• Title/Summary/Keyword: C-H activation

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Kinetics and Stereochemistry of CO Substitution Reactions of Half-Open Chromocene Carbonyls(Ⅰ): Reactions of Cp($C_{5}H_{7}$)CrCO and Phosphines

  • Chung, Jong-Jae;Roh, Byung-Gill;Park, Yu-Chul
    • Bulletin of the Korean Chemical Society
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    • v.14 no.2
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    • pp.207-211
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    • 1993
  • The CO substitution reactions in the complex, $Cp(S-C_5H_7)CrCO$ with $PR_3(PR_3=PMePh_2,\;P(OCH_3)_3,\;PMe_2Ph)$ were investigated spectrophotometrically at various temperatures. From the reaction rates, it was suggested that the CO substitution reaction takes place by first-order (dissociative) pathway. Activation parameters in decaline are ${\Delta}H^{\neq}\;=\;24.58\;kcal\;{\cdot}\;mol^{-1},\;{\Delta}S^{\neq}\;=\;3.05 cal\;{\cdot}\;mol^{-1}{\cdot}K^{-1}$. Unusually low value of ${\Delta}S^{\neq}$ suggests an ${\eta}^5-S\;{\to}\;{\eta}^5-U$ conversion of the pentadienyl ligand. This was confirmed by the extended-Huckel molecular orbital (EHMO) calculations, which revealed that the total energy Of $Cp(S-C_5H_7)CrCO$ is about 6.84 kcal/mol more stable than that of $Cp(U-C_5H_7)CrCO$ and the energy of $[Cp(U-C_5H_7)CrCO^{\neq}$ transition state is about 4.25 kcal/mol lower than that of $[Cp(S-C_5H_7)Cr]^{\neq}$ transition state.

Cation Flux-Mediated Activation of P-Type ATPase in Helicobacter pylori

  • Yun, Soon-Kyu;Ki, Mi-Ran;Park, Jeong-Kyu;Lim, Wang-Jin;Hwang, Se-Young
    • Journal of Microbiology and Biotechnology
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    • v.10 no.4
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    • pp.441-448
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    • 2000
  • The production and cation flux-mediated activation of the P-type ATPase in Helicobacter pylori was investigated. Using the polymerase chain reaction (PCR), the proton pump genotype of H. pylori was found to be positive for both F-type and P-type ATPases. Yet, their production in terms of enzyme specific activity varied substantially depending on H. pylori strains, ranging over 3-fold. Its main constituent appeared to be the P-type ATPase pool, in contrast to other common bacterial compositions. Interestingly, the F-type ATPase was observed only when intact H. pyloricells were exposed to pH 4.5 or above (37$^{\circ}C$ for 1 h). In contrast, significant amounts of the P-type ATPase still remained after 1 h of cell treatment even at pH below 4.5. By enriching the acidic medium with RPMI(pH 3.0), the P-type ATPase was stabilized, accompained by inactivation of the F-type ATPase. Using H. pylori membrane vesicles, it was found that ammionia-mediated cation flux increased the rate of ATP hydrolysis by the P-type ATPase. Accordingly, these data strongly suggest that the P-type ATPase is involved or functions as an effective regulator for the cation flux across the H. pylori membrane, thereby reducing the risk of excess proton influx.

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Ethanol Extract of Ganoderma lucidum Augments Cellular Anti-oxidant Defense through Activation of Nrf2/HO-1

  • Lee, Yoo-hwan;Kim, Jung-hee;Song, Choon-ho;Jang, Kyung-jeon;kim, Cheol-hong;Kang, Ji-Sook;Choi, Yung-hyun;Yoon, Hyun-Min
    • Journal of Pharmacopuncture
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    • v.19 no.1
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    • pp.59-69
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    • 2016
  • Objectives: The mushroom Ganoderma lucidum has been widely used as a traditional herbal medicine for many years. Although several studies have focused on the anti-oxidative activity of this mushroom, the molecular mechanisms underlying its activity have not yet been clearly established. The present study investigated the cytoprotective effect of ethanol extract of Ganoderma lucidum (EGL) against oxidative stress (hydrogen peroxide, $H_2O_2$) and elucidated the underlying mechanisms in a C2C12 myoblast cell line. Methods: Oxidative stress markers were determined by using the comet assay to measure reactive oxygen species (ROS) generation and deoxyribonucleic acid (DNA) damage. Cell viability and Western blotting analyses were employed to evaluate the cellular response to EGL and $H_2O_2$ in C2C12 cells. Transfection with nuclear factor erythroid 2-related factor 2 (Nrf2)-specific small interfering ribonucleic acid (siRNA) was conducted to understand the relationship between Nrf2 expression and $H_2O_2$-induced growth inhibition. Results: The results showed that EGL effectively inhibited $H_2O_2$-induced growth and the generation of ROS. EGL markedly suppressed $H_2O_2$-induced comet-like DNA formation and phosphorylation of histone H2AX at serine 139 ($p-{\gamma}H2AX$), a widely used marker of DNA damage, suggesting that EGL prevented $H_2O_2$-induced DNA damage. Furthermore, the EGL treatment effectively induced the expression of Nrf2, as well as heme oxygenase-1 (HO-1), with parallel phosphorylation and nuclear translocation of Nrf2 in the C2C12 myoblasts. However, zinc protoporphyrin IX, a HO-1 inhibitor, significantly abolished the protective effects of EGL against $H_2O_2$-induced accumulation of ROS and reduced cell growth. Notably, transient transfection with Nrf2-specific siRNA attenuated the cytoprotective effects and HO-1 induction by EGL, indicating that EGL induced the expression of HO-1 in an Nrf2-dependent manner. Conclusion: Collectively, these results demonstrate that EGL augments the cellular anti-oxidant defense capacity through activation of Nrf2/HO-1, thereby protecting C2C12 myoblasts from $H_2O_2$-induced oxidative cytotoxicity.

