• Bulletin of the Korean Chemical Society
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• v.28 no.11
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• pp.2009-2014
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• 2007

The aminolysis of diphenyl thiophosphinic chloride (2) with substituted anilines in acetonitrile at 55.0 oC is investigated kinetically. Kinetic results yield large Hammett ρX (ρnuc = ?3.97) and Bronsted βX (βnuc = 1.40) values. A concerted mechanism involving a partial frontside nucleophilic attack through a hydrogen-bonded, four-center type transition state is proposed on the basis of the primary normal kinetic isotope effects (kH/kD = 1.0-1.1) with deuterated aniline (XC6H4ND2) nucleophiles. The natural bond order charges on P and the degrees of distortion of 42 compounds: chlorophosphates [(R1O)(R2O)P(=O)Cl], chlorothiophosphates [(R1O)(R2O)P(=S)Cl], phosphonochloridates [(R1O)R2P(=O)Cl], phosphonochlorothioates [(R1O)R2P(=S)Cl], chlorophosphinates [R1R2P(=O)Cl], and chlorothiophosphinates [R1R2P(=S)Cl] are calculated at the B3LYP/ 6-311+G(d,p) level in the gas phase.

• Proceedings of the Korean Society of Tribologists and Lubrication Engineers Conference
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• 2004.11a
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• pp.66-74
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• 2004

The sliding wear behavior of $ZrO_2-22wt\%MgO\;(MZ)\;and\;ZrO_2-8wt\%Y_2O_3\;(YZ)$ deposited on a casting aluminum alloy with bond layer (NiCrCoAlY) by plasma spray against an SiC ball was investigated under dry test conditions at room temperature. At all load conditions, the wear mechanisms of the MZ and the YZ coatings were almost the same. The wear mechanisms involved the forming of a smooth film by material transferred on the sliding surface and pullout. The wear rate of the MZ coating was less than that of the YZ coating. With an increase normal load the wear rate of the studied coatings increased. The SEM was used to examine the sliding surfaces and elucidate likely wear mechanisms. The EDX analysis of the worn surface indicated that material transfer was occurred from the SiC ball to the disk. It was suggested that the material transfer played an important role in the wear performance.

• Proceedings of the Materials Research Society of Korea Conference
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• 2009.11a
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• pp.23.1-23.1
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• 2009

ZnO is of great interest for various technological applications ranging from optoelectronics to chemical sensors because of its superior emission, electronic, and chemical properties. In addition, vertically well-aligned ZnO nanorods on large areas with good optical and structural properties are of special interest for the fabrication of electronic and optical nanodevices. To date, several approaches have been proposed for the growth of one-dimensional (1D) ZnO nanostructunres. Several groups have been reported the MOCVD growth of ZnO nanorods with no metal catalysts at $400^{\circ}C$, and fabricated a well-aligned ZnO nanorod array on a PLD prepared ZnO film by using a catalyst-free method. It has been suggested that the synthesis of ZnO nanowires using a template-less/surfactant-free aqueous method. However, despite being a well-established and cost-effective method of thin film deposition, the use of magnetrons puttering to grow ZnO nanorods has not been reported yet. Additionally,magnetron sputtering has the dvantage of producing highly oriented ZnO film sat a relatively low process temperature. Currently, more effort has been concentrated on the synthesis of 1D ZnO nanostructures doped with various metal elements (Al, In, Ga, etc.) to obtain nanostructures with high quality,improved emission properties, and high conductance in functional oxide semiconductors. Among these dopants, Ga-doped ZnO has demonstrated substantial advantages over Al-doped ZnO, including greater resistant to oxidation. Since the covalent bond length of Ga-O ($1.92\;{\AA}$) is nearly equal to that of Zn-O ($1.97\;{\AA}$), high electron mobility and low electrical resistivity are also expected in the Ga-doped ZnO. In this article, we report the successful growth of Ga-doped ZnO nanorods on c-Sapphire substrate without metal catalysts by magnetrons puttering and our investigations of their structural, optical, and field emission properties.

