• Bulletin of the Korean Chemical Society
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• v.31 no.9
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• pp.2483-2487
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• 2010

Pseudo-first-order rate constants ($k_{obsd}$) were measured spectrophotometrically for nucleophilic substitution reactions of 4-nitrophenyl picolinate (6) with alkali metal ethoxides (EtOM, $M^+\;=\;K^+$, $Na^+$ and $Li^+$) in anhydrous ethanol at $25.0{\pm}0.1^{\circ}C$. The plot of $k_{obsd}$ vs. [EtOM] exhibits upward curvature regardless of the nature of $M^+$ ions. However, the plot for the reaction of 6 with EtOK is linear with significantly decreased $k_{obsd}$ values when 18-crown-6-ether (18C6, a complexing agent for $K^+$ ion) is added in the reaction medium. Dissection of $k_{obsd}$ into $k_{EtO^-}$ and $k_{EtOM}$ (i.e., the second-order rate constant for the reaction with dissociated $EtO^-$ and ion-paired EtOM, respectively) has revealed that ion-paired EtOM is 3~17 times more reactive than dissociated $EtO^-$. The reaction has been proposed to proceed through a 5-membered cyclic transition state, in which $M^+$ ion increases the electrophilicity of the reaction site. Interestingly, $Na^+$ ion exhibits the largest catalytic effect. The presence of a nitrogen atom in the pyridine moiety of 6 has been suggested to be responsible for the high $Na^+$ ion selectivity.

• Journal of the Korean Chemical Society
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• v.33 no.1
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• pp.31-36
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• 1989

The second-order rate constants for the nucleophilic substitution reactions of para-substituted benzyl nitrates with para-substituted anilines in acetonitrile were conductometrically determined. Hammett ${\rho}$x and ${\rho}$y values and Bronsted ${\beta}$ values were obtained from these kinetic data. The reactions of Benzyl nitrates with the series of anilines showed linear Hammett plots with negative slopes. For the change of substituents in the benzyl nitrates, nonlinear Hammett plots with a concave upwards curve were obtained. We applied the potential energy surface and the quantum mechanical models in order to examine the transition state variations caused by changes in substituents on the nucleophile and the substrate. The results showed that the reaction was proceeded via the $S_{N}2$-type reaction mechanism in which the extent of bond-formation was greatly changed depending on the property of the substituents in substrate.

• Transactions on Electrical and Electronic Materials
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• v.3 no.3
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• pp.21-24
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• 2002

Two kinds of $Nd_{1+X}Ba_{2-X}Cu_3O_{7-{\delta}}$, the sintering samples and zone melting samples, were heat-treated under pure Ar at 950$^{circ}C$. The substitution of Nd ion for Ba ion in the $Nd_{1+X}Ba_{2-X}Cu_3O_{7-{\delta}}$ before and after the heat treatment was investigated by XRD. In order to confirm the effects of the heat treatment, the Tc and Jc of samples with/without the heat treatment under Ar were comparatively studied. $Nd_{1+X}Ba_{2-X}Cu_3O_{7-{\delta}}$ samples were oxygenated under pure oxygen at $300^{circ}C$. From the XRD pattern it was found that the sample with x<0.4 was transferred from tetragonal phase to orthorhombic phase after the oxygenation, while the sample with x>0.4 did not show the phase transition even after a long time oxygenation. Therefore, the low oxygen partial pressure (Ar+1 % O$_2$) was used for the ambient atmosphere of the zone-melting samples, which could reduce the melting temperature and depress the substitution of Nd for Ba. After the improvement in the zone-melting process, the Jc value was increased to 2 x $10^4$A/$cm^2$ (0 T, 78 K). The particle orientation and the structure of zone-melted NdBaCuO were studied by the XRD and SEM analysis.

• Korean Journal of Materials Research
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• v.29 no.9
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• pp.559-566
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• 2019

$Lu(Nb,Ta)O_4:Eu^{3+}$ powders are synthesized by a solid-state reaction process using LiCl and $Li_2SO_4$ fluxes. The photoluminescence (PL) excitation spectra of the synthesized powders consist of broad bands at approximately 270 nm and sharp peaks in the near ultraviolet region, which are assigned to the $Nb^{5+}-O^{2-}$ charge transfer of $[NbO_4]^{3-}$ niobates and the f-f transition of $Eu^{3+}$, respectively. The PL emission spectra exhibit red peaks assigned to the $^5D_0{\rightarrow}^7F_J$ transitions of $Eu^{3+}$. The strongest peak is obtained at 614 nm ($^5D_0{\rightarrow}^7F_2$), indicating that the $Eu^{3+}$ ions are incorporated into the $Lu^{3+}$ asymmetric sites. The addition of fluxes causes the increase in emission intensity, and $Li_2SO_4$ flux is more effective for enhancement in emission intensity than is LiCl flux. The substitution of $Ta^{5+}$ for $Nb^{5+}$ results in an increase or decrease in the emission intensity of $LuNb_{1-x}Ta_xO_4:Eu^{3+}$ powders, depending on amount and kind of flux. The findings are explained using particle morphology, modification of the $[NbO_4]^{3-}$ structure, formation of substructure of $LuTaO_4$, and change in the crystal field surrounding the $Eu^{3+}$ ions.

