• 제목/요약/키워드: The ${\alpha}$-Effect

검색결과 6,756건 처리시간 0.038초

The α-Effect in Nucleophilic Substitution Reactions of Y-Substituted-Phenyl X-Substituted-Cinnamates with Butane-2,3-dione Monoximate

  • Kim, Min-Young;Son, Yu-Jin;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • 제34권10호
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    • pp.2877-2882
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    • 2013
  • Second-order rate constants ($k_{Ox^-}$) have been measured spectrophotometrically for nucleophilic substitution reactions of 4-nitrophenyl X-substituted-cinnamates (7a-7e) and Y-substituted-phenyl cinnamates (8a-8e) with butane-2,3-dione monoximate ($Ox^-$) in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The Hammett plot for the reactions of 7a-7e consists of two intersecting straight lines while the Yukawa-Tsuno plot exhibits an excellent linearity with ${\rho}_X$=0.85 and r=0.58, indicating that the nonlinear Hammett plot is not due to a change in the rate-determining step but is caused by resonance stabilization of the ground state (GS) of the substrate possessing an electron-donating group (EDG). The Br${\o}$nsted-type plot for the reactions of Y-substituted-phenyl cinnamates (8a-8e) is linear with ${\beta}_{lg}$ = -0.64, which is typical of reactions reported previously to proceed through a concerted mechanism. The ${\alpha}$-nucleophile ($Ox^-$) is more reactive than the reference normal-nucleophile ($4-ClPhO^-$). The magnitude of the ${\alpha}$-effect (i.e., the $k_{Ox^-}/k_{4-ClPhO^-}$ ratio) is independent of the electronic nature of the substituent X in the nonleaving group but increases linearly as the substituent Y in the leaving group becomes a weaker electron-withdrawing group (EWG). It has been concluded that the difference in solvation energy between $Ox^-$ and $4-ClPhO^-$ (i.e., GS effect) is not solely responsible for the ${\alpha}$-effect but stabilization of transition state (TS) through a cyclic TS structure contributes also to the Y-dependent ${\alpha}$-effect trend (i.e., TS effect).

Effects of the Peroxisome Proliferator Ciprofibrate and Prostaglandin $F_2\alpha$ Combination Treatment on Second Messengers in Cultured Rat Hepatocytes

  • Hong, Jin-Tae;Yun, Yeo-Pyo
    • Archives of Pharmacal Research
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    • 제21권2호
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    • pp.120-127
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    • 1998
  • Peroxisome proliferators induce hepatic peroxisome proliferation and hepatic tumors in rodents. These chemicals increase the expression of the peroxisomal $\beta$-oxidation pathway and the cytochrome P-450 4A family, which metabolizes lipids, including eicosanoids. Peroxisome proliferators transiently induce increased cell proliferation in vivo. However, peroxisome proliferators are weakly mitogenic and are not co-mitogenic with epidermal growth factor (EGF) in cultured hepatocytes. Earlier study found that the peroxisome proliferator ciprofibrate is cornitogenic with eicosanoids. In order to study possible mechanisms of the comitogenicity of peroxisome proliferator ciprofibrate and eicosanoids' we hypothesized that the co-mitogenicity may result from synergistic or additive increases of second messengers in mitogenic signal pathways. We therefore examined the effect of the peroxisome proliferator ciprofibrate, prostaglandin $F_2_{\alpha}$($PGF_2{\alpha}$) and the combination of ciprofibrate and $PGF_2{\alpha}$ with or without growth factors on the protein kinase C (PKC) activity, and inositol-1, 4, 5-triphosphate ($IP_{3-}$) and intracellular calcium ($[Ca^{2+}]_i$) concentrations in cultured rat hepatocytes. The combination of ciprofibrate and $PGF_2{\alpha}$ significantly increased particulate PKC activity. The combination of ciprofibrate and $PGF_2{\alpha}$ also significantly increased EGF, transforming growth factor-$\alpha$ ($TGF_2{\alpha}$) and hepatic growth factor (HGF)-induced particulate PKC activity. The combination of ciprofibrate and $PGF_2_\alpha$greatly increased $[Ca^{2+}]_i$. However, the increases of PKC activity and $[Ca^{2+}]_i$ by ciprofibrate and $PGF_2{\alpha}$ alone were much smaller. Neither ciprofibrate or $PGF_2{\alpha}$ alone nor the combination of ciprofibrate and $PGF_2{\alpha}$ significantly increased the formation of $IP_3$. The combination of ciprofibrate and $PGF_2{\alpha}$, however, blocked the inhibitory effect of $TGF-{\beta}$ on particulate PKC activity and formation of $IP_3$ induced by EGF. These results show that co-mitogenicity of the peroxisome proliferator ciprofibrate and eicosanoids may result from the increase in particulate PKC activity and intracellular calcium concentration but not from the formation of $IP_3$.

