• Journal of the Korean Chemical Society
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• v.44 no.5
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• pp.403-409
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• 2000

The formation and dissociation rates of $Zn^{2+}$ Complexes with l,4,7,10-tetraaza-13,16-diox-acyclooctadecane-N,N',N",N'"-tetraacetic acid (1), 1,4,7,10-tetraaza-13,16- dioxacyclooctadecane-N,N',N",N'"-tetramethylacetic acid (2), and 1,4,7,10-tetraaza-13,16- dioxacyclooctadecane-N,N',N",N'"-tetrapropionic acid(3) have been measured by stopped-flow and conventional spectrophotometry. Observations were made at 25.0$\pm$0.1 $^{\circ}C$ and at an ionic strength of 0.10 M NaClO$_4$. The formation reactions of $Zn^{2+}$ ion with 1 and 2 took place by the rapid formation of an intermediate complex (ZnH$_3L^+$) in which the $Zn^{2+}$ ion is incompletely coor-dinated. This might then lead to be a final product in the rate-determining step.ln the pH range 4.76-5.76, the diprotonated (H2L2-) form is the kinetically active species despite of its low concentration. The stability con-stants (log$K_{(ZnH$_3$3$L^+$)}$) and specific water-assisted rate constants (koH) of intermediate complexes have been deter-mined from the kinetic data. The dissociation reactions of $Zn^{2+}$ complexes of 1,2, and 3 were investigated with $Cu^{2+}$ ions as a scavenger in acetate buffer. All complexes exhibit acid-independent and acid-catalyzed con-tributions. The effect of buffer and $Cu^{2+}$ concentration on the dissociation rate has also been investigated. The ligand effect on t dissociation rate of $Zn^{2+}$ complexes is discussed in terms of the side-pendant armsand the chelate ring sizes of the ligands.

• Journal of the Korean Chemical Society
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• v.39 no.4
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• pp.244-251
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• 1995

The palladium(II) complexes(where, [Pd(L)2X2], L=isoxazole(isox), 3,5-dimethylisoxazole(3,5-diMeisox), 3-methyl, 5-phenylisoxazole(3-Me, 5-Phisox), and 4-amino, 3,5-dimethylisoxazole(4-ADI); X=Cl, Br] with isoxazole and its derivatives are investigated on antitumor activity by EHMO calculation. It is found that the net charge of the two halogen atoms in trans-isomers are greater than those in cis-ones, indicating that ionic character of Pd-X bond in trans-isomers is greater than that of cis-ones, and so dissociation of Cl- ion is easier than that of Br- ion in aqueous solution in body. Furthermore, it is found that the ${\sigma}MO$ energy of Pd(dx2-y2)-X(px) bond $(E{\sigma}(Pd-X))$ is higher than that of Pd(dx2-y2)-N(px) bond $(E{\sigma}(Pd-N))$ without exception, about all the complexes, and also the $E{\sigma}(Pd-X)$ of trans-isomers is higher than that of cis-isomers. From the above facts, the degree of dissociation in Pd-X bond would be related to antitumor activity. In fact, the linear equation of correlation coefficient 0.96 is fairly established between ${\Delta}E{\sigma}(N-X)(E\sigma(Pd-N)－E{\sigma}(Pd-X))$ and inhibitory activity coefficient, logIA.

• Journal of the Korean Chemical Society
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• v.23 no.4
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• pp.237-242
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• 1979

The equivalent conductances of sodium, potassium, ammonium, tetramethylammonium, triethylammonium, diethylammonium and ethylammonium iodide, and picrate salts of sodium and potassium in ethylene carbonate have been measured at 40.0 $^{\circ}C. The limiting equivalent conductances of the salts have been computed by Fuoss-Onsager-Skinner equation. The limiting ionic equivalent conductances of $Na^+,\;K^+,\;and\;NH^+$ are in order of $Na^+ which is the reverse order of solvation for the ions in any solution, And the order of limiting ionic equivalent conductances for alkylammonium ions is $(C_2H_5)_4N^+<(C_2H_5)_3NH^+<(CH_3)_4N^+<(C_2H_5)_2NH_2^+<(C_2H_5)NH_3^+$ which coincides with the order of mass transfer. From the dissociation constants of the saltss determinde by Fuoss-Kraus method, it is found that ethyene carbonate is a good ionizing solvent for the salts. In addition, Stokes radii and effective fadii of ions have been calculated by Stokes law and Nightingale method, repectively. From the results, it appears tha alkylammonium ions and picrate ion seem to be not solvated, and tha iodide ion is fairly solvated in ethylene carbonate.

