• Journal of the Korean Magnetics Society
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• v.7 no.4
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• pp.196-204
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• 1997

In order to study the effect of substituted $Al^{3+}$ of goethite, which was collected from Shinpyeongli in Cheju Island, we used X-ray diffractometer and Mossbauer spectrometer. In X-ray diffraction analysis, the X-ray diffraction peaks of goethite are not detected due to the high substituted Al contents of goethite. Isomer shifts indicated that the valence of Fe ions is almost oxidized trivalent of high spin state. It is believed that the contents of substituted diamagnetic $Al^{3+}$ for $Fe^{3+}$ is about 15.5 mol%. It seems that Neel temperature and saturated magnetic hyperfine field of the clay goethite are about 250 K and 498 kOe, respectively. For the temperature lower than Neel temperature, quadrupole splittings of the clay goethite are greatly influenced by $Al^{3+}$ substitution. It is believed that the high decrease of Neel temperature and magnetic hyperfine field of the clay goethite results from the magnetic dilution produced by substituting the diamagnetic $Al^{3+}$/TEX> for $Fe^{3+}$.

• Journal of the Korean Chemical Society
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• v.46 no.5
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• pp.412-429
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• 2002

Chiral separation of gemifloxacin, an quinolone antibacterial agent, using (+)-(18-crown-6)-tetracar-boxylic acid $(18C6H_4)$ as a chiral selector was performed by capillary electrophoresis (CE). Direct analysis of quinolone antibacterial agent in body fluid is beneficial in terms of fast analysis time, multicomponent analysis. However, high con-centration of sodium ion in body fluid can prevent gemifloxacin from interacting with $18C6H_4$ since sodium ion has high affinity with $18C6H_4$ due to the strong charge interaction. Ethylenediaminetetraacetic acid (EDTA), as a chelating ligand, was added in the running buffer in order to reduce the interaction between sodium ion and the chiral selector. Increased separation efficiency and reduced migration time were observed while sodium ion exists in the sample solution at the concentration up to 150 mM.

• Journal of the Korean Magnetics Society
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• v.8 no.3
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• pp.118-124
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• 1998

$Ni_{0.65}Zn_{0.35}Cu_{0.1}Fe{1.9}O_4$ has been studied with Mossbauer spectroscopy and X-ray diffraction. The crystal structure is found to be a cubic spinel with the lattice constant $a_0=8.390{\AA}$. Mossbauer spectra of $Ni_{0.65}Zn_{0.35}Cu_{0.1}Fe{1.9}O_4$ has been taken at various temperatures ranging from 12 K to 705 K. The isomer shift indicates that iron ions are ferric at tetrahedral [A] and octahedral sites [B], respectively. The Neel temperature is determined to be $T_N=705\;K$. As the temperature increases toward $T_N$ a systematic line broadening effect in the Mossbauer spectrum is observed and interpreted to originate from different temperature dependencies of the magnetic hyperfine fields at various iron sites. The quadrupole splitting just on $T_N$ is 0.41 mm/s whereas the quadrupole shift below $T_N$ vanishes. This implies that the orientation of the magnetic hyperfine field with respect to be principal axes of the electric field gradient is random.

• Journal of the Korean Magnetics Society
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• v.24 no.2
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• pp.41-45
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• 2014

By M$\ddot{o}$ssbauer spectroscopy and x-ray measurement $(Fe_{0.95}Ni_{0.05})_7Se_8$ has been studied. The crystal structure of $(Fe_{0.95}Ni_{0.05})_7Se_8$ is found to be a triclinic superstructure of the NiAs sturcture while $Fe_7Se_8$ has a orthohexagonal superstructure. Abrupt changes of quadrupole shifts near 125 K for $(Fe_{0.95}Ni_{0.05})_7Se_8$ suggests that the spin-rotation transition proceeds abruptly, in contrast with the gradual transition reported for $Fe_7Se_8$ with a triclinic superstructure. Isomer shifts indicate a ferrous state for the iron ions at all four states.