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산소함량에 따른 Ti-Al-Fe-Si-O 합금의 기계적 특성 및 미세조직 변화 (The Effects of Oxygen Content on Microstructure and Mechanical Properties of Ti-Al-Fe-Si-O alloy)

  • 배진주;염종택;박찬희;홍재근;김성웅;윤석영;이상원
    • 열처리공학회지
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    • 제29권6호
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    • pp.264-271
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    • 2016
  • The effect of the oxygen content and the annealing temperature on the tensile behavior of the Ti-1.5Al-3Fe-0.25Si-(0.1~0.5)O alloy was investigated. The tensile properties were dependent on the volume fraction of the microstructure constituents, i.e. the equixed ${\alpha}$, equixed ${\beta}$ and lamellar ${\alpha}$. The results showed that the O-partitioned equixed ${\alpha}$ had a much higher strength compared to the equixed ${\beta}$. The strength of the lamellar ${\alpha}$ increased with increasing the annealing temperature because the O content of the lamellar ${\alpha}$ increased. Ti-1.5Al-3Fe-0.25Si-0.3O alloy annealed to $900^{\circ}C$ where the volume fraction of lamellar ${\alpha}$ was the highest exhibited an excellent combination of the strength (1198.5 MPa) and ductility (27.5%). The effect of the lamellar ${\alpha}$ on the ductility was discussed.

유청단백질 Glycomacropeptide에서 분리한 NANA의 안전성 및 염증저하 메카니즘 구명 연구 (Anti-inflammatory Effects and Its Mechanisms of NANA (N-Acylneuraminic Acid) Isolated from Glycomacropeptide)

  • 김민호;김재홍;이윤경;김완식;김희경
    • Journal of Dairy Science and Biotechnology
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    • 제29권2호
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    • pp.17-23
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    • 2011
  • The focus of this study was to clarify the relation between the nitric oxide (NO) production and cytokine expression including tumor necrosis factor-${\alpha}$ (TNF) and interleukin-6 (IL-6), and also investigated the effect of G-NANA (N-acylneuraminic acid isolates from glycomacropeptide) or S-NANA (Synthetic N-acylneuraminic acid) on LPS stimuli from RAW264.7 cell. The NANA is the predominant sialic acid found in mammalian cells and G-NANA is isolation of GMP (GMP is a valuable bioactive peptide with a varying degree of glycosylation including sialic acid). The lipopolysaccharide (LPS) of Gram-negative bacteria induces the expression of cytokines and potent inducers of inflammatory cytokines such as TNF-${\alpha}$ and IL-6. In this experiment, upon stimulation with increasing concentrations of chitosan, the LPS-stimulated TNF-${\alpha}$ and IL-6 secretion was significantly recovered with in the incubation media of RAW264.7 cells. Consistently, RT-PCR with mRNA and immunoblot analysis with anti-cytokine antiserum including TNF-${\alpha}$ and IL-6 showed that the amount of TNF-${\alpha}$ and IL-6 secretion in the incubation media recovered with the concentration of chitosan. The LPS-stimulated NO secretion was significantly recovered with in the 6 and 12 h incubation media of RAW264.7 cells, too. The recovery effect of G-NANA on IL-6 and NO secretion may be induced via the stimulus of TNF-${\alpha}$ in RAW264.7 cell. These results once again suggest that G-NANA may have the anti-inflammatory effect via the stimulus of TNF-${\alpha}$ in the LPS-stimulated inflammation in RAW264.7 cells.

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The activation of α2-adrenergic receptor in the spinal cord lowers sepsis-induced mortality

  • Kim, Sung-Su;Park, Soo-Hyun;Lee, Jae-Ryung;Jung, Jun-Sub;Suh, Hong-Won
    • The Korean Journal of Physiology and Pharmacology
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    • 제21권5호
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    • pp.495-507
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    • 2017
  • The effect of clonidine administered intrathecally (i.t.) on the mortality and the blood glucose level induced by sepsis was examined in mice. To produce sepsis, the mixture of D-galactosamine (GaLN; 0.6 g/10 ml)/lipopolysaccharide (LPS; $27{\mu}g/27{\mu}l$) was treated intraperitoneally (i.p.). The i.t. pretreatment with clonidine ($5{\mu}g/5{\mu}l$) increased the blood glucose level and attenuated mortality induced by sepsis in a dose-dependent manner. The i.t. post-treatment with clonidine up to 3 h caused an elevation of the blood glucose level and protected sepsis-induced mortality, whereas clonidine post-treated at 6, 9, or 12 h did not affect. The pre-treatment with oral D-glucose for 30 min prior to i.t. post-treatment (6 h) with clonidine did not rescue sepsis-induced mortality. In addition, i.t. pretreatment with pertussis toxin (PTX) reduced clonidine-induced protection against mortality and clonidine-induced hyperglycemia, suggesting that protective effect against sepsis-induced mortality seems to be mediated via activating PTX-sensitive G-proteins in the spinal cord. Moreover, pretreatment with clonidine attenuated the plasma tumor necrosis factor ${\alpha}$ ($TNF-{\alpha}$) induced by sepsis. Clonidine administered i.t. or i.p. increased $p-AMPK{\alpha}1$ and $p-AMPK{\alpha}2$, but decreased p-Tyk2 and p-mTOR levels in both control and sepsis groups, suggesting that the up-regulations of $p-AMPK{\alpha}1$ and $p-AMPK{\alpha}2$, or down-regulations of p-mTOR and p-Tyk2 may play critical roles for the protective effect of clonidine against sepsis-induced mortality.

