• 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.

• Bulletin of the Korean Chemical Society
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• v.31 no.12
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• pp.3543-3548
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• 2010

A kinetic study on nucleophilic displacement reactions of 2-pyridyl X-substituted benzoates 1a-e with potassium ethoxide (EtOK) in anhydrous ethanol is reported. Plots of pseudo-first-order rate constants ($k_{obsd}$) vs. $[EtOK]_o$ exhibit upward curvature. The $k_{obsd}$ value at a fixed $[EtOK]_o$ decreases steeply upon addition of 18-crown-6-ether (18C6) to the reaction mixture up to [18C6]/$[EtOK]_o$ = 1 and then remains nearly constant thereafter. In contrast, $k_{obsd}$ increases sharply upon addition of LiSCN or KSCN. Dissection of $k_{obsd}$ into $k_{EtO^-}$ and $k_{EtOM}$ has revealed that ion-paired EtOK is more reactive than dissociated $EtO^-$, indicating that $K^+$ ion acts as a Lewis acid catalyst. Hammett plots for the reactions of 1a-e with dissociated $EtO^-$ and ion-paired EtOK result in excellent linear correlation with $\rho$ values of 3.01 and 2.67, respectively. The $k_{EtOK}/k_{EtO^-}$ ratio increases as the substituent X in the benzoyl moiety becomes a stronger electron-donating group. $K^+$ ion has been concluded to catalyze the current reaction by stabilizing the transition state through formation of a 6-membered cyclic complex.

• Proceedings of the Korean Vacuum Society Conference
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• 1999.07a
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• pp.29-29
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• 1999

The synthesis of layered structures on the nanometer scale has become essential for continued improvements in the operation of various electronic and magnetic devices. Abrupt metal-metal interfaces are desired for applications ranging from metallization in semiconductor devices to fabrication of magnetoresistive tunnel junctions for read heads on magnetic disk drives. In particular, characterizing the interface structure between various transition metals (TM) and aluminum is desirable. We have used the techniques of MeV ion backscattering and channeling (HEIS), x-ray photoemission (ZPS), x-ray photoelectron diffraction(XPD), low-energy ion scattering (LEIS), and low-energy electron diffraction(LEED), together with computer simulations using embedded atom potentials, to study solid-solid interface structure for thin films of Ni, Fe, Co, Pd, Ti, and Ag on Al(001), Al(110) and Al(111) surfaces. Considerations of lattice matching, surface energies, or compound formation energies alone do not adequately predict our result, We find that those metals with metallic radii smaller than Al(e.g. Ni, Fe, Co, Pd) tend to form alloys at the TM-Al interface, while those atoms with larger atomic radii(e.g. Ti, Ag) form epitaxial overlayers. Thus we are led to consider models in which the strain energy associated with alloy formation becomes a kinetic barrier to alloying. Furthermore, we observe the formation of metastable fcc Ti up to a critical thickness of 5 monolayers on Al(001) and Al(110). For Ag films we observe arbitrarily thick epitaxial growth exceeding 30 monolayers with some Al alloying at the interface, possible driven by interface strain relief. Typical examples of these interface structures will be discussed.

• Journal of Korean Society of Environmental Engineers
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• v.29 no.1
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• pp.68-73
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• 2007

In this study, we investigated the decomposition of highly concentrated hydrogen peroxide in the range of 1.04-2.55 M by transition metal ion catalysts such as $Fe^{2+}$ and $Cu^{2+}$. The effect of metal ion concentration on the decomposition of hydrogen peroxide was examined experimentally, and the decomposition rate constants were determined by combining the experimental data with a theoretical approach. The rate of the decomposition of hydrogen peroxide was found to be first order with respect to its concentration. The decomposition rate constant was able to be treated as a linear function of the initial metal ion concentration. The validity of the decomposition rate constants determined was verified by good agreements between the calculated and experimental results.

