• Title/Summary/Keyword: $S_{N}2$ mechanism

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sanN Encoding a Dehydrogenase is Essential for Nikkomycin Biosynthesis in Streptomyces ansochromogenes

  • Ling, Hong-Bo;Wang, Guo-Jun;Li, Jin-E;Tan, Hua-Rong
    • Journal of Microbiology and Biotechnology
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    • v.18 no.3
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    • pp.397-403
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    • 2008
  • Nikkomycins are a group of peptidyl nucleoside antibiotics with potent fungicidal, insecticidal, and acaricidal activities. sanN was cloned from the partial genomic library of Streptomyces ansochromogenes 7100. Gene disruption and complementation analysis demonstrated that sanN is essential for nikkomycin biosynthesis in S. ansochromogenes. Primer extension assay indicated that sanN is transcribed from two promoters (sanN-P1 and sanN-P2), and sanN-P2 plays a more important role in nikkomycin biosynthesis. Purified recombinant SanN acts as a dehydrogenase to convert benzoate-CoA to benzaldehyde in a random-order mechanism in vitro, with respective $K_{cat}/K_m$$ values of $3.8mM^{-1}s^{-1}\;and\;12.0mM^{-1}s^{-1}$ toward benzoate-CoA and NADH, suggesting that SanN catalyzes the formation of picolinaldehyde during biosynthesis of nikkomycin X and Z components in the wild-type stain. These data would facilitate us to understand the biosynthetic pathway of nikkomycins and to consider the combinatorial synthesis of novel antibiotic derivatives.

V-I Characteristics of $(Sr_{0.85}Ca_{0.15})TiO_3$ Thin Film by RF Sputtering Method (RF 스퍼터링법에 의한 $(Sr_{0.85}Ca_{0.15})TiO_3$ 박막의 전압-전류 특성)

  • Kim, J.S.;Cho, C.N.;Shin, C.G.;Choi, W.S.;Kim, C.H.;Lee, J.U.
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 2000.04b
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    • pp.88-91
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    • 2000
  • The $(Sr_{0.85}Ca_{0.15})TiO_3$(SCT) thin films are deposited on Pt-coated electrode(Pt/TiN/$SiO_2$/Si) using RF sputtering method. The crystallinity of SCT thin films is increased with increase of substrate temperature in the temperature range of 200~500$[^{\circ}C]$. V-I characteristics of SCT thin films show the increasing leakage current with the increases of deposition temperature. The conduction mechanism of the SCT thin films observed in the temperature range of 25~100$[^{\circ}C]$ can be divided into four characteristic regions with different mechanism by the increasing current.

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Cross-interaction Constants in the Nucleophilic Reactions of Carbonyl Compounds Involving a Tetrahedral Intermediate

  • Lee, Ik-Choon
    • Bulletin of the Korean Chemical Society
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    • v.15 no.11
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    • pp.985-990
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    • 1994
  • Cross-interaction constants, ${\rho}^e_{XY}$, ${\rho}_{YZ}$ and ${\rho}_{XZ}$ are defined using observed rate constant, k_N=(k_1/k_{-1})k_2=Kk_2$, for the stepwise carbonyl addition reactions involving the rate-limiting breakdown of a tetrahedral intermediate $(T^{\pm})$. Abundant experimental evidence in the literature enables us to determine signs for the three constants for such mechanism, ${\rho}^e_{XY}$>0, ${\rho}_{YZ}$<0 and ${\rho}_{XZ}$0. These are in contrast to those for the concerted $S_N2$ mechanism, ${\rho}_{XY}$<0, ${\rho}_{YZ}$>0 and ${\rho}_{XZ}$, and provide useful mechanistic criteria. In the light of these criteria, mechanisms of some nucleophilic reactions of carbonyl compounds are re-examined.

Kinetic Studies on the Mechanism of Hydrolysis of ${\alpha}$-Nitrobenzaldehydephenylhydrazone (${\alpha}$-Nitrobenzaldehydephenylhydrazone의 가수분해에 대한 반응속도론적 연구)

  • Tae-Rin Kim;Won-Sik Choi
    • Journal of the Korean Chemical Society
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    • v.22 no.1
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    • pp.30-36
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    • 1978
  • The kinetics of hydrolysis of ${\alpha}$-nitrobenzaldehydephenylhydrazone derivatives (p-$NO_2$, m-$NO_2$, p-Cl, p-$CH_3$) have been investigated by UV spectrometry in 25% dioxane-water at $25^{\circ}C$ and a rate equation which can be applied over wide pH range was obtained. From the rate equation and the effect of solvent, substituent and pKa on the rate equation, the following reaction mechanisms were proposed. Below pH 3.0 the hydrolysis of ${\alpha}$-nitrobenzaldehydephenylhydrazone proceeds by $S_N1$ mechanism, while above pH 4.0 the hydrolysis proceeds through 1,3-dipole ion mechanism. In the range of pH from 3.0 to 4.0 these two reactions occur competitively.

