Searching for new host compounds: synthesis and characterization of novel crown ether-functionalized dendrimers

Novel lipophilic dendrimers as host compounds, that is, 7-15, containing crown ether moieties with different sizes as the core, surrounded by first, second or third generation poly(aromatic ether) wedges, were synthesized by the use of bis(bromomethyl)-substituted crown ethers and Fréchet-type poly(benzyl ether) dendrons as building blocks. The compounds were fully characterized.     

Synthesis of chromogenic crown ethers and liquid-liquid extraction of alkali metal ions

New crown ethers carrying a pendent phenolic chromophore were synthesized. These crown ethers, on dissociation of the phenolic proton, provide lipophilic anions which can extract alkali metal cations into 1,2-dichloroethane by forming highly-colored uncharged metal complexes. Structural effects on the extraction were studied for possible use of these crown ethers as extraction—spectrophotometric reagents selective for alkali metals. The following factors are discussed in detail: (i) nature of the crown ether ring (ring size. aza-crown or standard crown ether), (ii) nature of the pendent phenolic group, and (iii) geometry between the crown ether center and pendent phenolic group. 15-Crown-5 or smaller ring-sized reagents favored the extraction of lithium ion when the basicity of the pendent phenolate was relatively high and a six-membered “chelate” ring was possible for the phenolate and the crown ether-bound metal. 15-Crown-5 type reagents were sodium-selective when an eight-membered “chelate” ring was possible between the phenolate and the crown ether-bound metal. 18-Crown-6 type reagents were generally potassium-selective. However, these selectivities were not absolute, and other structural parameters, steric and conformational, must be considered to explain in detail the selectivities of the individual reagents.     

Luminescent dendrimers as ligands for metal ions

Suitably designed luminescent dendrimers can play a role of ligands for luminescent and non-luminescent metal ions. This combination leads to species capable of exhibiting interesting and unusual properties, including (i) shielding excited states from quenching processes, (ii) light harvesting, (iii) conversion of incident UV light into visible or infrared emission, and (iv) metal ions sensing with signal amplification.     

Task-specific ionic liquid trioctylmethylammonium salicylate as extraction solvent for transition metal ions

A quaternary ammonium-based room temperature ionic liquid trioctylmethylammonium salicylate (TOMAS) has been studied as an extractant of transition metal ions (Fe³⁺, Cu²⁺, Ni²⁺, Mn²⁺) in aqueous solutions. The effect of pH value on the recovery of metal ions has been investigated. The mechanism of extraction into the ionic liquid has been proposed. The possibility of stripping voltammetric determination of transition metals in aqueous solutions using TOMAS-modified electrodes has been demonstrated.     

Some solvent effects on the solvent extraction of 8-quinolinol

The distribution constants of 8-quinolinol between water and a series of substituted aliphatic hydrocarbons, at 25 degrees , are reported. The results are discussed in terms of dielectric constant and solubility parameter of the solvents. For 8-quinolinol, and possibly for its chelates, bromochloromethane, dibromomethane and chloroform seem to be about the best solvents, in that order. Among the solvents studied, chloroform shows significantly higher values than expected; the deviation may be explained as a specific interaction of the hydrogen- bonding type.     

Synthesis of chromogenic crown ethers and liquid—liquid extraction of alkaline earth metal ions

New crown ether dyes carrying two pendent anionic side-arms were synthesized for the extraction-spectrophotometry of alkaline earth metal ions. In the extraction of alkaline earth metal ions by these dianionic reagents, size recognition by the crown ether ring was more remarkable than in the case of alkali metal ion extraction by a similar type of monoanionic reagents. Dramatic changes in metal selectivity were observed when the nature of the anionic side-arm was changed while the crown ether skeleton was kept the same. The structure/selectivity relationship is discussed in terms of “chelate” and “intramolecular ion-pair” formation. Typically, when the basicity of the pendent anions was relatively high and a six-membered chelate was structurally possible for the pendent anions and the crown-bound metal, the extraction of calcium was favored by up to a factor of 3000 in the ratio of the Ca/Ba extraction constants for reagents of the diaza-18-crown-6 type. In contrast, the reagents which had pendent anions with only poor coordination ability for metal ions seemed to form complexes of the ion-pair type, and calcium ion was 10⁵ times less extractable than barium ion for the same diaza-18-crown-6-skeleton. Strontium ion seemed to be extracted most effectively when the extracted complex assumed properties intermediate between the chelate and intramolecular ion-pair.     

Systematic study of the solvent extraction of metal oxinates

The extraction of 32 metals (Be, Mg, Ca, Sr, Ba, Sc, La, Ti, Zr, Th, V, Nb, Cr, Mo, W, U, Mn, Fe, Co, Ni, Pd, Cu, Ag, Zn, Cd, Hg, Al, Ga, In, Tl, Pb and Bi) with oxine solution has been studied. The effects of pH, oxine concentration and water-soluble complexing agents (oxalic acid, tartaric acid, hydrocyanic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid and 1,2-diaminocyclohexanetetraacetic acid) have been investigated. From these results the extraction constants and stability constants ot the metal complexes with the various complexing agents investigated have been calculated.     

Catalytic effects in solvent extraction

Catalytic phenomena in solvent extraction of metals with hydrophobic chelating extractants are reviewed. Interface modification by adsorption of additives, phase transfer catalysis, formation of micelles, reversed micelles and microemuslions are discussed and examples are given.     