• Bulletin of the Korean Chemical Society
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• v.24 no.1
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• pp.49-54
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• 2003

TiO₂nanoparticles were synthesized using the metallorganic chemical vapor deposition process. Particles with and without metal ion dopants were obtained. X-ray photoelectron and energy dispersive X-ray spectroscopic measurements confirmed the stoichiometry of the TiO₂nanoparticles. X-ray diffraction patterns showed a polycrystalline anatase structure of TiO₂. Transmission electron microscopy revealed that these particles are of nanoscale dimensions. Exact particle size and size distribution analyses were carried out by dynamic light scattering. The average particle size was determined to be 22 nm. The nanosize particles provided large surface area for photocatalysis and a large number of free surface-charge carriers, which are crucial for the enhancement of photocatalytic activity. To improve the photocatalytic activity, metal ions, including transition metal ions $(Pd^{2+},\;Pt^{4+},\;Fe^{3+})$ and lanthanide ion $(Nd^{3+})$ were added to pure TiO₂nanoparticles. The effects of dopants on photocatalytic kinetics were investigated by the degradation of 2-chlorophenol under an ultraviolet light source. The results showed that the TiO₂nanoparticles with the metal ion dopants have higher photocatalytic activity than undoped TiO₂. The $Nd^{3+}$ ion of these dopant metal ions showed the highest catalytic activity. The difference in the photocatalytic activity with different dopants is related to the different ionic radii of the dopants.

• Bulletin of the Korean Chemical Society
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• v.12 no.2
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• pp.130-137
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• 1991

The following new cryptand 221 complexes of lanthanides(Ⅲ) and dioxouranium(Ⅵ) nitrate have been synthesized: $(Ln(C_{16}H_{32}N_2O_5)(H_2O)_2(NO_3)_3\ and \((UO_2)_2(C_{16}H_{32}N_2O_5)(H_2O)_4(NO_3)_4$. These complexes have been identified by elemental analysis, moisture titration, conductivity measurements and various spectroscopic techniques. The proton and carbon-13 NMR as well as calorimetric measurements were used to study the interaction of cryptand 221 with La(Ⅲ), Pr(Ⅲ ), Ho(Ⅲ) and $UO_2(Ⅱ)$ ions in nonaqueous solvents. The bands of metal-oxygen atoms, metal-nitrogen atoms and O-U-O in the IR spectra shift upon complexation to lower frequencies, and the vibrational spectra ({\delta}NMN$) of metal-amide complexes in the crystalline state exhibit lattice vibrations below 300 $cm^{-1}$. The NMR spectra of the lanthanides(Ⅲ) and dioxouranium(Ⅵ) nitrate complexes in nonaqueous solvents are quite different, indicating that the ligand exists in different conformation, and also the $^1H$ and $^{13}C-NMR$ studies indicated that the nitrogen atom of the ring has greater affinity to metal ions than does the oxygen atom, and the planalities of the ring are lost by complexation with metal ions. Calorimetric measurements show that cryptand 221 forms more stable complexes with $La^{3+}$ and $Pr^{3+}$ ions than with $UO^{22+}$ ion, and $La^{3+}/Pr^{3+}$ and $UO^{22+}/Pr^{3+}$ selectivity depends on the solvents. These changes on the stabilities are dependent on the basicity of the ligand and the size of the metal ions. The absorption band (230-260 nm) of the complex which arises from the direct interaction of macrocyclic donor atoms with the metal ion is due to n-{\delta}*$ transition and also that (640-675 nm) of $UO^{22+}$-cryptand 221 complex, which arises from interaction between two-dioxouranium(Ⅵ) ions in being out of cavity of the ligand ring is due to d-d* transition.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 1999.11a
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• pp.409-414
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• 1999

The influence of ion beam energy and reactive oxygen partial pressure on the electrical and crystallographic characteristics of transition metal oxide compound(Cr0x) film was studied in this paper. Chromium oxide films were prepared onto the coverglass using Ion Beam Sputter Deposition(1BSD) technique according to the processing conditions of the partial pressure of reactive oxygen gas and ion beam energy. Crystallinity and grain size of as-deposited films were analyzed using XRD analysis. Thickness and Resistivity of the films were measured by $\alpha$-step and 4-point probe measurement. As results, according to the XRD, XPS and resistivity measurement, the deposited films were the cermet type films which has a crystal structure including amorphous oxide(a-oxide) phase and metal Cr phase simultaneously. The increasernent of the ion b m energy during the deposition process happened to decreasernent of metal Cr grain size and the rapid change of resistivity above the critical $O_2$ partial pressure.