Kinetics and Mechanism for Substitution of cis-[Co$(NH_3)_4$Cl($H_2O$)]$^{2+}$ and GlyOR (R = $C_2H_5$, $CH_3$, H) in Acidic Solution (Ⅰ) (산성용액내에서 cis-[Co$(NH_3)_4$Cl($H_2O$)]$^{2+}$ 와 GlyOR (R = $C_2H_5$, $CH_3$, H)과의 치환반응에 대한 속도론적 연구(Ⅰ))

  • Lee, Il Bong;Mun, Jin Hui;Park, Byeong Gak
    • Journal of the Korean Chemical Society
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    • v.38 no.10
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    • pp.719-725
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    • 1994
  • Kinetic studies were carried out for substitution reaction of $cis-[Co(NH_3)_4Cl(OH_2)]^{2+}(\mu$ = 0.75) with GlyOR (R = $C_2H_5$, $CH_3$, H) in pH 5 buffer solution at $20^{\circ}C$ by UV/Vis-spectrophotometry. We obtained cis-[Co$(NH_3)_4$Cl(glyOR)]$^{2+}$ as product. The reaction turns out to be first order for Co(III) and GlyOR, respectively. The rate constants are obtained as 9.21, 11.66 and 15.33 l${\cdot}\;mol^{-1}{\cdot}sec^{-1}$ for GlyOEt, GlyOMt and GlyOH, respectively. The activation parameters $E_a,\;{\Delta}H^{\neq}\;and\;{\Delta}S^{\neq}$ for GlyOEt were obtained as 65.77, 63.35 kJ/mol and -53.51(e.u.), respectively and were obtained as 70.91, 68.50 kJ/mol and -38.42(e.u.) for GlyOMt. In case of GlyOH, respectable values of 79.72, 77.30 kJ/mol and -26.59(e.u.) were obtained. On the basis of kinetic data and the observed activation parameters, we propose that the proper mechanism involves $S_N$2 step.

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Effect of Temperature, pH and Sugars on Kinetic Property of Maillard reaction (당의 종류, pH 및 온도가 마이야르 반응속도에 미치는 영향)

  • Chun, Young-Hye;Kim, Chong-Kun;Kim, Woo-Jung
    • Korean Journal of Food Science and Technology
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    • v.18 no.1
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    • pp.55-60
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    • 1986
  • The effects of temperature (70-$100^{\circ}C$), pH (3-8) and various sugars were investigated on the reaction rate, activation energy and z-value of Maillard reaction of 0.8m sugar and 0.8m glycine mixture. The sugars compared were glucose, fructose, lactose and sucrose, and the reaction was evaluated by absorbances at 278nm for pyrazine compounds and at 400nm for brown pigments. Fructose-glycine mixture showed a faster initial reaction rate than that of glucose-glycine, which was reversed by the order of glucose > fructose > lactose > sucrose after 10 hrs of reaction at pH 5.8 and $100^{\circ}C$. Generally, higher activation energy was required for forming pyrazines than that of brown pigment development. The highest z-value was obtained for lactose-glycine mixture, followed by glucose or fructose-glycine which had almost same z-value. The reaction rate was little affected by the pH change in the range of 4-6, while pH < 3 and pH 6-8 caused a significant increase in the rates.