Ligand-accelerated liquid membrane extraction of metal ions

A method has been developed to enhance the liquid membrane extraction of heavy metals such as cobalt, copper and nickel. The method consists of introducing anion ligands, such as acetate, to the aqueous solution containing metal ions. In the absence of a ligand in the aqueous phase, it takes about 15 min for a 80% cobalt recovery, while only 2 min are needed for a 95% recovery with the addition of 0.1 M acetate in the feed solution. The ligand effects on liquid membrane extraction are rationalized in terms of the labile nature of the ligand—metal complexes, the distribution coefficients of the metal ions, the interfacial and surface tensions, and by the nuclear magnetic r̀esonance (NMR) spectra of the metal—organic complexes.     

A theoretical approach to the solvent extraction of metal chelates

A simplified theory for the solvent extraction of metal chelates is presented. Factors which are taken into account include the metal ion, the chelating reagent, aqueous complexing agents, adduct-forming substances, the organic solvent, temperature, rates of extraction, and other effects. Equations are developed for estimating the stoichiometries and the association constants of the involved species.     

Temperature and solvent effects on the experimental dipole moments of three crown ethers

Dipole moments of 12-crown-4, 15-crown-5 and 18-crown-6 have been measured for solutions in benzene and in cyclohexane at 15, 20 , 25, and 30°, using the Guggenheim-Smith method. The dipole moments of the more common conformers of these crown ethers have also been calculated. The results indicate that these crown ethers exist in solution as mixtures of conformers. The conformational equilibria shift toward the more polar conformers as temperature increases. There is evidence that the more polar conformers of 12-crown-4 and 15-crown-5 are somewhat more favored in benzene solution than in cyclohexane, possibly as the result of a weak complexation with the former solvent.     

Separation of thorium from lanthanides by solvent extraction with ionizable crown ethers

Thorium and the lanthanides are extracted by alpha-(sym-dibenzo-16-crown-5-oxy)acetic acid and its analogues in different pH ranges. At pH 4.5, Th is quantitatively extracted by the crown ether carboxylic acids into chloroform whereas the extraction of the lanthanides is negligible. Separation of Th from the lanthanides can be achieved by solvent extraction under this condition. The extraction does not require specific counteranions and is reversible with respect to pH. Trace amounts of Th in water can be quantitatively recovered using this extraction system for neutron activation analysis. The nature of the extracted Th complex and the mechanism of extraction are discussed.     

Solvent extraction of several metal ions with mercaptotropone

Mercaptotropone was synthesized from tropone, and its acid dissociation constant (K_a) and distribution coefficient (K_D) between benze and aqueous solution were spectrophotometrically determined as 5.75 (pK_a) and 2.46 (log K_D); Extraction behaviour of Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Pb(II), Cr(III), Fe(III), Y(III), and Zr(IV) with this reagent into benzene was examined. Cu(II) and Fe(III) were completely extracted from acidic solution, Mn(II), Co(II), Ni(II), Zn(II), Pb(II), and Zr(IV) were also extracted from intermediate pH region, a part of Cr(III) was extracted, but Y(III) was not extracted.     

A theoretical study of the solvent extraction of multipolymeric metal complexes

A mathematical treatment is demonstrated which explores the simultaneous extraction of multipolymeric complexes. The theory will predict that there may be only a finite number of species which can exist.     

冠醚-离子液体体系对水相中锶离子的萃取研究

本文研究了以一系列离子液体作为介质时,萃取剂二环己基18冠6（DCH18C6）对水相中Sr^2＋的萃取行为．研究结果表明,DCH18C6／离子液体体系对Sr^2＋的萃取性能优于相应的DCH18C6／JE辛醇萃取体系,一定条件下其萃取Sr^2＋的分配比可达10^3量级．同时,体系对Sr^2＋的萃取性能随着离子液体的结构不同而有所差别．在离子液体萃取体系中,随着水相初始硝酸浓度的增加,对Sr^2＋的萃取性能下降．水相中Na^＋、K^＋等离子的存在也会对体系萃取Sr^2＋产生直接影响．本文还验证了离子液体体系萃取Sr^2＋的机理,即以阳离子交换机理为主实现对Sr^2＋的萃取．     

Investigation on the extraction of strontium ions from aqueous phase using crown ether-ionic liquid systems

The extraction of strontium ions using DCH18C6 as the extractant and various ionic liquids (ILs) as solvents has been investigated. The distribution ratio of Sr²⁺ can reach as high as 10³ under certain conditions, much larger than that in DCH18C6/n-octanol system. The extraction capacity depends greatly on the structure of ionic liquids. In IIs-based extraction systems, the extraction efficiency of strontium ions is reduced by increasing the concentration of nitric acid and can also be influenced directly by the presence of Na⁺ and K⁺ in the aqueous phase. It is confirmed that the extraction proceeds mainly via a cation-exchange mechanism.     

表面活性剂体系萃取分离贵金属离子的研究

研究了在TritonX 100 (NH4)2SO4 络合剂体系中,贵金属离子的萃取分离行为。考察了金属络合物的液 液两相间的分配行为及影响络合物萃取行为的各种因素,优化了萃取分离条件。实验结果表明,在pH7.0～7.5的溶液中,络合剂PAR能与Pd(Ⅱ)形成稳定的络合物,可被定量萃取,实现了Pd(Ⅱ)与Pt(Ⅵ)、Ir(Ⅵ)、Mo(Ⅵ)等混合离子间的定量分离。混合离子分离中,Pd(Ⅱ)的回收率为97.5%～100.8%。     

The solvent extraction of carrier-free90Y from90Sr with crown ethers

A simple solvent extraction method has been developed for the separation of⁹⁰Y from⁹⁰Sr. Crown ether dissolved in chloroform was used as a selective reagent and organic picrate anion was chosen as a counter ion. The effect of various factors on the extraction separation of strontium and yttrium in the system have been studied. The extraction equilibrium constant of strontium logK _ex=9.15 was obtained from the study of the distribution coefficient versus the crown ether concentration. The separation method was simple, resulted high purity (>99.9%) and quantitative yield, and took less than half an hour.