• Title/Summary/Keyword: Bond order

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Kinetics and Mechanism of Nucleophilic Displacement Reactions of Y-Substituted Phenyl Benzoates with Z-Substituted Phenoxides

  • Min, Se-Won;Seo, Jin-A;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.30 no.10
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    • pp.2403-2407
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    • 2009
  • Second-order rate constants have been measured for two series of nucleophilic displacement reactions, i.e., reactions of 4-nitrophenyl benzoate with Z-substituted phenoxides and those of Y-substituted phenyl benzoates (1a-h) with 4-chlorophenoxide (4-ClPhO–) in 80 mol% $H_2O$/20 mol% DMSO at 25.0 ${\pm}\;0.1\;{^{\circ}C}$. The Br$\phi$nsted-type plot for reactions of 4-nitrophenyl benzoate with Z-substituted phenoxides exhibits an excellent linear correlation with ${\beta}_{nuc}$ = 0.72. Reactions of 1a-h with 4-chlorophenoxide result in also a linear Br$\phi$nsted-type plot with ${\beta}_{lg}$ = –0.62, a typical ${\beta}_{lg}$ value for a concerted mechanism. The Hammett plots correlated with ${\sigma}^o\;and\;{\sigma}^-$ constants show many scattered points for reactions of 1a-h with 4-chlorophenoxide. In contrast, the corresponding Yukawa-Tsuno plot exhibits an excellent linear correlation with $\rho_Y$ = 2.26 and r = 0.53, indicating that expulsion of the leaving group occurs at the rate-determining step (RDS) either in a concerted mechanism or in a stepwise pathway. However, a stepwise mechanism with leaving group departure being the RDS is excluded since the leaving Y-substituted phenoxide is less basic and a better nucleofuge than the incoming 4-ClPh$O^-$. Thus, the reactions have been concluded to proceed through a concerted mechanism, in which bond formation between the nucleophile and electrophilic center is more advanced than expulsion of the leaving group in the transition state on the basis of the magnitude of ${\beta}_{nuc}\;and\;{\beta}_{lg}$ values.

Homology Modeling and Docking Study of β-Ketoacyl Acyl Carrier Protein Synthase Ⅲ from Enterococcus Faecalis

  • Jeong, Ki-Woong;Lee, Jee-Young;Kim, Yang-Mee
    • Bulletin of the Korean Chemical Society
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    • v.28 no.8
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    • pp.1335-1340
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    • 2007
  • β-Ketoacyl acyl carrier protein synthase (KAS) III is a particularly attractive target in the type II fatty acid synthetic pathway, since it is central to the initiation of fatty acid synthesis. Enterococcus faecalis, a Grampositive bacterium, is one of the major causes of hospital acquired infections. The rise of multidrug-resistant of most bacteria requires the development of new antibiotics, such as inhibition of the KAS III. In order to block the fatty acid synthesis by inhibition of KAS III, at first, three dimensional structure of Enterococcus faecalis KAS III (efKAS III) was determined by comparative homology modeling using MODELLER based on x-ray structure of Staphylococcus aureus KAS III (saKAS III) which is a gram-positive bacteria and is 36.1% identical in amino acid sequences with efKAS III. Since His-Asn-Cys catalytic triad is conserved in efKAS III and saKAS III, substrate specificity of efKAS III and saKAS III and the size of primer binding pocket of these two proteins are expected to be similar. Ligand docking study of efKAS III with naringenin and apigenin showed that naringenin docked more strongly with efKAS III than apigenin, resulting in the intensive hydrogen bond network between naringenin and efKAS III. Also, only naringenin showed antibacterial activity against E. faecalis at 256 μg/mL. This study may give practical implications of flavonoids for antimicrobial effects against E. faecalis.

