• Bulletin of the Korean Chemical Society
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• v.16 no.3
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• pp.265-269
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• 1995

Complexation of ortho-xylyl-17-crown-5 (X17C5) with alkali metal ions in acetonitrile was studied by 7Li and 23Na NMR spectroscopy. The complex formation constants of X17C5 with LiI, LiSCN, NaI, and NaSCN were determined by investigating the changes in the chemical shifts as a function of the concentration ratio of X17C5 to metal ion. It was found that X17C5 forms 1:1 complex with Li+ and Na+ ions and the log Kf's for the complexation with LiI, LiSCN, NaI, and NaSCN were determined to be 2.88, 2.43, 2.53, and 2.30, respectively. In particular, the kinetics of complexation of X17C5 with Na+ was investigated by the method of 23Na NMR lineshape analysis. Activation energies were determined from Arrhenius plot of the resultant rate constant data to be 25.4 kJ/mol for NaI and 15.1 kJ/mol for NaSCN. Other kinetic parameters were also calculated by employing the Eyring equation. The decomplexation rates measured were 1.82 × 104 M-1s-1 for NaI and 1.50 × 104 M-1s-1 for NaSCN. It is concluded that the decomplexation mechanism is predominantly a bimolecular cation exchange for both cases.

• 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.12 no.2
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• pp.130-137
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• 1991

The following new cryptand 221 complexes of lanthanides(Ⅲ) and dioxouranium(Ⅵ) nitrate have been synthesized: $(Ln(C_{16}H_{32}N_2O_5)(H_2O)_2(NO_3)_3\ and \((UO_2)_2(C_{16}H_{32}N_2O_5)(H_2O)_4(NO_3)_4$. These complexes have been identified by elemental analysis, moisture titration, conductivity measurements and various spectroscopic techniques. The proton and carbon-13 NMR as well as calorimetric measurements were used to study the interaction of cryptand 221 with La(Ⅲ), Pr(Ⅲ ), Ho(Ⅲ) and $UO_2(Ⅱ)$ ions in nonaqueous solvents. The bands of metal-oxygen atoms, metal-nitrogen atoms and O-U-O in the IR spectra shift upon complexation to lower frequencies, and the vibrational spectra ({\delta}NMN$) of metal-amide complexes in the crystalline state exhibit lattice vibrations below 300 $cm^{-1}$. The NMR spectra of the lanthanides(Ⅲ) and dioxouranium(Ⅵ) nitrate complexes in nonaqueous solvents are quite different, indicating that the ligand exists in different conformation, and also the $^1H$ and $^{13}C-NMR$ studies indicated that the nitrogen atom of the ring has greater affinity to metal ions than does the oxygen atom, and the planalities of the ring are lost by complexation with metal ions. Calorimetric measurements show that cryptand 221 forms more stable complexes with $La^{3+}$ and $Pr^{3+}$ ions than with $UO^{22+}$ ion, and $La^{3+}/Pr^{3+}$ and $UO^{22+}/Pr^{3+}$ selectivity depends on the solvents. These changes on the stabilities are dependent on the basicity of the ligand and the size of the metal ions. The absorption band (230-260 nm) of the complex which arises from the direct interaction of macrocyclic donor atoms with the metal ion is due to n-{\delta}*$ transition and also that (640-675 nm) of $UO^{22+}$-cryptand 221 complex, which arises from interaction between two-dioxouranium(Ⅵ) ions in being out of cavity of the ligand ring is due to d-d* transition.

• Bulletin of the Korean Chemical Society
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• v.29 no.3
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• pp.620-622
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• 2008

A new thiacalix[4]arene diamide (TCAm) has been prepared and its electrochemical property and complexation behavior toward various metal ions have been investigated by voltammetry. p-tert-Butylthiacalix[4]arene diamide (TCAm) exhibited selectivity toward Sr2+ ion over alkali, alkaline earth and transition metal ions while conventional calix[4]arene diamides showed selective binding property with Ca2+ ion. This is probably due to the bigger size of thiacalix[4]arene than those of calix[4]arene.