• Journal of the Korean Magnetics Society
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• v.16 no.5
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• pp.245-248
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• 2006

[ $Tb_{3-x}Bi_xFe_5O_{12}$ ] has been studied by x-ray diffraction (XRD), vibrating sample magnetometer, $M\"{o}ssbauer$ spectroscopy. The crystal structures were found to be a cubic garnet structure with space group Ia3d. The lattice constants increase linearly with increasing bismuth concentration. With increase of bismuth substitution, the $N\'{e}el$ temperature increases but the compensation temperature decreases. We have observed the negative magnetization in Bi-TbIG system which has not been reported in garnet systems. $M\"{o}ssbauer$ spectra were measured at various temperatures from 4.2 K to $N\'{e}el$ temperature. The isomer shifts at room temperature are ${\sim}0.26mm/s$ which is consistent with ferric state.

• Analytical Science and Technology
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• v.11 no.3
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• pp.179-188
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• 1998

The capacity factor of fifteen phenol derivatives was determined with respect to the concentration of ${\alpha}$- or ${\beta}$-cyclodextrin [CD], the type as well as the content of organic solvent in the mobile phase, and the temperature. The effect of the inclusion complex formation between solutes and ${\alpha}$- or ${\beta}$-cyclodextrin on their retention and selectivity has been investigated. The inclusion effect of ${\beta}$-cyclodextrin was the most effective in aqueous methanol, whereas only a poor effect was observed in aqueous tetrahydrofuran and aqueous acetonitrile. A plot of the reciprocal of the capacity factor against $[CD]_T$ gives a straight line and the dissociation constant, $K_D$ of the inclusion complex can be calculated from the slope. It was possible to estimate the $k_D$ values in 100% water from a linear plot of $pK_D$ vs. water content in the solution by extrapolation. The separation factor, ${\alpha}$, of two compounds has been found to be affected not only by the $[CD]_T$ but also by their $K_D$ values. Under optimum conditions, some mixtures of phenol derivatives were able to separate successfully.

• Analytical Science and Technology
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• v.7 no.2
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• pp.213-224
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• 1994

Several isotopomers of cyclooctanone were prepared by selective deuterium substitution. Intrinsic isotope effects on $^{13}C$ NMR chemical shifts of these isotopomers were investigated systematically at low temperature. These istope effects were discussed in relation to the preferred boat-chair conformation of cyclooctanone. Deuterium isotope effects on NMR chemical shifts have been known for a long time. Especially in a conformationally mobile molecule, isotope perturbation could affect NMR signals through a combination of isotope effects on equilibria and intrinsic effects. The distinction between intrinsic and nonintrinsic effects is quite difficult at ambient temperature due to involvement of both equilibrium and intrinsic isotope effects. However if equilibria between possible conformers of cyclooctanone are slowed down enough on the NMR time scale by lowering temperature, it should be possible to measure intrinsic isotope shifts from the separated signals at low temperature. $^{13}C$ NMR has been successfully utilized in the study on molecular conformation in solution when one deals with stable conformers or molecules were rapid interconversion occurs at ambient temperature. The study of dynamic processes in general requires analysis of spectra at several temperature. Anet et al. did $^1H$ NMR study of cyclooctanone at low temperature to freeze out a stable conformation, but were not able initially to deduce which conformation was stable because of the complexity of alkyl region in the $^1H$ NMR spectrum. They also reported the $^1H$ and $^{13}C$ NMR spectra of the $C_9-C_{16}$ cycloalkanones with changing temperature from $-80^{\circ}C$ to $-170^{\circ}C$, but they did not report a variable temperature $^{13}C$ NMR study of cyclooctanone. For the analysis of the intrinsic isotope effect with relation to cylooctanone conformation, $^{13}C$ NMR spectra are obtained in the present work at low temperatures (up to $-150^{\circ}C$) in order to find the chemical shifts at the temperature at which the dynamic process can be "frozen-out" on the NMR time scale and cyclooctanone can be observed as a stable conformation. Both the ring inversion and pseudorotational processes must be "frozen-out" in order to see separate resonances for all eight carbons in cyclooctanone. In contrast to $^1H$ spectra, slowing down just the ring inversion process has no apparent effects on the $^{13}C$ spectra because exchange of environments within the pairs of methylene carbons can still occur by the pseudorotational process. Several isotopomers of cyclooctanone were prepared by selective deuterium substitution (fig. 1) : complete deuterium labeling at C-2 and C-8 positions gave cyclooctanone-2, 2, 8, $8-D_4$ : complete labeling at C-2 and C-7 positions afforded the 2, 2, 7, $7-D_4$ isotopomer : di-deuteration at C-3 gave the 3, $3-D_2$ isotopomer : mono-deuteration provided cyclooctanone-2-D, 4-D and 5-D isotopomers : and partial deuteration on the C-2 and C-8 position, with a chiral and difunctional case catalyst, gave the trans-2, $8-D_2$ isotopomer. These isotopomer were investigated systematically in relation with cyclooctanone conformation and intrinsic isotope effects on $^{13}C$ NMR chemical shifts at low temperature. The determination of the intrinsic effects could help in the analysis of the more complex effects at higher temperature. For quantitative analysis of intrinsic isotope effects, the $^{13}C$ NMR spectrum has been obtained for a mixture of the labeled and unlabeled compounds because the signal separations are very small.