Metabolism of Pyrimidine Deoxyribonucleosides and Heat-resistivity of CdR-aminohydrolase in the Mouse Small Intestine (생쥐 小腸에서의 Pyrimidine Deoxyribonucleoside 代謝와 CdR-aminohydrolase의 熱抵抗性)

  • Kang, Man-Sik;Rhee, Juong-Gile;Cho, Joong-Myung
    • The Korean Journal of Zoology
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    • v.17 no.3
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    • pp.107-116
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    • 1974
  • The metabolism of CdR-2-$^14 C$ and UdR-2-$^14 C$ in mouse small intestine has been studied in connection with the effect of heat treatment on the enzymes concerned in vitro. CdR-2-$^14 C$ is deaminated reaidly by CdR-aminohydrolase at nucleoside level and then degraded into U by the action of nucleosidase which is quite resistant to cleave N-pentose bond of cytosine nucleosides, CdR and CR. High inactivation temperature of $80^\\circC$ was observed for CdR-aminohydrolase, while nucleosidase has an inactivation temperature of $60^\\circC$. CdR-aminohydrolases in various tissues of mouse were inactivated at $80^\\circC$, but not one in tissues of rabbit. It might be assumed that there are correlations between order specificity and inactivation temperature of the enzyme. A physiological significance of the appearance of CdR-aminohydrolase in differentiated tissues of mammals possibly be regarded as a main function in catabolic pathways.

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Rusty Images Applied Fashion Design - For Digital Textile Printing Method - (녹 이미지를 응용한 의상디자인 - 디지털 텍스타일 프린팅 기법을 중심으로 -)

  • Yoon, Ji-Ill;Lee, Youn-Hee
    • The Research Journal of the Costume Culture
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    • v.18 no.5
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    • pp.1003-1016
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    • 2010
  • The purpose of this study is to reorganize any rusty image including natural modeling characteristic presented from the natural phenomenon to certain patterns in order to create the fashion design that are valued in the expansion of independently expressional area and modeling art. As a method for research, the author analyzed the concept and characteristic for rust with a base of theoretical background by the documental research and realistic consideration, analyzed its modeling characteristic through domestic and overseas pictures, and e-documents as data, inspected the modeling activities of various categories that various images were adapted related to rust, looked into the concept of Digital Textile Printing and its producing procedure as an expressional method, and analyzed the examples of modern dress and its ornament making use of Digital Textile Printing. The conclusions of this study are as below. First, the rust occurred due to the natural phenomenon is the bond with different material like metal, each unique modeling characteristic occurs and harmony of various patterns has abundant aesthetic value. Second, the author could endowed sensible characteristic and speciality with works and could produce creative fashion design that painting, abstractive pattern and harmony of unique sense of colors are significant by using the image of rust, Third, to emphasize natural feeling of rust, the author could develop creative design that simple silhouette and impressive pattern look significant by reorganizing and applying rust according to repetition, increment, rhythm, contract, emphasis and harmony. Fourth, Digital Textile Printing method is used to induce visual effect by the expression of feels of rust, and the author could express the natural patterns, delicate expression for the feels of a material and unique design of emotion.

Solvent Effects on the Solvolysis of cis-$[Co(en)_2ClNO_2]^+$ Ion and Its Mechanism (cis-$[Co(en)_2ClNO_2]^+$ 착이온의 가용매 분해반응에 미치는 용매의 영향과 그 반응 메카니즘)

  • Jong-Jae Chung;Young-Ho Park
    • Journal of the Korean Chemical Society
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    • v.30 no.1
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    • pp.3-8
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    • 1986
  • The investigation of the effect of solvent structure on the first-order solvolysis of cis-$[Co(en)_2ClNO_2]^+$ion has been extended to water + co-solvent mixtures where the co-solvents are glycerol, ethylene glycol, isopropyl alcohol and t-butyl alcohol. Rates of solvolysis have been evaluated by spectrophotometric method at temperature 25∼30$^{\circ}$C. The polarity of solvent has influence on the variation of rate constant. The non-linear plot of the rate constant in log scale versus $\frac{D-1}{2D+1}$ implies that change in solvent structure with composition plays an important role in determining the variation of rate constant. The linearity of the plot of the rate constant in log scale versus the Grundwald-Winstein Y factor confirms that the solvolysis is an Id-type process with considerable extension of the metal chloride bond in the transition state. In the Kivinen equation the slope of the plot of log k versus $log(H_2O)$ suggests that the solvolysis is also an Id-type process. The application of free energy cycle shows that the effect of solvent structure is greater in the transition state than in the initial state.