• Journal of the Korean Ceramic Society
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• v.40 no.1
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• pp.37-45
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• 2003

The dielectric and sintering characteristics of composites made by substituting Ca ion to Ba-site and Zr ion to Ti site in $(Ba{1-x}Ca_x)(Ti{0.96-yZr_ySn_{0.04})O_3$ $(0.15{\leq}x{\leq}0.20,\;0.09{\leq}y{\leq}0.14)$ were investigated. As the content of Ca was more than 15 mol%, composite was formed by precipitating the second phase whose main element was $CaTiO_3$ and the fraction of the second phase was increased. The curie temperature of composites was depended on Ca concentration, $-1.7^{\circ}C$ per mol% and the maximum dielectric constant of composite was decreased by the rate of 200/mol%. The substitution of Zr ion decreased the curie temperature by the rate of $10^{\circ}C$ per mol% and the maximum dielectric constant was decreased by 217/mol% due to the increase of diffuse phase transition. The density and insulation breakdown characteristics were improved by suppressing the abnormal grain growth due to the increase of second phase. We developed the composition of Y5U (EIA standard) condenser which had high breakdown voltage and dielectric constant by controlling diffuse phase transition by the addition of Zr ion into composite.

• Journal of the Korean Crystal Growth and Crystal Technology
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• v.7 no.2
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• pp.253-258
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• 1997

The characteristics of crystal structure and phase transition with dopants ($Nb_2O_5$= 0.1~0.4 mol% and $Y_2O_3$ : 0.2~0.4 mol%) on the PTCR $BaTiO_3$ system were investigated. In the case of $Nb_2O_5$ additive, the lattice parameter of PTCR $BaTiO_3$ was changed linearly with the increasement of $Nb_2O_5$ which substituted B-site of BaTiO$_3$ and the lattice parameter of c-axis decreased abruptly at 0.3 mol%. These phenonmena were assumed to originate from the distortion of octahedron and we could confirm that the change of lattice parameter accorded with the characteristics of the phase transition temperature. $Y^{3+}$ ions substituted both of A- and B-site until the 0.3 mol% addition, but $Y^{3+}$ substitution preferred A- to B-site above 0.3 mol%. This was affirmed by the variation ,of lattice parameter and the characteristics of phase transition. It also was found that $Y^{3+}$ions in the A-site substituted both of $Ba^{2＋}$ and $Ca^{2＋}$ ions with equal ratio by Rietveld method.

• Molecules and Cells
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• v.19 no.1
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• pp.114-123
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• 2005

Nitropyrene, the predominant nitropolycyclic hydrocarbon found in diesel exhaust, is a mutagenic and tumorigenic environmental pollutant that requires metabolic activation via nitroreduction and ring oxidation. In order to determine the role of ring oxidation in the mutagenicity of 1-nitropyrene, its oxidative metabolites, 1-nitropyrene 4,5-oxide and 1-nitropyrene 9,10-oxide, were synthesized and their mutation spectra were determined in the coding region of hprt gene of CHO cells by a PCR amplification of reverse-transcribed hprt mRNA, followed by a DNA sequence analysis. A comparison of the two metabolites for mutation frequencies showed that 1-nitropyrene 9,10-oxide was 2-times higher than 1-nitropyrene 4,5-oxide. The mutation spectrum for 1-nitropyrene 4,5-oxide was base substitutions (33/49), one base deletions (11/49) and exon deletions (5/49). In the case of 1-nitropyrene 9,10-oxide, base substitutions (27/50), one base deletions (15/50), and exon deletions (8/50) were observed. Base substitutions were distributed randomly throughout the hprt gene. The majority of the base substitutions in mutant from 1-nitropyrene 4,5-oxide treated cells were $A{\rightarrow}G$ transition (15/33) and $G{\rightarrow}A$ transition (8/33). The predominant base substitution, $A{\rightarrow}G$ transition (11/27) and $G{\rightarrow}A$ transition (8/27), were also observed in mutant from 1-nitropyrene 9,10-oxide treated cells. The mutation at the site of adenine and guanine was consistent with the previous results, where the sites of DNA adduct formed by these compounds were predominant at the sites of purines. A comparison of the mutational patterns between 1-nitropyrene 4,5-oxide and 1-nitropyrene 9,10-oxide showed that there were no significant differences in the overall mutational spectrum. These results indicate that each oxidative metabolite exhibits an equal contribution to the mutagenicity of 1-nitropyrene, and ring oxidation of 1-nitropyrene is an important metabolic pathway to the formation of significant lethal DNA lesions.

