• Bulletin of the Korean Chemical Society
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• v.29 no.3
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• pp.541-545
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• 2008

Stable molecular isomers were calculated for the azobenzene crown ether p-tert-butylcalix[4]arene (1) in the host and their alkali-metal-ion complexes. The structures of two distinct isomers (cis and trans) have been optimized using DFT B3LYP/6-31G(d,p) method. Trans isomer of 1 is found to be 11.69 kcal/mol more stable than cis analogue. For two different kinds of complexation mode, the alkali-metal-cation in the crown-ether moiety (exo) has much better complexation efficiency than in the benzene-rings (endo) pocket for both isomers of 1. Sodium ion has much better complexation efficiency than potassium ion in all kinds of complexation mode with host 1. The Na+ complexation efficiency of the trans-complex (1) in the exo-binding mode is 8.24 kcal/mol better than cis-exo analogue.

• Bulletin of the Korean Chemical Society
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• v.25 no.6
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• pp.847-851
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• 2004

The complexation characteristics of tetramethyl (1) and tetraethyl esters (2) of p-tert-butylcalix[4]arene with alkali metal cations have been investigated by ab initio calculation. The structures of endo- or exocomplexation of the hosts in cone conformation with alkali metal ions have been optimized using HF/6-31G method followed by B3LYP/6-31G(d) single point calculation. B3LYP/6-31G(d) calculations suggest that exo-complexation efficiencies of sodium ion to the cavity of lower rim of hosts 1 and 2 are 27.1 and 25.8 kcal/mol better than that of potassium ion, respectively. The exo-complexation efficiencies of potassium ion to the cavity of lower rim of hosts 1 and 2 are 33.3 and 31.5 kcal/mol better than the endo-complexation inside the upper rim (four aromatic rings) as expected from the experimental results. B3LYP/6-31G(d) calculation of the ethyl ester 2 shows 29.5 and 30.8 kcal/mol better exo-complexation efficiency for both sodium and potassium ions than the methyl ester 1.

• Journal of Environmental Science International
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• v.8 no.2
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• pp.211-219
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• 1999

Surface complexation models(SCMs) have been performed to predict metal ion adsorption behavior onto the mineral surface. Application of SCMs, however, requires a self-consistent approach to determine model parameter values. In this paper, in order to determine the metal ion adsorption parameters for the triple layer model(TLM) version of the SCM, we used the zeta potential data for Zeolite and Kaolinite, and the metal ion adsorption data for Pb(II) and Cd(II). Fitting parameters determined for the modeling were as follows ; total site concentration, site density, specific surface area, surface acidity constants, etc. Zeta potential as a new approach other than the acidic-alkalimetric titration method was adopted for simulation of adsorption phenomena. Some fitting parameters were determined by the trial and error method. Modeling approach was successful in quantitatively simulating adsorption behavior under various geochemical conditions.

• Bulletin of the Korean Chemical Society
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• v.33 no.10
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• pp.3321-3330
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• 2012

The complexation characteristics of mixed [2 + 2'] calix[4]aryl derivatives (3 and 4) with alkali metal cations were investigated by the mPW1PW91 (hybrid HF-DF) calculation method. The total electronic and Gibbs free energies of the various complexes (cone, partial-cone, 1,2-alternate, and 1,3-alternate) of sodium and potassium cations with 3 and 4 were analyzed and compared. The structures of the endo- or exo-complexes of the alkali metal cation with the host 3 were optimized using the mPW1PW91/6-31G(d) method, followed by mPW1PW91/6-311+G(d) calculations. The structures of the endo- or exo-complexes of the alkali metal cation with the host 4 were optimized using the mPW1PW91/6-31G(d,p) method. The mPW1PW91 calculated relative energies of the various conformations of the free hosts (3 and 4) suggest that the cone conformers of 3 and 4 are the most stable. The mPW1PW91calculations also suggest that the complexation efficiencies of the sodium ion with hosts 3 and 4 are about 24 and 27 kcal/mol better than those of the potassium ion, respectively. These trends are in good agreement with the experimental results. The exo-complexation efficiencies of the sodium ion toward the conformers of hosts 3 and 4 are roughly 14 and 17 kcal/mol better than those for the endo-$Na^+$-complexes of 3 and 4, respectively. The exo-complexation of the cone isomer of 3 with cation could be confirmed by the differences of the diagnostic C=O bands in the free host and its complex's IR spectra.

