• Title/Summary/Keyword: sigma ($\sigma$) phase

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Theoretical Studies on the Gas-Phase Nucleophilic Aromatic Substitution Reaction

  • Lee, Ik-Choon;Park, Hyoung-Yeon;Bon-Su Lee
    • Bulletin of the Korean Chemical Society
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    • v.12 no.6
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    • pp.658-661
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    • 1991
  • The gas-phase nucleophilic substitution reaction of pentafluoroanisole with $OH^-$ and ${NH_2}^-$ nucleophiles have been studied theoretically using the AM1 method. Three reaction channels, $S_N2$, IPSO and $S_NAr$ (scheme 1), are all very exothermic so that all are accessible despite the varying central energy barriers which are much lower than the reactants level. In the IPSO and $S_NAr$ channels, the reactants form directly a stable ,${\sigma}$-anion complex which proceeds to form a proton transfer complex via a transition barrier corresponding to a loose ${\pi}$-type complex with the F-(or ${OCH_3}^-$) leaving group. Due to a greater number of probable reaction sites available for $S_NAr$ compared to the other two processes, the $S_NAr$ channel is favored as experimentally observed.

A Study for the Effect of Solvent and Temperature on the Retention Behavior of Phenols in Reversed-Phase Liquid Chromatography (역상 액체 크로마토그래피에서 페놀류의 머무름거동에 미치는 용매와 온도의 영향에 관한 연구)

  • Lee Dai Woon;Lee Hoo Keun;Yook Keun Sung;Lee, In Ho;Cho Byung Yun
    • Journal of the Korean Chemical Society
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    • v.37 no.5
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    • pp.503-512
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    • 1993
  • The purpose of this study was to investigate the retention behavior of phenols and to predict their retention in RPLC. The retention data of twenty-five phenols were measured on a $\mu-{Bondapak}\;C_{18}$ and a polymeric $C_{18}$ columns with methanol-water and acetonitrile-water as a mobile phase. From the observation of enthalpy-entropy compensation phenomenon, the following conclusions are drawn with regard to the retention mechanism: 1) the retention mechanism of nitrophenols in different from that of metheyl-and chlorophenols in both mobile phase; 2) in methanol-water mobile phase, the retention mechanism of methyl-and chlorophenols is consistent in the range of methanol-water composition; 3) on the other hand, in the case of acetonitrile-water mobile phase, the retention mechanism depends on the volume fraction of acetonitrile. It means that the retention mechanism can not be explained only by a simple interaction. Based on retention data as compared with two columns, it may be said that the hydrophobic interaction of phenols with polymeric $C_{18}$ column was greater than that with monomeric $C_{18}$ column. The equations for predicting the retention of phenols were derived by using hydrophobic substituent constant $(\pi)$ and the sum of Hammett's constant $(\sigma)$ and Taft's steric constant $(E_s)$.

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A Fractional-N Phase Locked Loop with Multiple Phase Frequency Detector (Fractional 스퍼 감쇄 위상/주파수검출기를 이용한 fractional-N 주파수 합성기)

  • Choi, Young-Shig;Choi, Hyek-Hwan
    • Journal of the Korea Institute of Information and Communication Engineering
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    • v.15 no.11
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    • pp.2444-2450
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    • 2011
  • In this paper, we propose the low fractional spur phase-locked loop(PLL) with multiple phase-frequency detector(PFD). The fractional spurs are suppressed by using a new PFD. The new PFD architecture with two different edge detection methods is used to suppress the fractional spur by limiting a maximum width of the output signals of PFD. The proposed PLL was simulated by HSPICE using a 0.35m CMOS parameters. The simulation results show that the proposed PLL is able to suppress fractional spurs with fast locking.

Functional Analysis of an Antibiotic Regulatory Gene, afsR2 in S. lividans through DNA microarray System (DNA 마이크로어레이 시스템 분석을 통한 S. lividans 유래 항생제 조절유전자 afsR2 기능 분석)

  • Kim, Chang-Young;Noh, Jun-Hee;Lee, Han-Na;Kim, Eung-Soo
    • KSBB Journal
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    • v.24 no.3
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    • pp.259-266
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    • 2009
  • AfsR2 in Streptomyces lividans, a 63-amino acid protein with limited sequence homology to Streptomyces sigma factors, has been known for a global regulatory protein stimulating multiple antibiotic biosynthetic pathways. Although the detailed regulatory mechanism of AfsK-AfsR-AfsR2 system has been well characterized, very little information about the AfsR2-dependent down-stream regulatory genes were characterized. Recently, the null mutant of afsS in S. coelicolor (the identical ortholog of afsR2) has been characterized through DNA microarray system, revealing that afsS deletion regulated several genes involved in antibiotic biosynthesis as well as phosphate-starvation. Through comparative DNA microarray analysis of afsR2-overexpressed S. lividans, here we also identify several afsR2-dependent genes involved in phosphate starvation, morphological differentiation, and antibiotic regulation in S. lividans, confirming that the AfsR2 plays an important pleiotrophic regulatory role in Streptomyces species.