• YAKHAK HOEJI
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• v.53 no.6
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• pp.342-350
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• 2009

The interaction of cadmium (II) ion with quercetin and (+)-catechin was investigated in aqueous solution at various pH. The flavonoid/cadmium stochiometries for cadmium (II) binding to quercetin and (+)-catechin have been determined by UV-vis spectroscopy. 1 : 1 Cd (II)-Flavonoid complex had a maximum absorbance and showed the bathochromic shift of the long-wavelength band of the UV-vis spectra in the alkaline pH, that occurs upon complexation, due to a ligandto-metal charge transfer. These results suggest that Cd (II)-flavonoid complex has the optimal condition of chelation in 0.2 M $NH_3$ - 0.2 M $NH_4Cl$ (pH 8.0) solution.

• Bulletin of the Korean Chemical Society
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• v.16 no.5
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• pp.406-409
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• 1995

The complex formation from Cu(Ⅱ) ion and 2,2-bis(hydroxymethyl)-2,2',2"-nitrilotriethanol (Bistris) in aqueous solution has been studied potentiometrically and spectrophotometrically. Bistris (L) coordinates to Cu(Ⅱ) as tridentate. The complex CuL2+ undergoes deprotonation in neutral and basic media. The deprotonated complexes involve metal-alcoholate coordinate bond in stable chelate structures.

• Korean Journal of Soil Science and Fertilizer
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• v.28 no.2
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• pp.114-122
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• 1995

Complexation experiment between humic acid and heavy metal cations was conducted to clear information on heavy metal adsorption by soil organic constituent. The absorbance of UV-visible light of humic acid-metal complexes increased with increasing wavelength, and the order of their absorbance was in the order of Zn->Cd->Cu- saturated humic acid. Carboxyl and phenolic OH groups participated in the complex formation between heavy metal cations and functional groups of humic acid, and the amounts complex was in the order of $Cu^{+{+}}$ > $Zn^{+{+}}$ $\geq$ $Cd^{+{+}}$. The stability constants of humic acid-metal complexes increased with increasing pH, and the order of first stability constants was $Zn^{+{+}}$ > $Cd^{+{+}}$ > $Cu^{+{+}}$, and those of second and overall stability constants were $Cu^{+{+}}$ > $Zn^{+{+}}$ > $Cd^{+{+}}$. With increasing pH, the average binding numbers betwen heavy metal cations and functional groups of humic acid increased the order of $Cu^{+{+}}$ > $Zn^{+{+}}$ > $Cd^{+{+}}$. It was postulated that two types of complexations between heavy metal cations and functional groups of humic acid. One was the reactions in which only carboxyl groups participated to form complexes, and the other was those in which both carboxyl and phenolic OH groups simultaneously participated.

• Bulletin of the Korean Chemical Society
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• v.17 no.9
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• pp.840-845
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• 1996

Rate constants have been measured spectrophotometrically for the reactions of p-and m-nitrophenyl 2-thiophenecarboxylate (5a and 5b, respectively) with alkali metal ethoxides (EtO-M+) in absolute ethanol at 25.0±0.1 ℃. The reactivity of EtO-M+ exhibits dependence on the size of alkali metal ions, i.e. the reactivity of EtO-M+ toward 5a decreases in the order EtO-K+ ≥ EtO-Na+ > EtO-Li+ > EtO-, while the one toward 5b does in the order EtO-Na+ ≥ EtO-K+ > EtO-Li+ > EtO-. This result indicates that ion paired EtO-M+ is more reactive than dissociated EtO-, and alkali metal ions form complexes with the substrate more strongly at the transition state than at the ground state. The catalytic effect shown by alkali metal ions appears to be less significant in the reaction of 5 than in the corresponding reaction of 4, indicating that complexation of alkali metal ions with 5 is not as strong as the one with 4.