• Analytical Science and Technology
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• v.5 no.3
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• pp.239-247
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• 1992

The complexations and selectivities of the 10 species of mono- and dimethylsubstituted anilinium ions with 18-crown-6 in methanol are examined at dropping mercury electrode. The stability constants of these complexes varies drastically due to the steric hindrance by the positions and numbers of methyl groups. And the analyses of the isomeric mixtures of methylanilinium, which are impossible to detect due to the overlapped peaks in normal conditions, were also accomplished by the additions of 18-crown-6 as the supporting complexing agent using the selective complexations by the steric hindrance effects. As results in case of the difference of stability, ${\Delta}log\;K$ were about 0.7~1.3, it was possible to confirm the existence of two species qualitatively. Otherwise when ${\Delta}log\;K$ were large than 1.6, the quantitative determinations of each species could be accomplished sucessfully. From these results it is deduced that the selective recongnition of the positions and numbers of methyl groups as the steric hindrance in anililniums by 18-crown-6 cause the large variation of the magnitudes of negative shift of reduction waves for guest ions in mixtures.

• Journal of the Korean Magnetics Society
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• v.10 no.5
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• pp.220-224
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• 2000

Ultra-fine $Co_{1+x}$F $e_{2-}$2x/ $Ti_{x}$ $O_4$ferrite powders have been prepared by the sol-gel method. The crystallographic and magnetic properties of the sample have been investigated by means of x-ray diffraction, Mossbauer spetroscopy and vibrating sample magnetometry. The formation of nano crystallized particles is confirmed. The x-ray diffractions of all samples with various compositions clearly indicate the presence of spinel structure. The Mossbauer spectra could be fitted as the superposition of two sextets due to F $e^{3+}$ A-site and B-site. The IS and QS values nearly constant with substituted Co-Ti contents, whereas $H_{hf}$ of B-site decreases with increasing Co-Ti substitution in $Co_{1+x}$F $e_{2-}$2x/ $Ti_{x}$ $O_4$. The magnetic behaviour of powders shows that the saturation magnetization and the coercivity decrease with increasing x in $Co_{1+x}$F $e_{2-}$2x/ $Ti_{x}$ $O_4$.$.X>.

• Journal of the Korean Chemical Society
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• v.55 no.3
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• pp.392-399
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• 2011

Two conformations of benzoic acid derivatives ($NH_2$, OH, H, F, Cl, CN, NO, $NO_2$) have been investigated at MP2, DFT and HF level using the 6-311++G(d,p) basis set. It was found that the cis isomers are more stable. Hydrogen bonding formation of benzoic acids has been estimated from stabilization energies. The calculated hydrogen-bonding energies of dimers showed a cooperative interaction in the cyclic ones. It was found that an electron-releasing group (ERG) into the phenyl rings resulted in the formation of more stable hydrogen bonding. Red shift of O-H bond was found from -565.3 to -589.3 for dimers. The natural bond orbital (NBO) analysis was applied to characterize nature of the interaction.