• Journal of Photoscience
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• v.10 no.1
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• pp.127-148
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• 2003

Zeolite is a porous highly interactive matrix. Zeolitic cations help to generate triplets from molecules that possess poor intersystem crossing efficiency. Certain zeolites act as electron acceptors and thus can spontaneously generate radical cations. Zeolites also act as proton donors and thus yield carbocations without any additional reagents. These reactive species, radical cations and carbocations, have long lifetime within a zeolite and thus lend themselves to be handled as ‘regular’ chemicals. Internal structure of zeolites is studded with cations, the counter-ions of the anionic framework. The internal constrained structure and the cations serve as handles for chemists to control the behavior of guest molecules included within zeolites.

• Bulletin of the Korean Chemical Society
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• v.21 no.7
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• pp.685-689
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• 2000

The complexation reaction between Pb2+,TI and Cd2+ions and macrocyclic ligands, 18-crown-6 ( 18C6) and dibenzo- 18-crown-6 (DB 18C6), was studied in dimethylsulfoxide (DMSO)-nitromethane (NM) and dimethyl-formamide (DMF)-nitromethane binary system s by square wave polarography (SWP) technique. The stoichiometry and stability of the complexes were determined by monitoring the shifts in half-waves or peak potentials of the polarographic waves of metal ions against the Iigand concentration. In most cases, the stability constants of complexes increase with increasing amounts of the nitromethane in mixed binary solvents used in this study. The complexes formed between 18C6 and DB18C6 and these metal cations in all cases had a stoichiometry of 1 : 1. The results obtained show that there is an inverse relationship between the formation constant of complexes and the donor number of solvents based on a Gatmann donocity scale and the stability constants show a high sensitivity to the composition of the mixed solvent systems. A linear behavior was observed for variation of log Kf of I8C6 complexes vs the composition of the mixed solvent systems in NM/DMSO and NM/DMF,but a non-linear behavior was observed in the case of DB 18C6 complexes in these binary systems. In most of the systems investigated, the Pb2+ cation forms a more stable complex with the 18C6 than other two cations and the order of selectivity of this Iigand for cations is: Pb2+ > TI+,Cd2+.

• Bulletin of the Korean Chemical Society
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• v.26 no.3
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• pp.393-398
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• 2005

The stability constants for the diaza-18-crown-6 ethers 2-6 and alkali metal cations ($Na^+,\;K^+,\;Rb^+\;and\;Cs^+$) were determined using potentiometry in 95% methanol. For each metal ion the stability constants of the partiallyfluorinated ligands 3-6 were larger than that of the non-fluorinated ligand 2, which might reflect an interaction between fluorine atoms and alkali metal cations. The stability constant of the ligand 4 was larger than that of the ligand 5 for each metal cation tested. This finding was also supported by the results of cation-induced chemical shifts in $^1H-,\;^{19}F$-NMR and extraction experiment. The potentiometry and NMR results as well as the X-ray crystal structures revealed that the position and number of fluorine atoms in the benzyl side arms was crucial for the enhanced interaction between a ligand and an alkali metal.

• Bulletin of the Korean Chemical Society
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• v.31 no.2
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• pp.453-456
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• 2010

The structural and energetic preferences of thiacalix[4]biscrown-5 with and without alkali metal ions ($Na^+$, $K^+$, $Rb^+$, and $Cs^+$) have been theoretically investigated for the first time using molecular dynamic (MD) simulations and density functional theory (MPWB1K/6-31G(d)//B3LYP/6-31G(d)) methods. The formation of the metal ion complex by the host is mainly driven by the electrostatic attraction between crown-5 oxygens and a cation together with the minor contribution of the cation-$\pi$ interaction between two facing phenyl rings around the cation. The computed binding energies and the atomic charge distribution analysis for the metal binding complexes indicate the selectivity toward a potassium ion. The theoretical results herein explain the experimentally observed extractability order by this host towards various alkali metal ions. The physical nature and the driving forces for cation recognition by this host are discussed in detail.