• Journal of the Korean Magnetics Society
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• v.24 no.2
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• pp.46-50
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• 2014

The crystallographic properties and cationic distribution of $M_{0.2}Fe_{2.8}O_4$ (M =Mn, Ni, Cu) and $Fe_3O_4$ thin films prepared by sol-gel method have been investigated by X-ray diffraction (XRD) and conversion electron M$\ddot{o}$ssbauer spectroscopy (CEMS). The ionic valence, preferred site, and hyperfine field of Fe ions of the ferrites could be obtained by analyzing the CEMS spectra. The $M_{0.2}Fe_{2.8}O_4$ films were found to maintain cubic spinel structure as in $Fe_3O_4$ with the lattice constant slightly decreased for Ni substitution and increased for Mn and Cu substitution from that of $Fe_3O_4$. Analyses on the CEMS data indicate that $Mn^{2+}$ and $Ni^{2+}$ ions substitute octahedral $Fe^{2+}$ sites mostly, while $Cu^{2+}$ ions substitute both the octahedral and tetrahedral sites. The observed intensity ratio $A_B/A_A$ of the CEMS subspectra of the samples exhibited difference from the theoretical value. It is interpreted as due to the effect of the M substitution for A and B on the Debye temperature of the site. The relative line-broadening of the B-site CEMS subspectra can be explained by the dispersion of magnetic hyperfine fields due to random distribution of M cations in the B sites.

• Journal of Powder Materials
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• v.9 no.6
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• pp.381-393
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• 2002

Recent developments in nanocrystalline and nanocomposite rare earth-transition metal magnets are reviewed and emphasis is placed on research work at IFW Dresden. Principal synthesis methods include high energy ball milling, melt spinning, mold casting and hydrogen assisted methods such as reactive milling and hydrogenation-disproportionation-desorption-recombination. These techniques are applied to NdFeB-, PrFeB- and SmCo-type systems with the aim to produce high remanence magnets with high coercivity. Concepts of maximizing the energy density in nanostructured magnets by either inducing a texture via anisotropic HDDR or hot deformation or enhancing the remanence via magnetic exchange coupling are evaluated. With respect to high temperature applications melt spun $Sm(Co_{0.74}Fe_{0.1}Cu_{0.12}Zr_{0.04})_{7.5}$ ribbons were prepared, which showed coercivities of up to 0.53 T at 50$0^{\circ}C$. Partially amorphous $Nd_{60}Fe_xCo_{30-x}Al_{10}(0{\leq}x{\leq}30)$ alloys were prepared by copper mold casting. The effect of transition metal content on the glass-forming ability and the magnetic properties was investigated. The $Nd_{60}Co_{30}Al_{10}$ alloy exhibits an amorphous structure shown by the corresponding diffraction pattern. A small substitution of Co by 2.5 at.% Fe results In the formation of Fe-rich crystallites embedded in the Nd-rich amorphous matrix. The Fe-rich crystallites show hard magnetic behaviour at room temperature with a coercivity value of about 0.4 T, relatively low saturation magnetization and a Curie temperature of 500 K.

• Bulletin of the Korean Chemical Society
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• v.35 no.6
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• pp.1749-1753
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• 2014

Pseudo-first-order rate constants ($k_{obsd}$) have been measured spectrophotometrically for the nucleophilic substitution reaction of Y-substituted-phenyl picolinates (7a-f) with potassium ethoxide (EtOK) in anhydrous ethanol at $25.0{\pm}0.1^{\circ}C$. The plot of $k_{obsd}$ vs. [EtOK] curves upward while the plot of $k_{obsd}/[EtO^-]_{eq}$ vs. $[EtO^-]_{eq}$ is linear with a positive intercept in all cases. Dissection of $k_{obsd}$ into $k_{EtO^-}$ and $k_{EtOK}$ (i.e., the second-order rate constants for the reactions with the dissociated $EtO^-$ ion and ion-paired EtOK, respectively) has revealed that the ion-paired EtOK is more reactive than the dissociated $EtO^-$. The ${\sigma}^{\circ}$ constants result in a much better Hammett correlation than ${\sigma}^-$ constants, indicating that the reaction proceeds through a stepwise mechanism in which departure of the leaving group occurs after the rate-determining step (RDS). $K^+$ ion catalyzes the reaction by increasing the electrophilicity of the reaction center through formation of a cyclic transition state (TS). The catalytic effect decreases as the substituent Y becomes a stronger electron-withdrawing group (EWG). Development of a positive charge on the N atom of the picolinyl moiety through resonance interactions is responsible for the decreasing $K^+$ ion catalysis.