• Title/Summary/Keyword: G2-phase

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Theoretical Studies of the Gas-Phase Identity Nucleophilic Substitution Reactions of Cyclopentadienyl Halides

  • Lee, Ik-Choon;Li, Hong-Guang;Kim, Chang-Kon;Lee, Bon-Su;Kim, Chan-Kyung;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • v.24 no.5
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    • pp.583-592
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    • 2003
  • The gas phase identity nucleophilic substitution reactions of halide anions (X = F, Cl, Br) with cyclopentadienyl halides (1) are investigated at the B3LYP/6-311+G**, MP2/6-311+G** and G2(+)MP2 levels involving five reaction pathways: σ-attack $S_N2$, β-$S_N$2'-syn, β-$S_N$2'-anti, γ-$S_N$2'-syn and γ-$S_N$2'-anti paths. In addition, the halide exchange reactions at the saturated analogue, cyclopentyl halides (2), and the monohapto circumambulatory halide rearrangements in 1 are also studied at the same three levels of theory. In the σ-attack $S_N2$ transition state for 1 weak positive charge develops in the ring with X = F while negative charge develops with X = Cl and Br leading to a higher energy barrier with X = F but to lower energy barriers with X = Cl and Br than for the corresponding reactions of 2. The π-attack β-$S_N$2' transition states are stabilized by the strong $n_C-{\pi}^{*}_{C=C}$ charge transfer interactions, whereas the π-attack γ-$S_N$2' transition states are stabilized by the strong $n_C-{\sigma}^{*}_{C-X}$ interactions. For all types of reaction paths, the energy barriers are lower with X = F than Cl and Br due to the greater bond energy gain in the partial C-X bond formation with X = F. The β-$S_N$2' paths are favored over the γ-$S_N$2' paths only with X = F and the reverse holds with X = Cl and Br. The σ-attack $S_N2$ reaction provides the lowest energy barrier with X = Cl and Br, but that with X = F is the highest energy barrier path. Activation energies for the circumambulatory rearrangement processes are much higher (by more than 18 kcal $mol^{-1}$) than those for the corresponding $S_N2$ reaction path. Overall the gas-phase halide exchanges are predicted to proceed by the σ-attack $S_N2$ path with X = Cl and Br but by the β-$S_N$2'-anti path with X = F. The barriers to the gas-phase halide exchanges increase in the order X = F < Br < Cl, which is the same as that found for the gas-phase identity methyl transfer reactions.

Formation of D-Glucose Isomerase by Streptomyces sp. (Streptomyces sp.에 의한 포도당 이성화효소의 생성)

  • Rhee, In-Koo;Seu, Jung-Hwn
    • Microbiology and Biotechnology Letters
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    • v.8 no.3
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    • pp.173-180
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    • 1980
  • A source of D-xylose was required for the enhanced production of D-glucose isomerase of Streptomyces sp. strain K-17. D-glucose supported the luxuriant growth of the organism as well as D-xylose, but D-glucose isomerase activity was hardly detected in the D-glucose-grown cells. When the D-glucose-grown cells were incubated aerobically for a few hours in 0.5% xylose solution in 0.05 M phosphate buffer, pH 7.0, it was found that inductive formation of D-glucose isomerase occurred in the cells without multiplication. In the non-growth phase of cells the inductive formation of D-glucose isomerase occurred because a source of nitrogen for the synthesis of enzymes was obtained from turnover of protein accumulated in cells. D-ribose, L-arabinose, D-glucose, D-mannose, citrate, succinate and tartrate could not induce the formation of D-glucose isomerase, but D-xylose could induce. Inductinn of D-glucose isomerase was repressed by D-glucose and its catabolites : glycerol, succinate and citrate. Inductive formation of the enzymes in the non-growth phase was stimulated by $Ba^{2+}$, $Mg^{2+}$ and $Co^{2+}$, and inhibited by C $u^{2+}$, C $d^{2+}$, A $g^{+}$and H $g^{2+}$. The synthesis of enzymes in the induction system composed of 0.5% xylose solution was disrupted by actinomycin D, streptomycin, chloramphenicol, kanamycin, tetracycline, p-chloromercuribenzo ate, arsenate and 2, 4-dinitrophenol, but not disrupted by mitomycin C and penicillin G.icillin G.