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Polymer-Metal Complexes(II). Catalytic Activity of Some Ni(II)-Polyethyleneimine Complexes (고분자-금속착물 (제2보). 몇가지 Ni(II)-Polyethyleneimine 착물의 촉매활성도)

  • Jung Hag Park;Tae Sub Cho
    • Journal of the Korean Chemical Society
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    • v.25 no.6
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    • pp.394-398
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    • 1981
  • Two types of Ni(II)-polyethyleneimine (PEI) complexes, [Ni(PEI)]$Cl_2$ and [Ni(P-EI)$Cl_2$] were synthesized and their catalytic activities in the decomposition reaction of hydrogen peroxide were investigated. For the purpose of comparison, the corresponding monomeric complexes, $[Ni(en)_3]Cl_2$ and $[Ni(en)_2Cl_2$ were also prepared; it was observed that their activities increase in the following order; $0{\approx}[Ni(en)_3]Cl_2{\le}[Ni(en)_2Cl_2]<[Ni(PEI)]Cl_2<[Ni(PEI)Cl_2]$ On the basis of structural analysis by means of visible and infrared spectroscopy, the catalytic activiy of these Ni(II)-PEI complexes is assumed to depend on the bond strength between the ligand and the nickel ion.

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CO Adsorption on Cation Exchaged Zeolite A and Mordenite (陽이온 交煥된 제올라이트 A 및 Mordenite 上의 CO 氣體 吸着)

  • Kim Jong Taik;Kim Heung Won;Kim Myung Chul;Lee Jong Ryul
    • Journal of the Korean Chemical Society
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    • v.36 no.1
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    • pp.137-146
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    • 1992
  • The adsorption properties of CO on the cation exchanged natural zeolite, $K_{111}$ and cation effects upon the CO adsorption were studied. $Na^+-,\;Cu^{2+}-\;and\;Ba^{2+}-\;K_{111}$ exhibited relatively good CO adsorption capacities and $Ba^{2+}- K_{111}$ treated by 0.4 N-$BaCl_2$ solution proved itself as the best adsorbent and superior to the synthetic zeolite 4A and 5A. The observed adsorption tendency due to the cations were in the order of $Ba^{2+}>Cu^{2+}>Na^+>K^+>Mg^{2+}>Ca^{2+}$. The cation exchanged number per unit cell as well as the kind of cation which forms bond with CO molecules in different intensities and other mineral factors such as pore size indicated to be important factors to the CO adsorption properties. The CNDO/2 calculations were performed to compare the adsorption tendencies and CO interaction energy of cations in $K_{111}$.

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Kinetic Study on Nucleophilic Displacement Reactions of 2-Chloro-4-Nitrophenyl X-Substituted-Benzoates with Primary Amines: Reaction Mechanism and Origin of the α-Effect

  • Um, Tae-Il;Kim, Min-Young;Kim, Tae-Eun;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.35 no.2
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    • pp.436-440
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    • 2014
  • The ${\alpha}$-Effect; Ground state; Transition state; Intramolecular H-bonding; Yukawa-Tsuno plot; Second-order rate constants for aminolysis of 2-chloro-4-nitrophenyl X-substituted-benzoates (1a-h) have been measured spectrophotometrically in 80 mol % $H_2O/20$ mol % DMSO at $25.0^{\circ}C$. The Br${\emptyset}$nsted-type plot for the reactions of 2-chloro-4-nitrophenyl benzoate (1d) with a series of primary amines curves downward, which has been taken as evidence for a stepwise mechanism with a change in rate-determining step (RDS). The Hammett plots for the reactions of 1a-h with hydrazine and glycylglycine are nonlinear while the Yukawa-Tsuno plots exhibit excellent linearity with ${\rho}_X=1.22-1.35$ and ${\gamma}= 0.57-0.59$, indicating that the nonlinear Hammett plots are not due to a change in RDS but are caused by stabilization of substrates possessing an electron-donating group (EDG) through resonance interactions between the EDG and C=O bond of the substrates. The ${\alpha}$-effect exhibited by hydrazine increases as the substituent X changes from a strong EDG to a strong electron-withdrawing group (EWG). It has been concluded that destabilization of hydrazine through the electronic repulsion between the adjacent nonbonding electrons is not solely responsible for the substituent dependent ${\alpha}$-effect but stabilization of the transition state is also a plausible origin of the ${\alpha}$-effect.