• Bulletin of the Korean Chemical Society
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• v.12 no.6
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• pp.674-678
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• 1991

Methanolysis of a ${\beta}$-lactam ring of a cephalosporin was simulated with AM1 semiempirical quantum mechanical calculation. The tetrahedral intermediate TD1 from an O-protonated cephalosporin and a methanol transfers the proton intramolecularly to the C-4 carboxylate to generate an oxyanion, i.e., second tetrahedral intermediate TD2, which undergoes the amide bond cleavage without further protonation on the N-5. For this cleavage a low-energy barrier TS2 was located. According to the energy diagram, tetrahedral intermediates easily undergo ring cleavage even without the protonation on the amide nitrogen.

• Bulletin of the Korean Chemical Society
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• v.32 no.6
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• pp.1907-1911
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• 2011

A kinetic study is reported for nucleophilic substitution reactions of 4-pyridyl X-substituted benzoates 7a-e with a series of alicyclic secondary amines in H2O. The Br${\o}$nsted-type plot for the reactions of 4-pyridyl benzoate 7c is linear with ${\beta}_{nuc}$ = 0.71. The corresponding reactions of 2-pyridyl benzoate 6, which is less reactive than 7c, resulted in also a linear Br${\o}$nsted-type plot with ${\beta}_{nuc}$ = 0.77. The fact that the more reactive 7c results in a smaller ${\beta}_{nuc}$ value appears to be in accord with the reactivity-selectivity principle. The aminolysis of 7c has been suggested to proceed through a stepwise mechanism in which breakdown of the intermediate is the rate-determining step (RDS). The Hammett plot for the reactions of 7a-e with piperidine consists of two intersecting straight lines, i.e., ${\rho}_X$ = 1.47 for substrates possessing an electron-donating group (EDG) and ${\rho}_X$ = 0.91 for those possessing an electron-withdrawing group (EWG). In contrast, the corresponding Yukawa-Tsuno plot exhibits excellent linear correlation with ${\rho}_X$ = 0.79 and r = 0.56. Thus, it has been concluded that the nonlinear Hammett plot is not due to a change in the RDS but is caused by stabilization of the ground state of the substrates possessing an EDG through resonance interaction between the EDG and the C=O bond of the substrates.

• Journal of the Korean Ceramic Society
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• v.40 no.2
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• pp.153-158
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• 2003

Self-patterning of thin films using photosensitive sol solution has advantages such as simple manufacturing process compared to photoresist/dry etching process. In this study,$La_{0.5}SR_{0.5}CoO_3$(LSCO) thin films as an electrode material for ferroelectric memories have been prepared by spin coating method using photosensitive sol solution. La-2methoxyethoxide, Sr-ethoxide, Co-2methoxyethoxide were used as starting materials. As UV exposure time to the LSCO gel thin film increased, the UV absorption peak intensity of metal${beta}$-diketonate decreased due to reduced solubility by M(metal)-O-M bond formation. Solubility difference by UV irradiation on LSCO gel thin film allows to obtain a fine patterning of thin film. The LSCO thin films annealed over$680{\circ}C$ in air showed perovskite phase and the lowest resistivity$(4{ imes}10^{-3}{Omega}cm)$ of the thin films were obtained by annealing at$740{\circ}C$.

• Archives of Pharmacal Research
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• v.3 no.1
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• pp.37-49
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• 1980

Chlorpropamide, $C_{10}H_{13}N_{2}O_{3}SCI$, forms orthofombic crystals of space group $P_{2}_{ 1}2_{1}2_{1}$ with a 9.066 $\pm$ 0.004, b = 5.218 $\pm$ 0.003, c = 26, 604 $\pm$, 0.008 $\AA$, and four molecules per cell. Three dimensional photographic data were collected with Mo-K$\alpha$ radiation. The structure was determined using Patterson, Fourier and Difference syntheses methods and refined by the block-diagonal least-squares methods with anisotropic thermal parameters for all nonhydrogen atoms and isotropic thermal parameters for all hydrogen atomes. The final R value was 0.10 for the 1823 observed independent reflections. The dihedral angle between the planes through the benzene ring and the urea goup is 99$^{\circ}$. The conformational angle formed by the projection of the S-C(1) with that of N(1)-C(7) when the projection is taken along the S-N(1) bond is 76$^{\circ}$. The molecule appears to form with neighbouring molecules two hydrogen bonds, N(1)..H...O(3) and N(2)-H...0(2) of lengths 2.774 and 2.954$\AA$ respectively related by screw diads parallel to the a axis. Adjacent molecules parallel to b and c axis are bound together by van der Wasls forces.