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cDNA cloning of a membrane-associated. magnesium-dependent 30kDa neutral sphingomyelinase

  • Jeon, Hyung-Jun;Jung, Sung-Yun;Kim, Dae-Kyong
    • Proceedings of the PSK Conference
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    • 2002.10a
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    • pp.328.1-328.1
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    • 2002
  • A major lipid-signaling pathway in mammalian cells implicated the activation of sphingomyelinase (SMase), which hydrolyses sphingomyeline to generate ceramide and phosphocholine. Sphingomyelinase is divided into many isoform groups dependent on optimal pH, and essential cation especially magnesium in their activation. Such as acidic sphingomyelinase, neutral sphingomyelinase and alkaline sphingomyelinase. Ceramide is known as a crucial second messenger in cell responses like cell proliferation. cell cycle arrest. cellular senescence, and apoptosis. (omitted)

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Early Development of Parthenogenetically Activated Porcine Oocyte after In Vitro Maturation for Various Periods (난자성숙시간에 따른 처녀발생유기 돼지난자의 초기발생)

  • Kim, S. B.;Lee, H.;Byun, T. H.;Jeon, J. T.;Lee, S. H.;Song, H. B.
    • Journal of Embryo Transfer
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    • v.9 no.1
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    • pp.117-125
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    • 1994
  • In vitro development of parthenogenetic embryo was examined after ethanol treatment of follicular oocytes matured in vitro for 42, 48, 54 and 60h in the pig. The follicular oocytes were matured in TCM 199 containing 15% FCS and gonadotrophins in an atmosphere of 39 $^{\circ}C$ 5% $CO_2$. The cumulus-free oocytes were activated by 10% ethanol treatment in M2+4mg /ml BSA for 10 min. The ethanol-activated oocytes were washed and further cultured in TCM199+20%FCS containing granulosa cell monolayer. Maturation rates at 42, 48, 54 and 60h of IVM were 75.0, 86.5, 81.6 and 87.9%, respectively. Thus the oocytes maturated in vitro for longer periods did not improve nuclear maturation much. Pronuclear formation rates at 18h post-activation in ethanol-activated oocytes were 21.9, 25.0, 47.4 and 32.6%. The cytoplasmic maturation leading to pronuclear formation upon activation increased when the I VM period was extended from 42 to 54h. When the activated oocytes were cultured for 96~120h to analyse early development of the activated oocytes, the rates of embryonic development upto $\leq$ 5~8 cell were 5.3, 5.8, 12.0 and 11.7% among the cultured embryos. The result indicate that earlier development of activated porcine occyte is dependent on the duration of oocyte maturation, and that better development could be obtained from the oocyte matured for 54h.

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A Study on the Prediction of Quality Chanties of Citrus unshiu during Short-term Storage and Marketing (조생온주 밀감의 단기 저장 및 유통 중 품질변화 예측을 위한 연구)

  • 정신교;이재호
    • Food Science and Preservation
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    • v.4 no.2
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    • pp.123-130
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    • 1997
  • To develop the prediction program for quality change of Citrus unshiu during marketing, we examined the quality characteristics of Citrus unshiu stored at experimental refrigerator set to 4, 8, 12 and 16$^{\circ}C$ for 2 months. According to the storage temperature the changes of quality characteristics were different respectively, but it was most severe during 16$^{\circ}C$ storage. Activation energy and Q10 value were 6683.16 cal/mol K and 1.53 respectively. The determination coefficient of regression equation of pH, acidity and vitamin C by surface response analysis were over 0.85. Using these regression equation, we developed the prediction program for the change of pH, acidity and vitamin C contents. The calculated values and experimental values of pH, acidity and vitamin C contents for short-term storage of Citrus unshiu were coincided well.

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Adsorbed Carbon Formation and Carbon Hydrogenation for CO2 Methanation on the Ni(111) Surface: ASED-MO Study

  • Choe, Sang-Joon;Kang, Hae-Jin;Kim, Su-Jin;Park, Sung-Bae;Park, Dong-Ho;Huh, Do-Sung
    • Bulletin of the Korean Chemical Society
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    • v.26 no.11
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    • pp.1682-1688
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    • 2005
  • Using the ASED-MO (Atom Superposition and Electron Delocalization-Molecular Orbital) theory, we investigated carbon formation and carbon hydrogenation for $CO_2$ methanation on the Ni (111) surface. For carbon formation mechanism, we calculated the following activation energies, 1.27 eV for $CO_2$ dissociation, 2.97 eV for the CO, 1.93 eV for 2CO dissociation, respectively. For carbon methanation mechanism, we also calculated the following activation energies, 0.72 eV for methylidyne, 0.52 eV for methylene and 0.50 eV for methane, respectively. We found that the calculated activation energy of CO dissociation is higher than that of 2CO dissociation on the clean surface and base on these results that the CO dissociation step are the ratedetermining of the process. The C-H bond lengths of $CH_4$ the intermediate complex are 1.21 $\AA$, 1.31 $\AA$ for the C${\cdot}{\cdot}{\cdot}H_{(1)}$, and 2.82 $\AA$ for the height, with angles of 105${^{\circ}}$ for ∠ $H_{(1)}$CH and 98${^{\circ}}$ for $H_{(1)} CH _{(1)}$.