The global regulator GacS of a biological bacterium Pseudomonas chlororaphis O6 regulates expression of the stationary-phase sigma factor rpoS and reduces survival in oxidative stress.

  • Kang, Beom-Ryong;Cho, Baik-Ho;Kim, Young-Cheol
    • Proceedings of the Korean Society of Plant Pathology Conference
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    • 2003.10a
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    • pp.100.2-101
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    • 2003
  • The global regulator, GacS (global antibiotic and cyanide sensor kinase), was required for the increased resistance to hydrogen peroxide occurring as cultures of the rhizobacterium, P. chlororaphis O6, matured. Specific stationary-phase peroxidase and catalase isozymes were absent in the GacS mutant, whereas a manganese-superoxide dismutase isozyme was expressed earlier and to a great extent than wild type. In the wild type cell, transcript accumulation of rpoS was higher in late logarithmic-phase cells than cells from mid logarithmic- or stationary-phase. Transcripts from rpoS in the GacS mutant were reduced in each of these growth phases compared to the wild type expression. The down stream sequence from rpoS lacked sequences encoding a small RNA, rsmZ, found in other pseudomonads and implicated in control of genes activated by the GacS system. These findings suggest that GacS-mediated regulation of RpoS plays role in control of oxidative stress in P. chlororaphis O6 by as yet an unknown mechanism.

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DFT/B3LYP Study of the Substituent Effects on the Reaction Enthalpies of the Antioxidant Mechanisms of Magnolol Derivatives in the Gas-Phase and Water

  • Najafi, Meysam;Najafi, Mohammad;Najafi, Houshang
    • Bulletin of the Korean Chemical Society
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    • v.33 no.11
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    • pp.3607-3617
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    • 2012
  • In this paper, the study of various ortho- and meta-substituted Magnolol derivatives is presented. The reaction enthalpies related to three antioxidant action mechanisms HAT, SET-PT and SPLET for substituted Magnolols have been calculated using DFT/B3LYP method in gas-phase and water. Calculated results show that electron-withdrawing substituents increase the bond dissociation enthalpy (BDE), ionization potential (IP) and oxidation/reduction enthalpy (O/RE), while electron-donating ones cause a rise in the proton dissociation enthalpy (PDE) and proton affinity (PA). In ortho- position, substituents show larger effect on reaction enthalpies than in meta-position. In comparison to gas-phase, water attenuates the substituent effect on all reaction enthalpies. In gas-phase, BDEs are lower than PAs and IPs, i.e. HAT represents the thermodynamically preferred pathway. On the other hand, SPLET mechanism represents the thermodynamically favored process in water. Results show that calculated enthalpies can be successfully correlated with Hammett constants (${\sigma}_m$) of the substituted Magnolols. Furthermore, calculated IP and PA values for substituted Magnolols show linear dependence on the energy of the highest occupied molecular orbital ($E_{HOMO}$).

Transcriptome Analysis of Bacillus subtilis by DNA Microarray Technique

  • Kang, Choong-Min;Yoshida, Ken-Ichi;Matsunaga, Masayuki;Kobayashi, Kazuo;Ueda, Minoru;Ogasawara, Naotake;Fujita, Yasutaro
    • Proceedings of the Korean Society of Life Science Conference
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    • 2000.06a
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    • pp.3-8
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    • 2000
  • The complete genome sequence of a Gram-positive bacterium .Bacillus subtilis has recently been reported and it is now clear that more than 50% of its ORFs have no known function (1). To study the global gene expression in B. subtilis at single gene resolution, we have tested the glass DNA microarrays in a step-wise fashion. As a preliminary experiment, we have created arrays of PCR products for 14 ORF whose transcription patterns have been well established through transcriptional mapping analysis. We measured changes in mRNA transcript levels between early exponential and stationary phase by hybridizing fluorescently labeled cDNA (with Cy3-UTP and Cy5-UTP) onto the array. We then compared the microarray data to confirm that the transcription patterns of these genes are well consistent with the known Northern analysis data. Since the preliminary test has been successful, we scaled up the experiments to ${\sim}$94% of the 4,100 annotated ORFs for the complete genome sequence of B. subtilis. Using this whole genomic microarray, we searched genes that are catabolite-repressive and those that are under the control of ${\sigma}^{Y}$, one of the functionally unknown ECF sigma factors. From these results, we here report that we have established DNA microarray techniques that are applicable for the whole genome of B. subtilis.

