• Bulletin of the Korean Chemical Society
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• v.15 no.8
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• pp.654-658
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• 1994

Rate constants have been measured spectrophotometrically for the nucleophilic substitution reactions of p-and m-nitrophenyl 2-furoates (4 and 5, respectively) with alkali metal ethoxides ($EtO^-M^+$) in absolute ethanol at 25$^{\circ}$C. The reactivity of $EtO^-M^+$ toward 4 is in the order $EtO^-K^+$ > $EtO^-Na^+$> $EtO^-Li^+$ > $EtO^-K^+$+ 18-crown-6 ether. This is further confirmed by an ion pairing treatment method. The present result indicates that (1) ion paired $EtO^-M^+$ is more reactive than dissociated $EtO^-$ ; (2) the alkali metal ions ($K^+,\;Na^+,\;Li^+$) behave as a catalyst; (3) the catalytic effect increases with increasing the size of the metal ion. A similar result has been obtained for the reaction of 5, however, the catalytic effects shown by the metal ions are more significant in the reaction of 5 than in that of 4.

• Journal of the Korean Magnetics Society
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• v.19 no.2
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• pp.43-46
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• 2009

The magnetic and structural properties of the (8, 0) BN nanotubes with transition metals (TM) of Fe, Co, or Ni substitution for B or N were investigated using a first-principles calculation. It was found that TM substitution makes the cross section being distorted and the bond length TM-B or TM-N being longer than that of the original B-N one. The magnetic moment is larger for the TM substitution for B than one for N, and it is mainly due to the 3d electrons of TM atoms.

• Journal of the Korean Ceramic Society
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• v.40 no.8
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• pp.725-729
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• 2003

The fluorine doping along with heavy metal oxides remarkably raised the $^3$H$_4$ lifetime and the quantum efficiency in Tm$^{3+}$-doped silicate glasses. 29 mol% of fluorine substitution for oxygen in 70SiO$_2$-15Pbo-12ZnO-3KO$_{1}$2/ glass raised $^3$H$_4$ lifetime to 193 $mutextrm{s}$. Refractive indices were raised by heavy metal oxide substitution, but hardly changed by fluorine substitution. The fluorine doping changed the local structure around Tm$^{3+}$ions, then low energy vibrations related to fluorine are considered to largely reduce the multi-phonon relaxation rates in the oxyfluoride silicate glasses. The $^3$H$_4$ lifetimes and absorption and emission spectra of Tm$^{3+}$doped silicate and oxyfluoride silicate glasses are reported, and Judd-Ofelt calculation results are discussed in this paper.

• Journal of the Korean Crystal Growth and Crystal Technology
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• v.8 no.1
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• pp.160-168
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• 1998

In order to investigate the color variation and the solubility limit in wagnerites by metal ion substitution, wagnerite ($A_2XO_4Z$) was synthesized and then, substituted by coloring metal ions, especially $CO^{2+},Ni^{2+}$ and $Cu^{2+}$ ions. When calcium was replaced with Mg, Co, Ni and Cu divalent ions, solid solutions were formed with a limited solubility. Single phase wagnerites were synthesized by the substitution of Ca with Mg and Co, and their colors were white and purple, respectively. Substitutions with $Li^+$ were succeeded in the specific composition and the substitution of vanadium for $X^{5+}$ were attempted, resulting in the wagnerites of dark purple, dark gold and light yellow colors. The substitution of chlorine was, also, attmepted for the fluorine site.

• Proceedings of the Petrological Society of Korea Conference
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• 2009.05a
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• pp.8-8
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• 2009

• Bulletin of the Korean Chemical Society
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• v.31 no.6
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• pp.1573-1576
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• 2010

Bacillus subtilis PerR is a metal-dependent peroxide-sensing transcription factor which uses metal-catalyzed histidine oxidation for peroxide-sensing. PerR contains two metal binding sites, one for structural $Zn^{2+}$ and the other for the regulatory/peroxide-sensing metal. Here we investigated the effect of mutations at both the structural and regulatory metal binding sites on the oxidation of either H37 or H91, two of the peroxide-sensing ligands. All four serine substitution mutants at the structural $Zn^{2+}$ site (C96S, C99S, C136S and C139S) exhibited no detectable oxidation at histidine residues. Two of the alanine substitution mutants at regulatory metal site (H37A and D85A) exhibited selective oxidation preferentially at the H91-containing tryptic peptide, whereas no oxidation was detected in the other mutants (H91A, H93A and D104A). Our results suggest that the cysteine residues coordinating structural $Zn^{2+}$ are essential for peroxide sensing by PerR, and that the C-terminal regulatory metal binding site composed of H91, H93 and D104 can bind $Fe^{2+}$, providing a possible explanation for the peroxide sensing mechanisms by PerR.

