitric acid solution with N,N,N′,N′-Tetraisobutyl diglycolamide

The extraction behaviors of strontium from nitric acid solution were investigated with N,N,N′,N′-tetraisobutyl diglycolamide (TiBDGA). Effects of acidity, diluents, concentration of extractant and temperature on the distribution ratio of strontium (D _Sr) were examined. The stoichiometry of the extracted molecule was Sr²⁺:TiBDGA of 1:3. The apparent extraction equilibrium concentration constant logK _ex was 3.25. The enthalpy change ΔH and entropy change ΔS were ?55.6 kJ mol^-1 and ?124 J mol^-1 K^-1, respectively. The extraction is an exothermic process. Through two strip stages, strontium could be stripped effectively by 0.01 M nitric acid solution.     

Automatic potentiometric two-phase titration in pharmaceutical analysis : Part 3. Titrimetric Identification of Drugs

The conditional acidity constant in a liquid-liquid two-phase system (pK^*_HA + value) can be used as an identity parameter for drug compounds. The pK^*_HA + value can be calculated if the phase ratio and the acidity and distribution constants are known. Selectivity is obtained mainly by the choice of the organic phase. An excess of hydrochloric acid is first added to the sample in the two-phase system. The hydrochloric acid and the sample are then titrated sequentially with sodium hydroxide. The proposed titration procedure makes it possible to calibrat the electrodes, determine the pK^*_HA + value(s), quantify one or more compounds, and check the performance of the electrodes in one and the same experimental run. Lidocaine was “identified” and assayed in different dosage forms such as ointment and solution for injection. The results were in agreement with those obtained by liquid chromatography.     

Solvent extraction of univalent and bivalent metal picrates with 1,2-bis[2-(2-methoxyethoxy)ethoxy] benzene (noncyclic crown ether) into CHCl3

The overall extraction equilibrium constants, K_ex, of 1:1:m complexes of 1,2-bis[2-(2-methoxyethoxy)ethoxyjbenzene (AC · B18C6) with uni- and bivalent metal picrates, MA _m were determined at 25°C between CHCl₃ and water, and thereby the ion-pair complex-formation constants,K _MLA,o, of AC · B18C6 with the univalent metal picrates in CHCl₃ were calculated. The AC · B18C6 is an open-chain analog of benzo-18-crown-6 (B18C6). The equilibrium constants of AC · B18C6 were compared with those of B18C6. K_ex sequences of AC · B18C6 for uni- and bivalent metals are Tl⁺ > K⁺ > Rb⁺ > Cs⁺ > Na⁺ > Li⁺ and Pb²⁺ > Ba²⁺ > Sr²⁺, respectively. The same extraction-selectivity was observed for B18C6, but the extractability of AC · B18C6 for the same cation is much lower than that of B18C6; the extraction selectivity of AC · B18C6 for alkali metals is lower than that of B18C6. TheK _MLA,o sequence of AC · B18C6 is K⁺ > Rb⁺ > Tl⁺ > Cs⁺ Na⁺, which is consistent with that of B18C6. ButK _MLA,o of AC · B18C6 is much smaller than the correspondingK _MLA,o of B18C6; the selectivity of AC · B18C6 among alkali metal picrates in CHCl₃ is lower than that of BI8C6. This reflects the difference in the structures between AC · B18C6 (acyclic and flexible) and B18C6 (cyclic and rigid).     

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.     

Radiochemische Bestimmung der Beständigkeitskonstanten des Komplexes aus Triphenyltetrazoliumchlorid und Antimon(V) in stark salzsaurer Lösung

It is possible to extract Sb(V), even in traces, nearly completely from 6M HCl by 2,3,5-Triphenyltetrazoliumchloride (TTC). The molar ratio of the ion associate in the organic phase is found to be 1∶1. Graphic evaluation of radiometric measurements using¹²⁵Sb as tracer give the following results: extraction constant K_ex=1.65·10⁴, distribution constant K_D=19.95, stability constant of the ion associate β=0.83·10³.     