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Determination of Adsorption Isotherms of Hydrogen on Zirconium in Sulfuric Acid Solution Using the Phase-Shift Method and Correlation Constants

  • Chun, Jang-H.;Chun, Jin-Y.
    • Journal of the Korean Electrochemical Society
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    • v.12 no.1
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    • pp.26-33
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    • 2009
  • The phase-shift method and correlation constants, i.e., the unique electrochemical impedance spectroscopy (EIS) techniques for studying the linear relationship between the behavior ($-{\varphi}$ vs. E) of the phase shift ($90^{\circ}{\geq}-{\varphi}{\geq}0^{\circ}$) for the optimum intermediate frequency and that ($\theta$ vs. E) of the fractional surface coverage ($0{\leq}{\theta}{\leq}1$), have been proposed and verified to determine the Langmuir, Frumkin, and Temkin adsorption isotherms of H and related electrode kinetic and thermodynamic parameters at noble metal (alloy)/aqueous solution interfaces. At a Zr/0.2 M ${H_2}{SO_4}$ aqueous solution interface, the Frumkin and Temkin adsorption isotherms ($\theta$ vs. E), equilibrium constants (K = $1.401{\times}10^{-17}\exp(-3.5{\theta})mol^{-1}$ for the Frumkin and K = $1.401{\times}10^{-16}\exp(8.1{\theta})mol^{-1}$ for the Temkin adsorption isotherm), interaction parameters (g = 3.5 for the Frumkin and g = 8.1 for the Temkin adsorption isotherm), rates of change of the standard free energy (r = $8.7\;kJ\;mol^{-1}$ for g = 3.5 and r = $20\;kJ\;mol^{-1}$ for g = 8.1) of H with $\theta$, and standard free energies ($96.13{\leq}{\Delta}G^0_{\theta}{\leq}104.8\;kJ\;mol^{-1}$ for K = $1.401{\times}10^{-17}\exp(-3.5{\theta})mol^{-1}$ and $0{\leq}{\theta}{\leq}1$ and ($94.44<{\Delta}G^0_{\theta}<106.5\;kJ\;mol^{-1}$ for K = $1.401{\times}10^{-16}\exp(-8.1{\theta})mol^{-1}$ and $0.2<{\theta}<0.8$) of H are determined using the phase-shift method and correlation constants. At 0.2 < $\theta$ < 0.8, the Temkin adsorption isotherm correlating with the Frumkin adsorption isotherm, and vice versa, is readily determined using the correlation constants. The phase-shift method and correlation constants are probably the most accurate, useful, and effective ways to determine the adsorption isotherms of H and related electrode kinetic and thermodynamic parameters at highly corrosion-resistant metal/aqueous solution interfaces.

3-Phase and 2-Phase Modulated SRP-PWM Technique with a Fixed Frequency for Power Electronics Converters (전력전자 변환장치를 위한 고정 스위칭 주파수로 동작하는 3상 및 2상 변조 SRP-PWM기법)

  • Oh S. Y.;Jung Y. G.;Lim Y. C.;Wi S. O.
    • Proceedings of the KIPE Conference
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    • 2004.07a
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    • pp.397-401
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    • 2004
  • In this paper, Inverter drives adopting 3-phase and 2-phase SRP-PWM (Separately Randomized Pulse Position PWM) with fixed switching frequency is proposed. In the proposed SRP-PWM scheme, each of 3 or 2 phase pulses Is located randomly in each switching interval. The experimental results show that the voltage / current harmonics and the switching noise harmonics are spread to a wide band area. Also, the performance of the 3-phase SRP-PWM and the 2-phase SRP-PWM are compared to each other. In result, the speed response is nearly similar to each other from the viewpoint of the v/f constant control.

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Thermal Stability of Cesium Reacted with Fly Ash in Hydrogen Atmosphere (환원분위기하 석탄회 세슘 반응생성물의 열적 안정성)

