• Journal of the Korean Chemical Society
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• v.25 no.2
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• pp.75-84
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• 1981

Ultraviolet spectrophotometric investigations have been carried out on the systems of mesitylene with iodine, bromine, iodine monochloride and iodine monobromide in carbon tetrachloride. The results reveal the formation of the charge transfer complexes of the type, $C_6H_3(CH_3)_3{\cdot}X_2$ or $C_6H_3(CH_3)_3{\cdot}IX$ (X denotes halogen atoms). The equilibrium constants were obtained in consideration of that absorption maxima due to the formation of the charge transfer complexes shift to blue with the increasing temperatures. Thermodynamic parameters, ${\Delta}H$, ${\Delta}G$ and ${\Delta}S$ for the formation of the charge transfer complexes were calculated from these values. These results indicate that the relative stabilities of the mesitylene complexes at each temperature decrease in the order, ICl > IBr > $I_2$ > $Br_2$. This order may be a measure of their relative acidities toward mesitylene, which is explaned in terms of the relative polarizabilities of halogen molecules and the relative electronegativities of halogen atoms. These results combined with previous study of this series indicated that the relative stabilities of the polymethylbenzene complexes with iodine increase in the order Benzene < Toluene < Xylene < Mesitylene Thus, analysis of these findings is discussed.

• Journal of the Korea Academia-Industrial cooperation Society
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• v.16 no.11
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• pp.7555-7563
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• 2015

The complex formation from Zn(II) ion and 2-(2-hydroxyethylamino)-2-(hydroxymethyl)-1,3-propanediol (Monotris), Bis(2-hydroxyethyl)imino-tris(hydroxymethyl)methane(Bistris) in aqueous solution at $25^{\circ}C$ and at an ionic strength of 0.10 M have been studied potentiometrically. For the Zn(II)-Monotris system, in the Monotris (L) complex $ZnL^{2+}$, one of the hydroxyl oxygen atoms as well as the amine nitrogen of the ligand are coordinated. In basic media, the coordinated hydroxyl group is deprotonated. For the Zn(II)-Bistris system, in the Bistris(L) complex $ZnL^{2+}$, two of the hydroxyl oxygen atoms as well as the amine nitrogen of the ligand are coordinated. In basic media, one of the coordinated hydroxyl groups is deprotonated. In very high basic media, an additional hydroxyl group undergoes deprotonation. The equilibrium constants for the formation of $ZnL^{2+}$, $ZnLH_{-1}{^+}$, $ZnLH_{-2}$, $Zn_2L_2H_{-2}{^{2+}}$ and $Zn_2L_2H_{-3}{^+}$ have been determined.

• Applied Biological Chemistry
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• v.17 no.2
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• pp.143-148
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• 1974

The interaction of the carcinogenic mycotoxin, Aflatoxin $B_1$, with the electron-donating molecule, benzene, was studied spectrophotometrically. The formation of charge-transfer complex between Aflatoxin $B_1$ and benzene in the presence of zinc chloride was observed and the apparent equilibrium constant of this charge-transfer complex was found to be 0.198 (liter $mole^{-1}$). It is assumed that, as the result of this study, some charge-transfer complexes could be formed between the weak electron-accepting Aflatoxin $B_1$ and strong electron-donating molecules, and the spectral changes occurred in the binding of Aflatoxin $B_1$ with proteins or DNA is attributed to the existence of charge-transfer type interaction.

• Journal of the Korean Chemical Society
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• v.36 no.6
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• pp.840-848
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• 1992

An ionizable macrocyclic ligand, diaza-18-crown-6-diisopropionic acid(K22DAP) has been synthesized. Protonation constants of this compound and stability constants with some lanthanides were determined by potentiometric titration method. The protonation constants are log$K_1$ = 9.05, log$K_2$ = 8.37, log$K_3$ = 1.88 and log$K_4$ = 0.99. The logarithmic values of stability constants with La(III), Nd(III), Gd(III) and Lu(III) are 11.14, 11.43, 11.74 and 10.88 respectively. Extraction behavior of Ln(III) ion was investigated using TTA(thenoyltrifluoroacetone) as extractant in the presence of K22DAP as macrocyclic ionophore. It was observed that Ln(K22DAP)TTA is the dominating species in aqueous complexes of La(III) and Nd(III).

• Journal of the Korean Chemical Society
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• v.53 no.6
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• pp.693-703
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• 2009

The complex formation of anti-inflamatory drug piroxicam (PX, 4-hydroxy-2-methyl-N-2--pridyl-2H-1,2-benzothiazine-3-carboxadiamide-1,1-dioxide) with transition metal ions Co(II), Ni(II), Cu(II) and Zn(II) in methanol(MeOH)/water binary mixtures were studied by spectrophotometric method at 25$^{\circ}C$, constant pH = 5.0 and I = 0.1 M. The computer program SQUAD was used to extract the desired information from the spectral data. The outputs of the fitting processes were stability constants, standard deviations of the estimated stability constants, concentration distribution diagrams and spectral profiles of all species. The sequence of the stability constants of PX complexes with Co(II), Ni(II), Cu(II) and Zn(II) follow the Cu(II) > Co(II) > Ni(II) ${\approx}$ Zn(II) order. This may be due to different geometry tendencies of these metal ions. The acidity constants of the PX were also determined under above condition from its absorption spectra at different pH values. The computer program DATAN was used for determination of acidity constants of PX. The validity of the obtained acidity constants was checked by a well known computer program SPECFIT/32. The effects of the different parameters like solvent nature, cations characteristics on the stability and acidity constants were thoroughly discussed.

