• Journal of the Korean Applied Science and Technology
• /
• v.22 no.1
• /
• pp.50-55
• /
• 2005

A comparison of alkali metal cation and alkaline earth cation solvent extraction was made for three additional monoionizable crown ethers and one diionizable crown ether. sym-(n-Octyldibenzo)-16-crown-5-oxyacetic acid $\underline{1}$ exhibited high efficiency and selecvity in solvent extraction of alkali metal cations with respect to that observed with alkaline earth cations. Sizes of $Na^+$ and $Ca^{2+}$ appropriately match with the cavity size of monoethyl sym-bis[4(5)-tert-butylbenzo]-16-crown-5-oxymethylphosphonic acid $\underline{3}$. As the result, $Na^+$ and $Ca^{2+}$ are the best extracted. sym-(n-Octyldibenzo)-16-crown-5-oxymethyldiphosphonic acid $\underline{4}$was found to be somewhat selective for $Na^+$ over $Li^+$ and other alkaline earth metal cations. In the complexation of alklaine earth cations by crown ether diphosphonic acid $\underline{4}$, $Ca^{2+}$ and $Sr^{2+}$ are the appropriate sizes, but lager $Ba^{2+}$ may be due to favorable formation of a sandwich type complex between the crown ether cavity and the dianion of the deprotonated crown ether phoaphonic acid moiety.

• Journal of the Korean Applied Science and Technology
• /
• v.22 no.1
• /
• pp.9-14
• /
• 2005

Competitive solvent extraction of alkaline earth metal cations from water into organic solvent containing the carboxylic acid crown ether and analogous crown ether phosphonic acid monoethyl esters were investigated. sym-(n-Decyldibenzo)-16-crown-5xyacetic acid $\underline{1}$ and monoethyl sym-(n-decyldibenzo)-16-crown-5-oxymethylphosphonic acid $\underline{3}$ are structurally identical except for the ionizable groups. Both of them provide similar extraction behavior in terms of efficiency and selectivity, but monoethyl sym-(n-decyldibenzo)-16-crown-5-oxymethylphosphonic acid $\underline{3}$ showed higher alkaline earth metals loadings at acidic or neutral media. Monoethylsym-(n-octyldibenzo)-16-rown-5-oxymethylphosphonic acid $\underline{2}$ showed better selectivity and alkaline earth metals loading than did the analogous sym-(n-octyldibenzo)-16-crown-5-oxymethyldiphosphonic acid $\underline{6}$.

• Analytical Science and Technology
• /
• v.10 no.1
• /
• pp.60-65
• /
• 1997

Solvent extraction of alkali metal and alkaline earth metal cations by mono-crown ether(benzo-15-crown-5) and bis-(crown ether)s(ethylenediamine bis(4'-formyl benzo-15-crown-5)) containing benzo-15-crown-5 moieties were investigated with water-chloroform system at $25^{\circ}C$. The order of the extraction equilibrium constants($K_e$) and the complexation constants($K_c$) for the alkali metal and alkaline earth metal cations with mono-crown ether and bis-(crown ether)s were Ca(II)>Na(I)>Sr(II)>K(I)>Mg(II)>Rb(I) and Sr(II)>Ca(II)>K(I)>Rb(I)>Mg(II)>Na(I) respectively. These results were explained in terms of the size effect of metal cation and electron density effect. Also, the bis-(crown ether)s was found to extract metal cations more effectively than the corresponding mono-crown ether.

• Archives of Pharmacal Research
• /
• v.9 no.4
• /
• pp.211-214
• /
• 1986

A simultaneous determination method of alkaline earth metals was attempted with the conventional high performance liquid chromatographic system. Four cations, namely, magnesium, calcium, strontium and barium ion, were injected directly as aqueous solution into an eluent containing copper chloride solution and and were successfully separated and determined on a separating column (Zipax SCX, 4.6 mm i.d. ${\times}25$ cm length, Du Pont, USA) by using a variable wavelength UV detector. The linear calibration curves were obtianed in the range from $1.0{\times}10^{-4}M$ to $5.0{\times}10^{-4}M$ and the correlation coefficient of the calibration curve for each metal of magnesium and calcium in tap water. Alkaline earth metals were determined with the conventional high performance liquid chromatographic system.

• Bulletin of the Korean Chemical Society
• /
• v.32 no.11
• /
• pp.3979-3990
• /
• 2011

Eight ionizable nano-baskets of cone 25,26-di(carboxymethoxy)calix[4]arene-crown-3,4,5,6 were synthesized and were verified by $^1H$ and $^{13}C$ NMR spectroscopy, IR spectroscopy and elemental analysis. The competitive solvent extractions of alkali and alkaline earth metal cations were studied using such nano-baskets. The novelty of this study is including three binding units of calixarene's bowl, crown ether's ring and electron-donor ionizable moieties in a unique scaffold to assess the binding tendency towards the cations. The objective of this work is to study the extraction efficiency, selectivity and $pH_{1/2}$ of such complexes. The result of solvent extraction experiments indicated that these compounds were effective extractants of alkali and alkaline earth metal cations. Their selectivities were greatly influenced by the acidity of solution and the conformations of the calixcrown. One conformer was selective to $Na^+$ in pH ${\geq}$ 4, while the other was highly selective to $Ba^{2+}$ in pH 6 and upper.