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Numerical Computation of Bearing Capacity Factor $N_{\gamma}$ (지지력 계수 $N_{\gamma}$의 수치적 산정법)

  • Kim, Won-Cheul
    • Proceedings of the Korean Geotechical Society Conference
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    • 2004.03b
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    • pp.565-573
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    • 2004
  • This study is to present explicit analytical expressions for calculating bearing capacity factor $N_{\gamma}$, to provide results of the numerical computation instead of the graphical method. In this study, $N_{\gamma}$ is proposed in the critical failure surface on assumption that the center of log spiral in the radial shear zone can be located at the any points of around footing. The critical failure surface is one which yields minimum passive pressure $P_{\gamma}$ on the radial shear zone from the family of log spirals accoding to change of the center of log spiral. This study adoptes Terzaghi's bearing capacity principle(e.g., Prandtl's mechanism, limit equilibrium equation, superposition principle) but the soil wedge in an elastic zone makes angle $45^{\circ}+{\phi}/2$ with the horizontal and the location of the log spiral's center.

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The Effects of Pressure, Temperature and Solvent Composition on Solvolysis of trans-[Co(N-eten)$_2Cl_2]^+$ in Water-t-butyl Alcohol Mixture

  • Park Yu Chul;Cho Young Je
    • Bulletin of the Korean Chemical Society
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    • v.9 no.1
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    • pp.1-4
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    • 1988
  • Rates of solvolysis of trans-[Co$(N-eten)_2Cl_2$]$^+$ have been investigated using spectrophotometric method at various pressures and temperatures in the mixtures of water with the t-butyl alcohol which possesses a high structure inducing capacity in water. The values of ${\Delta}V^{\neq}$ obtained from pressure effect on the rate constants were 2.55∼ 5.83 $cm^3mol^{-1}$. These values were discussed in terms of dissociative mechanism. Extrema found in the variation of ${\Delta}H^{\neq}$ and ${\Delta}S^{\neq}$ with solvent composition correlated with extrema in the variation of the physical properties of the mixtures. The logarithms of rate constants correlated linearly with both Grunwald-Winstein parameter and the reciprocal of dielectric constant ($Ds^{-1}$). The gradient, m of Grunwald-Winstein plot for the trans-[Co$(N-eten)_2Cl_2$]$^+$ was 0.09, which is significantly lower than those for the other cobalt (Ⅲ)-dichloro complexes. It was suggested that the reaction is an Id mechanism with long extension of Co-Cl bond in the transition state, as found for the C-Cl bond in the transition state for the solvolysis of t-butyl chloride.

A Study of Nitrous Oxide Thermal Decomposition and Reaction Rate in High Temperature Inert Gas (고온 불활성 기체 분위기에서 아산화질소 열분해 및 반응속도에 관한 연구)

  • Lee, Han Min;Yun, Jae Geun;Hong, Jung Goo
    • Journal of ILASS-Korea
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    • v.25 no.3
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    • pp.132-138
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    • 2020
  • N2O is hazardous atmosphere pollution matter which can damage the ozone layer and cause green house effect. There are many other nitrogen oxide emission control but N2O has no its particular method. Preventing further environmental pollution and global warming, it is essential to control N2O emission from industrial machines. In this study, the thermal decomposition experiment of N2O gas mixture is conducted by using cylindrical reactor to figure out N2O reduction and NO formation. And CHEMKIN calculation is conducted to figure out reaction rate and mechanism. Residence time of the N2O gas in the reactor is set as experimental variable to imitate real SNCR system. As a result, most of the nitrogen components are converted into N2. Reaction rate of the N2O gas decreases with N2O emitted concentration. At 800℃ and 900℃, N2O reduction variance and NO concentration are increased with residence time and temperature. However, at 1000℃, N2O reduction variance and NO concentration are deceased in 40s due to forward reaction rate diminished and reverse reaction rate appeared.