• Applied Chemistry for Engineering
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• v.34 no.5
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• pp.556-565
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• 2023

Fast industrial and agricultural expansion result in the production of heavy metal ions (HMIs). These are exceedingly hazardous to both humans and the environment, and the necessity to eliminate them from aqueous systems prompts the development of novel materials. In the present study, a UIO-66 (COOH)₂ metal-organic framework (MOF) containing free carboxylic acid groups was post-synthetically modified with L-glutamic acid via the solid-solid reaction route. Pristine and glutamic acid-treated MOF materials were characterized in detail using several physicochemical techniques. Single-ion batch adsorption studies of Pb(II) and Hg(II) ions were carried out using pristine as well as amino acid-modified MOFs. We further examined parameters that influence removal efficiency, such as the initial concentration and contact time. The bare MOF had a higher ion adsorption capacity for Pb(II) (261.87 mg/g) than for Hg(II) ions (10.54 mg/g) at an initial concentration of 150 ppm. In contrast, an increased Hg(II) ion adsorption capacity was observed for the glutamic acid-modified MOF (80.6 mg/g) as compared to the bare MOF. The Hg(II) ion adsorption capacity increased by almost 87% after modification with glutamic acid. Fitting results of isotherm and kinetic data models indicated that the adsorption of Pb(II) on both pristine and glutamic acid-modified MOFs was due to surface complexation of Pb(II) ions with available -COOH groups (pyromellitic acid). Adsorption of Hg(II) on the glutamic acid-modified MOF was attributed to chelation, in which glutamic acid grafted onto the surface of the MOF formed chelates with Hg(II) ions.

• Bulletin of the Korean Chemical Society
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• v.14 no.6
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• pp.687-691
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• 1993

Complexation of $Cd^{2+},\;Pb^{2+}\;and\;Hg^{2+}$ ions with four cryptands were studied by potentiometry and solution calorimetry in various weight percent methanol-aqueous solvent at 25${\circ}$C under $CO_2$free nitrogen atmosphere. The stabilities of the complexes were dependent on the cavity size of macrocycles. The $Hg^{2+}$ ion stability constants are higher than those of $Cd^{2+}\;and\;Pb^{2+}$ ion. All the cryptands formed complexes having 1 : 1 (metal to ligand) mole-ratio except for $Hg^{2+}-L_1$ (cryptand 1,2b: 3,5-benzo-9,14,17-trioxa-1,7-diazabicyclo-(8,5,5) heptadecane) and $Cd^{2+}-L_2$ (cryptand 2,2b: 3,5-benzo-10,13,18,21-tetraoxa-1,7-diazabicyclo (8,5,5) eicosane) complexes. $Hg^{2+}-L_1$ complex was a sandwitch type, and the $Cd^{2+}-L_2$ complex showed two stepwise reactions. Thermodynamic parameters of the $Cd^{2+}-L_2$ complex were $6.08(log\;K_1)$, -7.28 Kcal/mol $({\Delta}H_1)$, and $4.78\;(log\;K_2)$, -4.62 Kcal/mol $({\Delta}H_2)$, respectively, for 1 : 1 and 2: 1 mole-ratio. The sequences of the selectivity were increased in the order of $Hg^{2+}\;>Pb^{2+}\;>Cd^{2+}$ ion for $L_3\;and\;L_4$ macrocycles, and the $L_2$-macrocycle has a selectivity for $Cd^{2+}$ ion relative to $Zn^{2+},\;Ni^{2+},\;Pb^{2+}\;and\;Hg^{2+}$ ions. Thus, it is expected that the $L_2$ can be used as carrier for seperation of the post transition metals by macrocycles-mediated liquid membrane because $L_2$ is not soluble in water, and the difference of stability constants of the metal complexes with $L_2$ are large as compared with the other transition metal complexes. The $^1H\;and\;^{13}C-NMR studies indicated that the nitrogen atoms of cryptands have greater affinity to the post transition metal ions than the oxygen atoms, and that the planarities of the macrocycles were lost by complexation with the metal ions because of the perturbation of ring current of benzene molecule attached to macrocycles and counter-anions.