Liquid-liquid extraction of copper(I) by cyclic tetrathio ethers

The liquid-liquid extraction of copper(I) with 12-, 13-, 15- and 16-membered cyclic tetrathio ethers ([n]aneS₄, where n represents the total number of carbon and sulphur atoms in the cyclic ligand ring) was examined stoichiometrically using picrate ion (Pic^?) for the formation of the ion pair. Copper(I) was extracted with four ligands (L) into 1,2-dichloroethane as the ion-pair compound, [Cu(I)L]⁺Pic^?. The extraction constant, K_ex, with each ligand was determined. As the ring size of cyclic tetrathio ethers increases, the log K_ex values, including that previously reported for [14]aneS₄, increase from 7.7 to 9.4. The value of Δ log K_ex, which represents the increase in log K_ex due to the addition of one carbon atom to the macrocyclic ring, was large between [13]aneS₄ and [14]aneS₄ (Δ log K_ex=1.0) and small between [14]aneS₄ and [15]aneS₄ (Δ log K_ex=0.1).     

Solvent extraction and self-assembly of nanosized aggregates of p-tert-butyl thiacalix[4]arenes tetrasubstituted at the lower rim by tertiary amide groups and monocharged metal cations in the organic phase

New p-tert-butyl thiacalix[4]arenes functionalized with morpholide and pyrrolidide groups at the lower rim in cone, partial cone, and 1,3-alternate conformations were synthesized, and their receptor properties for monocharged cations (alkali metal and silver ions) were studied using the picrate extraction method and dynamic light scattering (DLS). To evaluate the ability of the p-tert-butyl thiacalix[4]arene derivatives to recognize metal ions, liquid-liquid extraction of their picrate salts has been carried out in a mutually saturated water-dichloromethane system. The degrees of extraction and the extraction constants for monocharged metal cations (Li⁺, Na⁺, K⁺, Cs⁺) have been determined. The ability of the systems, consisting of host and guest molecules, to self-assembly was proved by DLS using a Zetasizer Nano ZS particle size analyzer. It was shown that all the investigated thiacalix[4]arenes are able to form nanoscale particles with silver cations under the experimental conditions. The pyrrolidide derivative in the cone conformation showed both self-association and aggregation processes with lithium cations. The degree of extraction for all the investigated systems that formed nanoscale aggregates in the organic phase was more than 67% and the extraction constants, log K_ex determined by the picrate extraction method, more than 6.     

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.     

New heavy metal ion-selective macrocyclic ligands with mixed-donor atoms and their extractant properties

Synthetic procedures for new macrocyclic diamides with N₂S₄O₃- and N₂S₅O₃-donors were given. The corresponding macrocyclic ligands were prepared by reaction of NaBH₄ with the macrocyclic diamides in the presence of boron triflouride ethyl etherate in dry tetrahydrofuran. The solvent extraction method was used to evaluate metal-ion binding properties of the new ligands. The values of the extraction constants (log K _ex) and the complex compositions were determined for the extracted complexes. The solvent extraction experiments suggested that the reduced N₂S₅O₃-donor macrocycle has Ag⁺ selectivity compared to Pb²⁺, Co²⁺, Ni²⁺, Mn²⁺, and Cd²⁺ for chloroform as organic solvent.     

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.     

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.     

Liquid ion-exchange extraction study of hexacyanoferrate(III) with trioctylmethylammonium chloride (aliquat-336)

Liquid-liquid ion-exchange extraction of various anions including hexacyanoferrate(III) with a chlorobenzene solution of trioctylmethylammonium chloride (TOMA-Cl; Aliquat-336 chloride) is described. The ion-pair extraction constant of TOMA-Cl (K^Q.Cl_ex = 10⁴) and the ion-exchange extraction constants of TOMA-Cl for each anion (K^Cl.X_ex) are reported. The order of selectivity of anion extraction is Fe(CN)^3-₆ (log K^Q.X_ex = 22.41) > ClO^-₄(8.47) > PAR^- (7.80) > I^-(7.32) > NO^-₃(5.81) > Br^-(5.34) > Cl^-(4.00).     

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.