• Bulletin of the Korean Chemical Society
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• v.23 no.6
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• pp.879-884
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• 2002

A series of novel 1,3-alternate calix[4]-mono-thiacrown and -bis-thiacrowns were synhesized within good yields. The three dimensional 1,3-alternate conformation was confimed by X-ray crystal structure. From the results of two phase extraction and NMR studies on the ligand-metal complex, one can conclude that the calix[4]thiacrown ethers showed the very high selectivity for silver ion over other metal ions by an electrostatic interaction between sulfur atom and silver ion and by a $\pi-metal$ complexation.

• Bulletin of the Korean Chemical Society
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• v.18 no.12
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• pp.1256-1260
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• 1997

A series of acyclic polyethers bearing amide end-groups and lipophilic alkyl chains (3-5) were successfully synthesized with quantitative yields. Based upon the transport experiment in a bulk liquid membrane (BLM) system and solvent extraction, a very high selectivity of Pb2+ over other transition metal cations was observed. Measurement of thermodynamic parameters for complexation in methanol at 25 ℃ gave a strong evidence for excellent selective complexation for lead ion over other transition metal ions.

• Bulletin of the Korean Chemical Society
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• v.10 no.2
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• pp.155-158
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• 1989

The rates of complexation of the 18-C-6 (1,4,7,10,13,16-hexaoxacyclooctadecane) with $K^+,\;Ca^{2+},\;Sr^{2+},\;and\;Ba^{2+}$ in methanol solution have been determined at 25$^{\circ}C$ by a pressure-jump technique. The Eigen Winkler mechanism has been applied to interprete the kinetic data. The results suggest that the rate determining step of the complexation in methanol is the rearrangement of the ligand in the outer sphere ion-dipole pair to form a stable encapsulated complex of the metal ion by the crown ether.

• Bulletin of the Korean Chemical Society
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• v.32 no.10
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• pp.3773-3774
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• 2011

• Economic and Environmental Geology
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• v.45 no.2
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• pp.205-215
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• 2012

Metal ions, toxic or potentially toxic to biota and human beings, can be immobilized by sorption onto the mineral surfaces in soils and sediments. This article briefly explains theories regarding the chemical properties of mineral surfaces to sorb metal ions and processes of extended X-ray absorption fine structure (EXAFS) analysis for sorption study, and reviews atomic-scale findings on metal sorption on mineral surfaces. The theoretical understanding on the chemistry of mineral surfaces and metal sorption is fundamental to the proper analysis of the atomic-scale spectroscopy to determine the sorption phases. Atomic-scale findings on metal sorption phases discussed here include co-precipitation, ternary complexation, aging effects, and desorption possibilities, as well as outer-sphere complexation, inner-sphere complexation, and surface precipitation.

• Journal of Soil and Groundwater Environment
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• v.13 no.1
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• pp.101-109
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• 2008

The adsorption characteristics of cationic metals such as copper, cadmium, and lead onto the amorphous aluminum oxide, AMA-L, which was mineralized from raw sanding powder at $550^{\circ}C$ were investigated. Additionally, surface complexation reaction of cationic heavy metals onto AMA-L was simulated with MINEQL + software employing a diffuse layer model. From the batch adsorption tests in a single element system, the adsorption affinity of each metal ion onto AMA-L was following order: lead > copper > cadmium. In a binary system composed with copper and cadmium, quite a similar adsorption affinity was observed in each metal ion compared to the single element system. When the surface complexation constants obtained in the single system were used in the prediction of experimental adsorption results, model predictions were well fitted with experimental results of both single and binary systems.