Magnetic and Electrical Properties of Ln0.7Ca0.3MnO3 (Ln = Nd, Sm, La) (Ln0.7Ca0.3MnO3(Ln = Nd, Sm, La)의 자기적 전기적 특성)

  • Chon, Gom-Bai;Im, Hung-Su;Lee, Chan-Gyu;Koo, Bon-Heun;Lee, Sang-Min;Jung, Myung-Hwa;Jo, Young-Hun
    • Korean Journal of Materials Research
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    • v.17 no.4
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    • pp.203-206
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    • 2007
  • Effects of doping rare earth elements on Ln site of $Ln_{0.7}Ca_{0.3}MnO_3$ (Ln = N d, Sm and La) were examined from structure, magnetic and electrical properties. Size of a-axis increased as following order of La < Nd < Sm, whereas c-axis was not much changed. Curie temperatures of 170 K for $Nd_{0.7}Ca_{0.3}MnO_3$, 110 K for $Sm_{0.7}Ca_{0.3}MnO_3$ and 250 K for $La_{0.7}Ca_{0.3}MnO_3$ were obtained. This result coincides with change of Mn-O bond length causing by a-axis lattice constant. The highest magnetroresistance ratios were 22% at 77 K for $Sm_{0.7}Ca_{0.3}MnO_3$, 32% at 110 K for $Nd_{0.7}Ca_{0.3}MnO_3$, and 33% at 180 K for $La_{0.7}Ca_{0.3}MnO_3$.

Effects of Plasma Surface Treatments Using Dielectric Barrier Discharge to Improve Diamond Films

  • Kang, In-Je;Ko, Min-Guk;Rai, Suresh;Yang, Jong-Keun;Lee, Heon-Ju
    • Proceedings of the Korean Vacuum Society Conference
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    • 2013.02a
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    • pp.552-552
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    • 2013
  • In our study we consider Al2O3 ceramic substrates for Plasma Surface Treatments in order to improve deposited diamond surface and increase diamond deposition rate by applying DBD (Dielectric Barrier Dischrge) system. Because Plasma Surface Treatments was used as a modification method of material surface properties like surface free energy, wettability, and adhesion. By applying Plasma Surface Treatments diamond films are deposited on the Al2O3 ceramic substrates. DC Arc Plasmatron with mathane and hydrogen gases is used. Deposited diamond films are investigated by SEM (Scanning Electron Microscopy), AFM (Atomic Force Microscopy) and XRD (X-ray Diffractometer). Then the C-H stretching of synthetic diamond films by FTIR (Fourier Transform Infrared Spectroscopy) is studied. As a result, nanocrystalline diamond films were identified by using SEM and diamond properties in XRD peaks at (111, $43.8{\Box}$, (220, $75.3{\Box}$ and (311, $90.4{\Box}$ were shown. Absorption peaks in FTIR spectrum, caused by CHx sp3 bond stretching of CVD diamond films, were identified as well. Finally, we improved such parameters as depostion rate ($2.3{\mu}m$/h), diamond surface uniformity, and impurities level by applying Plasma Surface Treatments. These experimental results show the importance of Plasma Surface Treatments for diamond deposition by a plasma source.

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