  • Shin Jin-Myeong;Kim Kwang-Ryul;Park Jang-Jin;Shin Seol-Woo
    • Journal of environmental and Sanitary engineering
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    • v.19 no.4 s.54
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    • pp.1-8
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    • 2004
  • This study has been investigated to analyze the thermal stability of cesium reacted with fly ash with changing mole ratio of Cs/Al in hydrogen atmosphere. When the $CsNO_3$ and fly ash were reacted at $1000^{\circ}C$ in hydrogen atmosphere, cesium $nepheline(CsAlSiO_4)$ Phase began to emerge in addition to $pollucite(CsAlSi_2O_6)$ phase when the cesium loading quantity was greater than $0.32(g-Cs_2O/g-fly\; ash)$. Cesium $nepheline(CsAlSiO_4)$ Phase increased with increasing cesium loading quantity. When cesium trapped on a fly ash was exposed to $1200^{\circ}C$ in hydrogen atmosphere, no weight loss due to the volatilization was shown until the cesium loading quantity was reached at $0.32(g-Cs_2O/g-fly\; ash)$. In the case of the cesium loading quantity of $0.48-0.74(g-Cs_2O/g-fly\;ash)$ in hydrogen atmosphere, the weight loss increased with increasing the cesium loading quantity. This is considered to be due to the cesium $nepheline(CsAlSiO_4)$ whose vapor pressure is higher than that of $pollucite(CsAlSi_2O_6)$.

Rapid Isolation of Cyanidin 3-Glucoside and Peonidin 3-Glucoside from Black Rice (Oryza sativa) Using High-Performance Countercurrent Chromatography and Reversed-Phase Column Chromatography

  • Jeon, Heejin;Choi, Janggyoo;Choi, Soo-Jung;Lee, Chang Uk;Yoon, Shin Hee;Kim, Jinwoong;Yoon, Kee Dong
    • Natural Product Sciences
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    • v.21 no.1
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    • pp.30-33
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    • 2015
  • Anthocyanins are water soluble plant pigments which are responsible for the blue, red, pink, violet colors in several plant organs such as flowers, fruits, leaves and roots. In recent years, anthocyanin-rich foods have been favored as dietary supplements and health care products due to diverse biological activities of anthocyanins including antioxidant, anti-allergic, anti-diabetic, anti-microbial, anti-cancer and preventing cardiovascular disease. High-performance countercurrent chromatography (HPCCC) coupled with reversed-phase medium pressure liquid chromatography (RP MPLC) method was applied for the rapid and efficient isolation of cyanidin 3-glucoside (C3G) and peonidin 3-glucoside (P3G) from black rice (Oryza sativa L., Poaceae). The crude black rice extract (500 mg) was subjected to HPCCC using two-phase solvent system composed of tert-butyl methyl ether/n-butanol/ acetonitrile/0.01% trifluoroacetic acid (TBME/B/A/0.01% TFA, 1 : 3 : 1 : 5, v/v, flow rate - 4.5 mL/min, reversed phase mode) to give enriched anthocyanin extract (37.4 mg), and enriched anthocyanin extract was sequentially chromatographed on RP-MPLC to yield C3G (16.5 mg) and P3G (8.7 mg). The recovery rate and purity of isolated C3G were 76.0% and 98.2%, respectively, and those of P3G were 58.3% and 96.3%, respectively. The present study indicates that HPCCC coupled with RP-MPLC method is more rapid and efficient than multi-step conventional column chromatography for the separation of anthocyanins.

Characterization of FePtN Nano-particles Synthesized by Thermal Decomposition and Mixed-gas Nitrification (열분해법과 혼합가스 질화법으로 합성한 FePtN 나노 입자의 특성)

  • Oh, Young Woo
    • Journal of the Korean Magnetics Society
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    • v.26 no.4
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    • pp.129-132
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    • 2016
  • The effect of thermal-nitrification on L1o transfomation in nano-sized FePt particles was studied. As-synthesized FePt nanoparticles by thermal decomposition method have fcc structured phase and their Hc and Ms were 247.34 Oe and 27.308 emu/g, respectively. According to the XRD analysis, phase transformation from fcc (face centered cubic) to fct (face centered tetragonal) structure was revealed by heating under $NH_3+H_2$ mixed-gas atmosphere. Also a slight shift of each (111) peak indicated phase transformation from fcc to fct structure. Hc and Ms of fct FePtN were 1058.2 Oe and 32.718 emu/g, respectively. The nano-sized FePtN magnetic particles synthesized by thermal decomposition method and mixed-gas nitrification are expected for advanced applications such as high density magnetic recording media and biomedical materials.