• Nuclear Engineering and Technology
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• v.27 no.1
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• pp.18-24
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• 1995

Characteristics of poly(vinyl alcohol)-poly(methacrylic acid) system (PVA.-PMAA system) for fixation of radioactive contaminant on sand were studied. Dissociation of carboxyl group in PMAA was found to be suppressed by PVA Permeability of sand layer treated with PVA-PMAA solution is directly proportional to the PMAA concentration when the ［PMAA］ is below 0.082 M and the empirical proportional constant (k) is -8.95$\times$10￣$^4$cm$^{5}$ /mole. The change of permeability can be explained by the formation of an intermacromolecular complex between PVA and PMAA The polymer bridge formed on a sand surface combines sand yams more firmly. The PVA-PMAA system is more effective than the PVA system for the fixation of deposited condensational radionuclides.

• Journal of the Korean Chemical Society
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• v.37 no.5
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• pp.491-495
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• 1993

Synthesis of polymer-supported azacrown ether ion exchanger, {(4,5): (13,14)-dibenzo-6,9,12-trioxa-3,15,21-triazazabicyclo[15.3.1]heneicosa-1(21),17,19-triene-2,16-dione : DBPDA ion exchanger}, and its ion binding ability to alkali metal $(Li^+,\;Na^+,\;K^+)$ picrates were studied. The binding constants $(K_b)$ of DBPDA ion exchanger to the alkali metal picrates in ether type solvents were obtained by spectrophotometry. Binding constants of alkali metal ions were in the order to Li < Na < K, and alkali metal ions were formed 1 : 1 complexes with ligands of DBPDA ion exchanger. Also, $K_b$ was found to depend on the variables such as solvent and temperature. The binding constants for the complexes were obtained in the ranges of $2{\times}10^3{\sim}4{\times}10^4M^{-1}$. In order to obtain the enthalpy (${\Delta}$H) and entropy changes (${\Delta}$S)n the complexation process, Kb were plotted against the temperature in the ranges of 10∼40$^{\circ}C$ according to the van't Hoff theory. Enthalphy and entropy changes were found in the ranges of -2.71∼-3.79 kcal/mol, and -16.52∼-20.57 eu, respectively.

• Journal of the Korean Chemical Society
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• v.32 no.6
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• pp.528-535
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• 1988

The rates of oxygen ring formation of $[Mo_2O_3(Ox)_2(OxH)_2(NCS)_2]$ have been investigated spectrophotometric method in binary aqueous mixtures. Temperature was $20^{\circ}C$ to $40^{\circ}C$ and pressure was varied up to 1500 bar. The observed rate constants are increased by hydrogen ion and decreased by thiocyanate. The more increasing of co-solvents dielectric constant, the more stable intermediate is formed. The observed rate constant is given by, $k_{obs}^{-1} = k^{-1} (1 + K^{-1}[H_2O]^{-1}) All activation parameters are positive values. The oxygen ring formation of [Mo_2O_3(Ox)_2(OxH)_2(NCS)_2]$ is believed to be a interchange-dissociative mechanism..

• Journal of the Korean Chemical Society
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• v.38 no.1
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• pp.41-49
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• 1994

Exchange reaction mechanisms of the Pb(II) ion for the complexes between Pb(II) ion and nitrogen oxygen donor macrocyclic ligands, such as 1,13-diaza-3,4 : $1011-dibenzo-59-dioxacyclohexa-decane(NtnOtnH_4)$, 1,15-diaza-3,4 : $1213-dibenzo-5811-trioxacycloheptadecane(NenOdienH_4)$, and 1,15-diaza-3,4 : $1213-dibenzo-5811-trioxacyclooctadecane(NtnOdienH_4)$, were studied by $^{207}Pb-NMR$ spectroscopy in N,N'-dimethylformamide(DMF) solutions. The associative-dissociative mechanism dominated in $NtnOtnH_4-Pb(II)$ and $NtnOdienH_4-Pb(II)$ system. For $NenOdienH_4-Pb(II)$ system, the bimolecular exchange mechanism prevailed below $-5^{\circ}C$, and both bimolecular exchange and associative-dissociative mechanism dominated above $+5^{\circ}C.$ The order of activation energies for dissociation was $NtnOdienH_4\;<\;NtnOtnH_4\;<\;NenOdienH_4$ which was reverse to the order of stabilities.

• Journal of the Korea Academia-Industrial cooperation Society
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• v.14 no.11
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• pp.6000-6007
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• 2013

Cr(VI)-heterocyclic complex[Cr(VI)-isoquinoline] was synthesized by the reaction between of heterocyclic compound(isoquinoline) and chromium trioxide, and characterized by IR and ICP analysis. The oxidation of benzyl alcohol using Cr(VI)-isoquinoline in various solvents showed that the reactivity increased with the increase of the dielectric constant(${\varepsilon}$), in the order : cyclohexene$CH_3$, m-Br, m-$NO_2$). Electron- donating substituents accelerated the reaction, whereas electron acceptor groups retarded the reaction. The Hammett reaction constant(${\rho}$) was -0.69(308K). The observed experimental data have been ratiolized. The hydride ion transfer causes the prior formation of a chromate ester in the rate-determining step.