• Bulletin of the Korean Chemical Society
• /
• v.20 no.5
• /
• pp.556-558
• /
• 1999

Lead-selective PVC membrane electrodes based on newly synthesized bis(crown ether)s containing 18-crown-6 moiety was prepared using standard PVC membrane composition. In order to monitor lead in environmental samples by lead sensor, especially good selectivity over alkali and alkaline earth metals has to be obtained. Thus, responses of the PVC membrane prepared with new bis(crown ether)s and Fluka ionophore V (crown ether) base to various cations include lead, alkali and alkaline earth metal ions were investigated for their use as a lead sensor. The polymeric liquid membrane based on trans-1 8-crown-6 ether exhibits the best overall potentiometric performances as a lead-selective electrode in terms of a wide linear dynamic range (between 10-6 and 10-2 M, Pb2+), excellent detection limit (less than 10-6 M) and good durability within limited error. The preferences of lead over other cations, such as Ag+, Hg2+, Na+, Ca2+ and even K+ in the aforementioned electrode are much better than the Fluka ionophore V system.

• Journal of the Korean Chemical Society
• /
• v.27 no.3
• /
• pp.208-212
• /
• 1983

The stability constants for the complexes formed between dibenzo-18-crown-6 compound and alkaline earth metal cations in dimethylsulfoxide, dimethylformamide, and acetonitrile have been obtained by conductometry at $25{\circ}C\;and\;35{\circ}C$respectively. The stability constants were increased in order of $Ca^{2+} in any solvent, and the magnitudes were found to be reversely proportional to the solvent donicities. The result could be understood in terms of ion-cavity radius concept, solvent basicity, and solvation of the cations.

• Journal of the Korean Chemical Society
• /
• v.38 no.2
• /
• pp.129-135
• /
• 1994

Acyclic polyether dicarboxylic acid have been studied as metal cation carriers in a bulk liquid membrane system. The proton-ionizable ligands feature allows the coupling of a cation transport to reverse proton transport. This feature offers promise for the effective separation and concentration of metal cations with the metal cation transport being driven by a pH gradient. Metal cation transport increased regularly with increasing hydroxide($H^-$) concentration of source phase and with proton($H^+$) concentration of receiving phase. Competitive transport by the acyclic polyether dicarboxylic acids is selective for calcium ion over other alkaline-earth cations.

• Bulletin of the Korean Chemical Society
• /
• v.19 no.2
• /
• pp.207-211
• /
• 1998

Potentiometric characteristics of DOS plasticized PVC-based membranes containing upper-rim calix[4]crown neutral carrier to various metal cations and protonated alkylamines have been examined. Although the calix[4]crown-based membrane electrodes exhibited substantial emf responses to alkali and alkaline earth metal cations, their high detection limits (- log[Cs+]=4.5) and sub-Nernstian response slopes (48 mV/pCs+) to the most selective cation, cesium, indicate that the metal cation complexing ability of calix[4]crown is much weaker than that of macrocyclic crown ethers. However, the calix[4]crown-based membrane electrodes exhibited near-Nernstian response slopes (56 mV/decade for hexylNH3+) with low detection limits (log[hexylNH3+]= - 6.7) to most alkylammonium ions compared to those of blank (DOS plasticized PVC membrane with no ionophore) or crown ether-based membranes. While the selectivity patterns of blank and crown ether-based membranes are determined primarily by the lipophilicity of alkylammonium ions, the membranes doped with calix[4]crown ionophore could effectively discriminate the steric shapes of nonpolar alkyl groups of alkylammonium ions.

• Bulletin of the Korean Chemical Society
• /
• v.33 no.8
• /
• pp.2669-2674
• /
• 2012

Crown ether is one of well-known host molecules and able to selectively sequester metal cation. We employed M06-2X density functional theory with IEFPCM and SMD continuum solvation models to study selectivity of dibenzo-18-crown-6-ether (DB18C6) for alkaline earth dications, $Ba^{2+}$, $Sr^{2+}$, $Ca^{2+}$, and $Mg^{2+}$ in the gas phase and in aqueous solution. $Mg^{2+}$ showed predominantly strong binding affinity in the gas phase because of strong polarization of CO bonds by cation. In aqueous solution, binding free energy differences became smaller among these dications. However, $Mg^{2+}$ had the best binding, being incompatible with experimental observations in aqueous solution. The enthalpies of the dication exchange reaction between DB18C6 and water cluster molecules were computed as another estimation of selectivity in aqueous solution. These results also demonstrated that $Mg^{2+}$ bound to DB18C6 better than $Ba^{2+}$. We speculated that the species determining selectivity in water could be 2:1 complexes of two DB18C6s and one dication.