• Korean Journal of Soil Science and Fertilizer
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• v.28 no.2
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• pp.105-113
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• 1995

Adsorption experiments of heavy metal cations by Fe- and Al-hydroxides was conducted to obtain clear information on their adsorption mechanisms. The adsorption isothermal curves of heavy metal cations by Fe- and Al-hydroxides conformed to Langmuir's equation. Increasing the crystallinity degree of Fe- and Al-hydroxides tended to decrease the adsorption capacity and binding energy of heavy metal cations. At the same crystallinity degree, Al-hydroxide showed higher adsorption capacity and energy for the heavy metal cations than Fe-hydroxide. The adsorption capacity and energy of heavy metal cations were directly related to CEC, specific surface area and charge density of hydroxides, and the sequence was in the order of $Cu^{+{+}}$ > $Zn^{+{+}}$ > $Cd^{+{+}}$. The adsorption mechanism of $M^{+{+}}$ form of heavy metal could be presumed as the specific adsorption of $M^{+{+}}$ and the desorption of two $H^+$ from the surface aquo($OH_2$) and/or hydroxo(-OH) group for each mole of $M^{+{+}}$ adsorbed. A ring structure between $M^{+{+}}$ and two surface aquo and/or hydroxo groups was postulated. Nonspecific adsorption involved the adsorption of $MCl^+$ and the desorption of one H+ from the surface aquo and/or hydroxo groups for each mole of $M^{+{+}}$ adsorbed. A single bond structure in which $MCl^+$ replaced one $H^+$ from the surface aquo and/or hydroxo groups was postulated. The ratio of specific to nonspecific adsorption increased with increasing pH.

• Journal of Electrochemical Science and Technology
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• v.2 no.3
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• pp.143-145
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• 2011

Metal-binding antibiotics are very attractive choices as cation selective ionophores. The ability of tetracycline (TC) antibiotics to bind to metal ions has obtained much attention. TCs exhibit the potentiometric performance changes for various cations dependant on several experiment conditions. In this report, we investigated the potentiometric performance changes of TC as the modification of TC's possible metal binding site. We found that the selectivity alter with the blocking main binding site of ionophores for cations. And, additionally it is possible to control the selectivity of sensors with chemical modification of ionophores.

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

• Analytical Science and Technology
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• v.19 no.4
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• pp.309-315
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• 2006

Two piperazine-templated metal sulfate complexes, $(C_4N_2H_{12})[Ni(H_2O)_6](SO_4)_2$, I and ($C_4N_2H_{12}$) $[Co(H_2O)_6](SO_4)_2$, II, have been synthesized by hydro/solvothermal reactions and their crystal structures analyzed by single crystal X-ray diffraction methods. Complex I crystallizes in the monoclinic system, $P2_1/n$ space group, a=12.920(3), b=10.616(2), $c=13.303(2){\AA}$, ${\beta}=114.09(1)^{\circ}$, Z=4, $R_1=0.030$ for 3683 reflections; II: monoclinic $P2_1/n$, a=12.906(3), b=10.711(2), $c=13.303(2){\AA}$, ${\beta}=114.10(2)^{\circ}$, Z=4, $R_1=0.032$ for 4010 reflections. The crystal structures of the piperazine-templated metal(II) sulfates demonstrate zero-dimensional compound constituted by diprotonated piperazine cations, metal(II) cations and sulfate anions. The structures of complex I and II are substantially isostructural to that of the previously reported our piperazine-templated copper(II) sulfate complex $(C_4N_2H_{12})[Cu(H_2O)_6](SO_4)_2$. The central metal(II) atoms are coordinated by six water molecules in the octahedral geometry. The crystal structures are stabilized by three-dimensional networks of the $O_{water}-H{\cdots}O_{sulfate}$ and $N_{pip}-H{\cdots}O_{sulfate}$ hydrogen bonds between the water molecules and sulfate anions and protonated piperazine cations. Based on the results of thermal analysis, the thermal decomposition reactions of the complex I was analyzed to have three distinctive stages whereas the complex II proceed through several stages.

• Bulletin of the Korean Chemical Society
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• v.18 no.2
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• pp.139-141
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• 1997

• Bulletin of the Korean Chemical Society
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• v.22 no.5
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• pp.527-530
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• 2001