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Glass Forming Ability and Characteristic Evaluation in Ca-Mg-Zn Alloy System (Ca-Ma-Zn 합금계에서 비정질 형성능 및 특성 평가)

  • Park, Eun-Soo;Kim, Won-Tae;Kim, Do-Hyang
    • Journal of Korea Foundry Society
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    • v.26 no.2
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    • pp.77-84
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    • 2006
  • The effect of alloy composition on the glass forming ability (GFA) of the Ca-rich Ca-Mg-Zn alloys has been investigated in $Ca_{65}Mg_{5+x}Zn_{30-x}$ and $Ca_{55+x}Mg_{15}Zn_{30-x}$ (x=0, 5, 10, 15, 20) alloys. In a wide composition range of 15-25% Zn and 10-20% Mg bulk metallic glass (BMG) samples with the diameter larger than 6 mm are fabricated by conventional copper mold casting method in air atmosphere. Among the alloys investigated, the $Ca_{65}Mg_{15}Zn_{20}$ alloy exhibits the highest GFA enabling to form BMG sample with the diameter of at least 15 mm. The crystalline phase formed during solidification of $Ca_{65}Mg_{15}Zn_{20}$ ($D_{max}=15\;mm$) could be identified as a mixture of $Ca_3Zn$ and $CaMg_2$ cause by the redistribution of the constituent elements on long-range scale. The compressive fracture strength and fracture elongation of the $Ca_{65}Mg_{15}Zn_{20}$ BMG are 602 MPa and 2.08% respectively. The ${\sigma}$ parameter which has been recently proposed for evaluating GFA exhibits better correlation with GFA of Ca-Mg-Zn alloys than other parameters suggested so far such as ${\Delta}T_x$, $T_{rg}$, K, ${\gamma}$, and ${\Delta}T^*$ parameters.

Influence of truncated gaussian beam on read-out signal in optical disc (단락된 가우스 광이 광학 디스크 재생 신호에 미치는 영향)

  • 박성종;정창섭
    • Korean Journal of Optics and Photonics
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    • v.7 no.4
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    • pp.434-439
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    • 1996
  • To investigate influence of the incident beams which have the truncated Gaussian amplitude and of the shapes of bump on read-out signal is an optical disc, and the point spread function on bump, the scalar diffraction theory is used in this paper. We consider the truncated Gaussian amplitudes which are $\sigma$=0, 0.5, 1.5, and 2.5, the height of bump which is given by $n{\Delta}_0={\lambda}/4$, and the phase height of bump which is then given by ${\Phi}_0={\pi}$. We also consider the shapes of the bump which are a rectangular shape, a frustoconical shape, and a conical shape. It is shown that as the truncation of incident beam reduces the radius of central spot on bump decreases, the maximum value of read-out signal increases, and that the size of bump decreases. From these results, we get better read-out signal and the reduced cross-talk in optical disc when the truncation of incident beam reduces. Therefore a laser beam having less truncated Gaussian amplitude may useful for an actual optical disc.

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Theoretical Analysis on a Liquid-Liquid Static Extractor Using Highly Packed Fiber Bundle (고밀집 섬유 집합체를 이용한 정적 액-액 추출 장치의 이론적 해석)

  • Kim, Kwang-Wook;Byeon, Kee-Hoh;Lee, Eil-Hee;Yoo, Jae-Hyung;Park, Hyun-Soo
    • Applied Chemistry for Engineering
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    • v.8 no.3
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    • pp.416-424
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    • 1997
  • Mass transfer mechanism and concentration profiles in the axial direction at each phase were analyzed and simulated by a theoretical modeling on a liquid-liquid static contactor using highly packed fiber bundle. The concentrations at the end of the fiber extractor calculated at several operational conditions were compared with experimental results. The fiber extractor could be completely predicted by a plug flow model without axial dispersion. A parameter used in the model equations, $k_a{\sigma}$ called the product of mass transfer coefficient and mass transfer area per unit length of the fiber extractor in the axial direction, which was determined by a curve-fitting, was confirmed to be a unique characteristic value of the fiber extractor, and was about 0.0327cm2/sec.

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