• Bulletin of the Korean Chemical Society
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• v.29 no.1
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• pp.117-121
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• 2008

Pseudo-first-order rate constants (kobsd) have been measured spectrophotometrically for nucleophilic substitution reactions of 5-nitro-8-quinolyl benzoate (5) with alkali metal ethoxides, EtO?M+ (M+ = Li+, Na+ and K+) in anhydrous ethanol (EtOH) at 25.0 0.1 C. The plots of kobsd vs. [EtO?M+] exhibit upward curvatures, while the corresponding plots for the reactions of 5 with EtO?Na+ and EtO?K+ in the presence of complexing agents, 15-crown-5-ether and 18-crown-6-ether are linear with rate retardation. The reactions of 5 with EtO?Na+ and EtO?Li+ result in significant rate enhancements on additions of Na+ClO4, indicating that the M+ ions behave as a catalyst. The dissociated EtO and ion-paired EtOM+ have been proposed to react with 5. The second-order rate constants for the reactions with EtO (kEtO) and EtOM+ (kEtOM+) have been calculated from ion-pairing treatments. The kEtO and kEtOM+ values decrease in the order kEtONa+ > kEtOK+ > kEtOLi+ > kEtO, indicating that ion-paired EtOM+ species are more reactive than the dissociated EtO ion, and Na+ ion exhibits the largest catalytic effect. The M+ ions in this study form stronger complex with the transition state than with the ground state. Coordination of the M+ ions with the O and N atoms in the leaving group of 5 has been suggested to be responsible for the catalytic effect shown by the alkali metal ions in this study.

• Bulletin of the Korean Chemical Society
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• v.35 no.8
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• pp.2438-2442
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• 2014

A kinetic study is reported for $S_NAr$ reaction of 1-fluoro-2,4-dinitrobenzene (5a) and 1-chloro-2,4-dinitrobenzene (5b) with alkali-metal ethoxides (EtOM, M = Li, Na, K and 18-crown-6-ether complexed K) in anhydrous ethanol. The second-order rate constant increases in the order $k_{EtOLi}$ < $k_{EtO^-}$ < $k_{EtONa}$ < $k_{EtOK}$ < $k_{EtOK/18C6}$ for the reaction of 5a and $k_{EtOLi}$ < $k_{EtONa}$ < $k_{EtO^-$ < $k_{EtOK}$ < $k_{EtOK/18C6}$ for that of 5b. This indicates that $M^+$ ion behaves as a catalyst or an inhibitor depending on the size of $M^+$ ion and the nature of the leaving group ($F^-$ vs. $Cl^-$). Substrate 5a is more reactive than 5b, although the $F^-$ in 5a is ca. $10pK_a$ units more basic than the $Cl^-$ in 5b, indicating that the reaction proceeds through a Meisenheimer complex in which expulsion of the leaving group occurs after the rate-determining step (RDS). $M^+$ ion would catalyze the reaction by increasing either the nucleofugality of the leaving group through a four-membered cyclic transition state or the electrophilicity of the reaction center through a ${\pi}$-complex. However, the enhanced nucleofugality would be ineffective for the current reaction, since expulsion of the leaving group occurs after the RDS. Thus, it has been concluded that $M^+$ ion catalyzes the reaction by increasing the electrophilicity of the reaction center through a ${\pi}$-complex between $M^+$ ion and the ${\pi}$-electrons in the benzene ring.

• Mycobiology
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• v.35 no.3
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• pp.150-153
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• 2007

New $N_2O_2$ donor type Schiff base has been designed and synthesized by condensing acetoacetanilido-4-aminoantipyrine with 2-aminobenzoic acid in ethanol. Solid metal complexes of the Schiff base with Cu(II), Ni(II), Co(II), Mn(II), Zn(II), VO(IV), Hg(II) and Cd(II) metal ions were synthesized and characterized by elemental analyses, magnetic susceptibility, molar conduction, fast atom bombardment (FAB) mass, IR, UV-Vis, and $^1H$ NMR spectral studies. The data show that the complexes have the composition of ML type. The UV-Vis. and magnetic susceptibility data of the complexes suggest a square-planar geometry around the central metal ion except VO(IV) complex which has square-pyramidal geometry. The in vitro antifungal activities of the compounds were tested against fungi such as Aspergillus niger, Aspergillus flavus, Rhizopus stolonifer, Candida albicans, Rhizoctonia bataicola and Trichoderma harizanum. All the metal complexes showed stronger antifungal activities than the free ligand. The minimum inhibitory concentrations (MIC) of the metal complexes were found in the range of $10{\sim}31{\mu}g/ml$.