• Journal of the Korean Electrochemical Society
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• v.12 no.3
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• pp.203-218
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• 2009

The development of lithium-ion battery (LIB) technologies and their application in the field of large-scale power sources, such as electric vehicles (EVs), hybrid EVs, and plug-in EVs require enhanced reliability and superior safety. The main components of LIBs should withstand to the inevitable heating of batteries during high current flow. Carbonate solvents that contribute to the dissociation of lithium salts are volatile and potentially combustible and can lead to the thermal runaway of batteries at any abuse conditions. Recently, an interest in nonflammable materials is greatly growing as a means for improving battery safety. In this review paper, novel approaches are described for designing highly safe electrolytes in detail. Non-flammability of liquid electrolytes and battery safety can be achieved by replacing flammable organic solvents with thermally resistive materials such as flame-retardants, fluorinated organic solvents, and ionic liquids.

• Analytical Science and Technology
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• v.12 no.5
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• pp.397-402
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• 1999

The open-chain hexadentate $N_6$, ligand containing two pyridyl groups, 1,15-bis(2-pyridyl)-2,6,10,14-tetraazapentadecane (bpyped) has been synthesized as its tetrahydroehloride salt and characterized by EA, IR, NMR, and Mass. Its proton dissociation constants($logK{^n}_H$) and stability constants ($log\;K_{ML}$) for Co(II), Ni(II), Cu(II) and Zn(II) ions were determined at $25^{\circ}C$ and ionic strength 0.10 M($KNO_3$) in aqueous solution by potentiometry and compared with those or analogous $N_6$ ligands contain one or two propylenic spacers, which make six-membered chelate rings, between the aliphatic nitrogen atoms.

• Journal of the Korean Chemical Society
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• v.27 no.3
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• pp.178-182
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• 1983

The conductances of sodium, potassium, ammonium, tetramethylammonium, and tetraethylammonium iodides, picrates(Pic) of sodium and potassium, and tetrabutylammonium tetraphenyl-boride have been measured in ethylene carbonate-acetone mixtures at $25{\circ}C$. The limiting equivalent conductances of the electolytes were computed by Fuoss-Kraus equation and the order was $(C_4H_9)_4NB(ph)_4 at any composition of the mixtures. The dissociation constants of the salts showed that the mixtures are good ionizing solvents for the salts. The order of limiting ionic equivalent conductance, $Na^+, is consistent with exactly the reverse order found for solvation number. Effective solvated radii calibrated by the Nightingale method showed that picrate ion seems to be unsolvated and that iodide ion seems to be solvated to some extent in the mixtures.

• Restorative Dentistry and Endodontics
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• v.26 no.2
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• pp.111-120
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• 2001

Calcium hydroxide pastes is widely used in conventional endodontics. Along with the expanded clinical use of calcium hydroxide, literatures suggest mixing calcium hydroxide with other substance. Among added substances the vehicle plays the most importance role in the overall process because it is directly related with the velocity of ionic dissociation of $Ca^{2+}$ and OH ion. In this study, we evalutated and compared periapical tissue response and root resorption after canal was filled with mixture of saline and calcium hydroxide(Junsei Chemical Co.. Japan) as a aqueous vehicle, Metapaste(Meta Co., Korea) as a viscous vehicle paste, Vitapex(Neo Dental, Japan) as a oily vehicle paste and IRM(Caulk Dentsply, USA) in replantation of rat molar. A total of 31 maxillary first molars of Sprague-Dawley female rats, 30 days old were used. The upper 1st molar was extracted and the mesiobuccal canal was filled with mixture of saline and calcium hydroxide, Metapaste, Vitapex. IRM and then replanted. Rats were sacrificed 3 weeks after replantation. the maxillae were removed. section of 4 micron were cut and stained with hematoxylin-eosin, Apical tissue response were observed under light microscope. The results were as follows: 1. Saline mixing group and Metapaste group were significant different in fibrous capsule width compared to Vitapex group and IRM group(P<0.05). 2. Saline mixing group. Metapaste group. Vitapex group and IRM group did not prevent root resorption and there were no statistical difference. 3. In saline mixing group and Metapaste group. loss of pastes were observed in all samples. From the results of our study. we observed loss of pastes in saline mixing group and Metapaste group because of water soluble property and assumed it was related to inflammation in apical area and sealing ability of material. So, we should study and develop calcium hydroxide vehicle which is easily removed and more stable and because of only 3 weeks observation we need more evaluation in long period.