• 한국정보디스플레이학회:학술대회논문집
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• 2009.10a
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• pp.1279-1282
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• 2009

The luminescence properties of a potential blue-emitting $RbBaPO_4:Eu^{2+}$ phosphor substituted with various metal ions have been investigated. The main emission wavelength of the phosphor samples was red-shifted by the substitution with K and Sr ions. The maximum peak intensity was obtained from the sample $Rb_{0.25}K_{0.75}Ba_{0.99}Eu_{0.01}PO_4$ which showed 144% relative intensity versus that of BAM:$Eu^{2+}$ phosphor under 254 nm excitation.

• Bulletin of the Korean Chemical Society
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• v.17 no.2
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• pp.138-142
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• 1996

The transition metal carbonylate, PPN+(${\eta}^5-MeCp)Mn(CO)_2Cl^-$ undergoes a novel ligand substitution reaction with PR3 (R=Me, Et, OEt, $C_6H_5$ in THF at elevated temperatures (40 $^{\circ}C$ up to 60 $^{\circ}C)$ under the pseudo-first-order reaction conditions (usually 20-fold excess of PR3 with respect to metal carbonylate concentrations) where chloride is displaced by PR3. The reaction follows overall first order dependence on [(${\eta}^5-MeCp)Mn(CO)_2Cl^-$]; however, the negative entropy changes of activation (${\Delta}S^{\neq}$=-19.3 e.u. for $P(OEt)_3$; ${\Delta}S^{\neq}$=-16.4 e.u. for $PPh_3$) suggest the existence of the intermediate, ((η3-MeCp)Mn(CO)2(THF)Cl-, which eventually transforms to the product (${\eta}^5-MeCp)Mn(CO)_2(PR_3)$.

• Bulletin of the Korean Chemical Society
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• v.31 no.2
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• pp.303-308
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• 2010

Pseudo-first-order rate constants ($k_{obsd}$) have been measured spectrophotometrically for nucleophilic substitution reactions of 4-nitrophenyl benzoate (5a), 4-nitrophenyl 4-methoxybenzoate (5b), and 4-nitrophenyl 4-hydroxybenzoate (5c) with alkali metal ethoxides, $EtO^-M^+$ ($M^+=Li^+$, $Na^+$ and $K^+$) in anhydrous ethanol (EtOH) at $25.0{\pm}0.1^{\circ}C$. The plots of $k_{obsd}$ vs. [$EtO^-M^+$] exhibit upward curvatures in all cases, indicating that $M^+$ ions catalyze the reactions and ionpaired $EtO^-M^+$ species are more reactive than dissociated $EtO^-$. Second-order rate constants for reactions with dissociated $EtO^-$ and ion-paired $EtO^-M^+$ (i.e., $k_{EtO^-}$ and $k_{EtO^-M^+}$, respectively) have been calculated from ion-pair treatment for the reactions of 5a and 5b. However, such ion-pair treatment has failed to determine $k_{EtO^-}$ and $k_{EtO^-M^+}$ values for the reactions of 5c. It has been concluded that reactions of 5a and 5b are catalyzed by one metal ion, which increases electrophilicity of the reaction center through coordination on the carbonyl oxygen. In contrast, reactions of 5c have been suggested to involve two metal ions, i.e., the one coordinated on the carbonyl oxygen increases the electrophilicity of the reaction center while the other one associated on the phenoxy oxygen decreases the charge repulsion between the anionic reagents (i.e., $EtO^-$ and deprotonated 5c). It has been found that the rate equation derived from the mechanism involving two metal ions fits nicely to the kinetic results obtained for the reactions of 5c.

• Journal of Korean Society for Atmospheric Environment
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• v.14 no.1
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• pp.25-33
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• 1998

We have studied the reduction of NO by propane over perovskite-type oxides prepared by malic acid method. The catalysts were modified to enhance the activity by substitution by substitution of metal into A or B site of perovskite oxides. In addition, the reaction conditions, such as temperature, $O_2$ concentration, space velocity have been studed. In the $LaCoO_3$ type catalyst, the partial substitution of Ba, Sr into A site enhanced the catalytic activity in the reduction of NO. In the $La_{0.6}Sr_{0.4}Co_{1-x}Fe_xO_3(x=0 \sim 1.9)$ catalyst, the partial substitution of Fe into B site enhanced the conversion of NO, but excess amount of Fe decreased the conversion of NO. The surface area and catalytic activity of perovskite catalysts prepared by malic acid method showed higher values than those of solid reaction method. In the $La_{0.6}Sr_{0.4}Co_{1-x}Fe_xO_3$ catalyst, the conversion of NO increased with increasing $O_2$ concentration and contact time. The introduction of water into reactant feed decreased the catalytic activity.