• Journal of Microbiology and Biotechnology
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• v.34 no.6
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• pp.1270-1275
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• 2024

Human gut bacterium Dorea sp. MRG-IFC3 is unique in that it is capable of metabolizing puerarin, an isoflavone C-glycoside, whereas it shows broad substrate glycosidase activity for the various flavonoid O-glycosides. To address the question on the substrate specificity, as well as biochemical characteristics, cell-free biotransformation of flavonoid glycosides was performed under various conditions. The results showed that there are two different enzyme systems responsible for the metabolism of flavonoid C-glycosides and O-glycosides in the MRG-IFC3 strain. The system responsible for the conversion of puerarin was inducible and comprised of two enzymes. One enzyme oxidizes puerarin to 3"-oxo-puerarin and the other enzyme converts 3"-oxo-puearin to daidzein. The second enzyme was only active toward 3"-oxo-puerarin. The activity of puerarin conversion to daidzein was enhanced in the presence of Mn²⁺ and NAD⁺. It was concluded that the puerarin C-deglycosylation by Dorea sp. MRG-IFC3 possibly adopts the same biochemical mechanism as the strain PUE, a species of Dorea longicatena.

• Journal of the Korean Vacuum Society
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• v.6 no.2
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• pp.159-164
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• 1997

We have studied initial oxidation of the alkali metal(AM)/Si(111) surface using X-ray photoelectron spectroscopy(XPS) and reflection high energy electron diffraction(RHEED) at room temperature(RT) and high temperature(HT)(300~50$0^{\circ}C$). The oxidation of the Si(111)7$\times$7 surface was promoted by the adsorption of 1 momolayer(ML) AM, whereas no promotion occurred for submonolayer(<0.5 ML) adsorbed Si(111)7$\times$7 surface at RT. O Is core level spectra were measured with increasing oxygen exposure. It was found that the oxygen adsorbed on the Si(111)7$\times$7-AM surface have two different bond configuration, Si-O and Am-O, respectively. From these results, we discussed the role of AM-O bonding in the promoted oxidation. At HT(300~50$0^{\circ}C$), the AM-adsorbed surface became very inactive with the structural transformation to the 3$\times$1-AM. We present the results of the oxidation of the Si(111)3$\times$1-AM(Na, K, Cs) surface.

• Proceedings of the Korean Vacuum Society Conference
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• 2013.02a
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• pp.265-265
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• 2013

We have investigated the influences of dangling bonds generated by alpha particle irradiation on friction and adhesion properties of graphene. Single layer of graphene grown with chemical vapor deposition on copper foil was irradiated by the alpha beam with the average energy of 3.04 MeV and the irradiation dosing between $1{\times}10^{14}$ and $1{\times}10^{15}$/$cm^3$. Raman spectroscopic showed that the ${\pi}$ electron states below Fermi level arises and the $I_D$/$I_G$ increases as increasing the dosing of alpha particle irradiation. The core level X-ray photoelectron (XPS) revealed that these defects represent the creation of various carbon-related defects and dangling bond. The nanoscale tribological properties were investigated with atomic force microscopy in ultrahigh vacuum. The friction appeared to increase remarkably as increasing the amount of dosing, indicating that the dangling bonds on graphene layers enhances the energy dissipations in friction. This trend can be explained by the additional channel of energy dissipation by dangling bond or O- and H- terminated clusters created by alpha particle irradiation.