• Korean Journal of Soil Science and Fertilizer
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• v.37 no.6
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• pp.378-382
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• 2004

Soil pH is an important indicator for soil reactions and crop growth. pH buffer capacity and lime requirements are necessary to comprehend and manage soils well. The characteristics related with soil pH were analyzed and 5 field trials were conducted to elucidate pH buffer capacity of soil and lime requirements and liming factor for Korean acid soils. Soil minerals were analyzed for the soil of 2 years after treating $CaCO_3$ using X-ray diffraction. The amount of neutralized $H^+$ was regarded as the exchangeable aluminium overcoming ${\Delta}pH$, because pH buffer capacity of soil depended on exchangeable aluminium. Lime requirement was somewhat similar to the KCl exchangeable aluminium and it was also affected by the exchangeable cation by added lime. X-ray diffraction analyses revealed that an aluminium dissociation from Korean acid soils was equilibrated with kaolin minerals and changed into anorthite ($CaAl_2Si_2O_8$) by neutralizing with $CaCO_3$. Neutralizing process was composed of changing process of $Al^{3+}$ into $H^+$ and $Al(OH)_4{^-}$ ionic species and of neutralizing $H^+$ by, the amount of which was lime requirement. The fact that anorthite dissociates an aluminium ion higher than kaolinite does enabled to consider a liming factor (LF) the content of exchangeable cation and ${\Delta}pH$, $LF=1.5+0.2{\times}{\sum} Cations{\times}{\Delta}pH$.

• Journal of the Korean Chemical Society
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• v.41 no.6
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• pp.277-283
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• 1997

Platinum(II) complexes(where, $[Pt(L)_2X_2]$; L=isoxazole(isox), 3,5-dimethylisoxazole(3,5-diMeisox), 3-methyl,5-phenylisoxazole(3-Me,5-Phisox), and 4-amino-3,5-dimethylisoxazole(4-ADI); X=Cl, Br) with planar ligands are investigated on antitumor activity by MM2 and EHMO calculations. It was found that, the net atomic charges of the halogen atoms in all of cis-, trans-isomers are greater than that of the nitrogen with planar form, indicating that ionic character of Pt-X bond is greater than that of Pt-N. Also, the ${\sigma}MO$ energy level($E{\sigma}_{(Pt-X)}$) of the interaction between $d_{x2-y2}$ orbital of Pt atom and $p_x$ orbital of X found to be higher than that of between $d_{x2-y2}$ orbital of Pt atom and $p_x$ orbital of N about all the complexes. It is found that bond strength of between Pt and X atom is weaker than that of between Pt and N atom. The ${\sigma}MO$ energy level($E{\sigma}_{(Pt-X)}$) of trans- complexes found to be higher than that of cis- complexes, as a result of bond strength of Pt-X in cis- and trans-complexes, for all the complexes. The degree of dissociation of X atom in Pt-X bond for trans-complexes are related to antitumor activity and the logIA value of inhibitory activity coefficient(IA).

• Analytical Science and Technology
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• v.13 no.2
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• pp.173-178
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• 2000

A new open-chain ligand containing two phenol groups, 1, 14-Bis (2-hydroxybenzyl)-2, 6, 9, 12-tetraazatetradecane(bsated) was synthesized as its tetrahydrochloride salt and characterized by elemental analysis, mass, infrared and NMR. Its proton dissociation constants ($logK^n{_H}$) and stability constants ($logK_{ML}$) toward $Co^{2+}$, $Ni^{2+}$, $Cu^{2+}$ and $Zn^{2+}$ were determined at $25^{\circ}C$ and 0.10M($KNO_3$) ionic strength in aqueous solution by potentiometry. The X-ray structure of its copper (II) complex [Cu(bsated)]$(ClO_4)_2$ was reported: Monoclinic space group $P2_1/n$, $a=17.856(4){\AA}$, $b=17.709(1){\AA}$, $c=8.539(2){\AA}$, $V=2700(2){\AA}$ with Z=4. Electrochemical studies of [Cu(bsated)]$(ClO_4)_2$ complex in dimethyl sulfoxide (DMSO) solution containing tetrabutylammonium perchlorate (supporting electrolyte) were carried out by cyclic voltammograms (CV) and normal pulse voltammetry (NPV).