Qualitative Enzyme-Linked Immunosorbent Assay (ELISA) for the Diagnosis of Edwardsiellosis (Edwardsiellosis의 진단을 위한 정성적 ELISA법)

  • Kim, Myoung-Sug;Hwang, Eun-A;Huh, Min-Do;Jeong, Hyun-Do
    • Journal of fish pathology
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    • v.12 no.1
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    • pp.24-31
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    • 1999
  • Optimization and standardization of solid phase enzyme immunoassay were done for the diagnosis of edwardsiellosis in fish. The analyzed degree of immobilized antibody on surface of solid phase with peroxidase saturation method showed the optimized result by using partially purified $50{\mu}g/ml$ of rabbit anti-E. tarda Edk-2 antibody in sodium bicarbonate buffer for overnight incubation to cover the surface of polystyrene beads. Optimized immunoreaction was observed in the treatment of $50{\mu}g/ml$ of biotin conjugated antibody followed extravidin-peroxidase diluted 1 : 2,000 in PBS. The detectable concentrations of the this method were $1{\times}10^5$ cells/ml and $1{\times}10^5$ cells/ml expressed as the source of antigen amount for EDTA extraction and heat extraction, respectively. High cross-reaction of solid phase ELISA with the prepared rabbit and-E. tarda Edk-2 was observed against E. tarda strains isolated from flounder suffering from edwardsiellosis in aquatic farms of Korea. It suggested that the potential of this solid phase of ELISA technique is very powerful for the application to different strains of E. tarda isolated in farms of many different areas.

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Analysis Method of N-Nitrosamines in Human Urine by LC-MS/MS System (LC-MS/MS 시스템을 이용한 소변 중 N-니트로사민류 분석법 확립)

  • Park, Na-Youn;Jung, Woong;Kho, Younglim
    • Journal of the Korean Chemical Society
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    • v.61 no.2
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    • pp.51-56
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    • 2017
  • N-nitrosamines are the nitroso compounds which are produced by nitrosation reactions of the secondary amine and nitrite under acidic conditions. Approximately 300 species of N-nitrosamine have been tested for carcinogenicity in laboratory experiments, with 90% of them demonstrated carcinogenic effects different animal species, including higher primates. In 1978, IARC classified NDMA and NDEA as Group 2A, and NDPA, NDBA, NPIP, NPYR and NMOR as Group 2B. In this study, we established pretreatment and analytical method for N-nitrosamines (NDMA, NDEA, NMEA, NDPA, NDBA, NPIP, NPYR and NMOR) in human urine for biological monitoring of N-nitrosamines. The analytes were extracted using solid phase extraction (SPE), then quantitative analysis was performed by LC-(APCI)-MS/MS. The accuracies of the established method were between 85.8~108.7% and precisions were lower than 20%. The limit of detection (LOD) were between 0.0002 (NDBA) and 0.0793 (NDMA) ng/ml. The linearity obtained was satisfying for the 8 N-nitrosamines, with a coefficient of determination ($r^2$) higher than 0.999. The mean concentrations of N-nitrosamines in the urine were 2.645 mg/g creatinine for NDMA, 0.067 mg/g creatinine for NDEA, 0.009 mg/g creatinine for NMEA, 0.011 mg/g creatinine for NDBA, 0.271 mg/g creatinine for NPIP and 0.413 mg/g creatinine for NPYR. NDPA and NMOR were not detected. It can be used as a instrumental methodology for evaluation and risk assessment of human exposure to N-nitrosamines for the further research.

Effect of Glucose Concentration on the Production of Erythritol by Trichosporon sp.

  • Park, Jin-Byung;Seo, Byung-Cheol;Kim, Jung-Ryul;Pek, Un-Hua;Park, Yong-Kun
    • Journal of Microbiology and Biotechnology
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    • v.8 no.5
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    • pp.543-546
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    • 1998
  • The effect of glucose concentration on the production of erythritol by Trichosporon sp. was mainly studied. The specific growth rate and production rate of erythritol gave the highest values of $0.23 h^{-1}\; and\; 4.2 g/\ell/h,\; respectively,\; on\; 100 g \; glucose/\ell$ of medium. The conversion yield of erythritol during the exponential phase and the stationary phase was constantly maintained at 19% and 51 %, respectively, while the glucose concentration in the medium varied from 100 g/$\ell$ to 400 g/$\ell$. The maximum overall erythritol conversion yield of 47% was obtained when the glucose concentration in the medium was 400 g/$\ell$. It corresponded to a 74% increase compared with the 100 g/$\ell$ glucose medium. The diauxy growth of this microbe was also observed. It grew exponentially consuming glucose, then after the second lag phase, biomass slowly increased using glycerol and erythritol.

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