Studies on the Effect and Mechanism of Geupoongjibo-dan's Relaxation on a Blood Vessel (거풍지보단(祛風至寶丹)의 혈관이완 효능과 기전에 관한 연구)

  • Kim, Dong-Eun;Park, Dong-Wan;Jeong, Sung-Hyun;Shin, Gil-Cho;Lee, Won-Chul;Han, Sung-Ho
    • The Journal of Internal Korean Medicine
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    • v.22 no.2
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    • pp.119-125
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    • 2001
  • Objectives : This study was conducted to evaluate the effect and mechanism of Geupoongjibo-dan's relaxation of the tension of the blood vessel caused by Phenylephrine and KCI. Methods : In order to study the effect of Geupoongjibo-dan's relaxation of the blood vessel tension, Geupoongjibo-dan extract was infused into Phenylephrine and KCI-induced contracted rabbit aorta strips. To analyze the mechanism of Geupoongjibo-dan's effect on the blood vessel, Geupoongjibo-dan extract infused into Phenylephrine and KCI-induced contracted strips induced by agonists after treatment of N${\omega}$-nitro-L-arginine, Methylene Blue. Results : 1. Geupoongjibo-dan was very effective in relaxing the blood vessels contracted by Phenylephrine. 2. Geupoongjibo-dan was effective against Phenylephrine, than against KCI. 3. Geupoongjibo-dan's more relaxation effect on a blood vessel was terminated by N${\omega}$-nitro-L-arginine and methylene treatment. Conclusion : THis study showed that Geupoongjibo-dan's relaxation effect on a blood vessel is irrelevant to ${\alpha}$-adrenalin receptor, and it relaxes contracted vessels through cGMP channel.

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Hydrothermal Kinetics and Mechanisms of Lime and Quartz Used Solid State Reaction Equations (고상반응식을 이용한 석회-석영의 수열반응속도와 반응메카니즘)

  • Lim, Going
    • The Journal of Engineering Research
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    • v.3 no.1
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    • pp.223-233
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    • 1998
  • The kinetic and mechanism of the hydrothermal reaction between lime and quartz used solid state reaction equations have been investigated. Hydrothermal reaction on the starting materials was carried out in an autoclave that quartz mixed with calcium hydroxide in CaO/$SiO_2$ ratio of 0.8-1.0 for 0.5-8 hour at saturated steam pressure of $180-200^{\circ}C$. The rate of reaction was given from the ratio of uncombined lime and quartz content to the total lime and quartz content. The rate of reaction was obtained the results by the Jander's equation $[1-(1-\alpha)^{1/3}]^N=Kt$. The reaction of lime is controlled mainly by the dissolution such as N=1, and the reaction of quartz is controlled mostly by the diffusion such as $N\risingdotseq2$. The rate of hydrothermal reaction in the calcium silicate hydrates system is suggested to be determined generally by the mass transfer through the product laver formed around the reactant particles. The rate equation for whole hydrothermal reaction is shown that it is converted into the rate determining step by the diffusion from the boundary reaction such as approximately $N=1-2$.

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Effects of 3-Phenyl-1-isoquinolinamine on the Metabolism of ${\beta}$-Amyloid Precursor Protein in Neuroblastoma Cells (3-페닐-1-이소퀴놀린아민이 신경세포에서 베타 아밀로이드 전구단백질의 대사에 미치는 영향)

  • Leem, Jae-Yoon;Cho, Won-Jea
    • YAKHAK HOEJI
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    • v.54 no.6
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    • pp.529-534
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    • 2010
  • Alzheimer's disease (AD) is characterized pathologically by the presence of intracellular neurofibrillary tangles and deposition of ${\beta}$-amyloid ($A{\beta}$) peptides, which are generated by processing of amyloid precursor protein (APP). It is urgent to develop effective therapies for the treatment of AD, since our society rapidly accelerate aging. $A{\beta}$ peptides have been believed to be neurotoxic and now are also considered to have effects on the mechanism of memory formation. Recently, we investigated that a quinoline compound from natural product reduced the secretion of $A{\beta}$ from the neuroblastoma N2a cells (NL/N cell line) overexpressing APPswe. In this study, 3-phenyl-1-isoquinolinamine, a synthetic isoquinoline compound was analyzed to determine its effects on the metabolism of APP. It inhibited the secretion of $A{\beta}$ peptides from the N2a NL/N cell line. Beta-site APP cleaving enzyme (BACE) fluorescence resonance energy transfer (FRET) assay revealed that it inhibited BACE activity in a dose dependent manner. Immunoblotting study showed that it inhibited APP stabilization and expression and it slightly increased the stablization and the expression of ${\gamma}$-secreatase component from the N2a NL/N cell line. We suggest that 3-phenyl-1-isoquinolinamine inhibits APP metabolism and $A{\beta}$ generation by the means of BACE inhibitory mechanism. This is the first report that 3-phenyl-1-isoquinolinamine inhibits the secretion of $A{\beta}$ peptides from neuroblastoma cells.