Reduction of TNE ${\alpha}-induced$ Oxidative DNA Damage Product, 8-Hydroxy-2'-Deoxyguanosine, in L929 Cells Stably Transfected with Small Heat Shock Protein

  • Park, Young-Mee;Choi, Eun-Mi
    • The Korean Journal of Physiology and Pharmacology
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    • 제1권2호
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    • pp.209-219
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    • 1997
  • Previous studies have demonstrated that oxidative stress involving generation of reactive oxygen species (ROS) is responsible for the cytotoxic action of $TNF{\alpha}$. Protective effect of small heat shock proteins (small HSP) against diverse oxidative stress conditions has been suggeted. Although overexpression of small hsp was shown to provide an enhanced survival of $TNF{\alpha}$-sensitive cells when challenged with $TNF{\alpha}$, neither the nature of $TNF{\alpha}$-induced cytotoxicity nor the protective mechanism of small HSP has not been completely understood. In this study, we have attempted to determine whether $TNF{\alpha}$ induces oxidative DNA damage in $TNF{\alpha}$-sensitive L929 cells. We chose to measure the level of 8-hydroxy-2'-deoxyguanosine (8 ohdG), which has been increasingly recognized as one of the most sensitive markers of oxidative DNA damage. Our results clearly demonstrated that the level of 8 ohdG increased in L929 cells in a $TNF{\alpha}$ dose-dependent manner. Subsequently, we asked whether small HSP has a protective effect on $TNF{\alpha}$-induced oxidative DNA damage. To accomplish this goal, we have stably transfected L929 cells with mouse small hsp cDNA (hsp25) since these cells are devoid of endogenous small hsps. We found that $TNF{\alpha}$-induced 8 ohdG was decreased in cells overexpressing exogenous small hsp. We also found that the cell killing activity of $TNF{\alpha}$ was decreased in these cells as measured by clonogenic survival. Taken together, results from the current study show that cytotoxic mechanism of $TNF{\alpha}$ involves oxidative damage of DNA and that overexpression of the small hsp reduces this oxidative damage. We suggest that the reduction of oxidative DNA damage is one of the most important protective mechanisms of small HSP against $TNF{\alpha}$.

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Bisphenol A가 점 망둑 (Chasmichthys dolichognothus)의 난소 스테로이드 호르몬 대사에 미치는 영향 (Effect of Bisphenol A on Ovarian Steroidogenesis in Longchin Goby (Chasmichthys dolichognathus))

  • 백혜자;박명희;이영돈;김형배;김재원;유명숙
    • 한국수산과학회지
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    • 제37권3호
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    • pp.192-196
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    • 2004
  • The in vitro effect of bisphenol A (BPA) on ovarian steroidogenesis of the longchin goby (Chasmichthys dolichognathus) was investigated. Oocytes taken during the maturing phase (vitellogenic, fully vitellogenic or germinal vesicle breakdown stage) were incubated with BPA (100 ng/mL) in the presence of exogenous precursor $^{3}H-17\alpha\;hydroxyprogesterone\;(^{3}H-17\alphaOHP).$ Steroids were extracted from the media and the isolated oocytes, and the extracts were separated and identified by thin layer chromatography and gas chromatography-mass spectrometry. The identities of the major metabolites were progestogens $[17{\alpha}-hydroxy,20{\alpha}-dihydroprogesterone\;(17{\alpha}20{\alpha}OHP)\;and\;17{\alpha}-hydrxy,20{\beta}-dihydroprogesterone\;(17{\alpha}20{\beta}OHP),$ androgens [androstenedione (A4) and testosterone (T)] and estrogens [estrone $(E_1)\;and\;estradiol-17{\beta}(E_2)].$ BPA treatment inhibited production of estrogens in all the maturing phases and progestogens in the germinal vesicle migrating stage. Percentage yield of estrogens was decreased with increased yield of androgens. In conclusion, BPA had an inhibitory effect on the conversion of $^3H-17\alphaOHP$ to estrogens and progestogens. These results demonstrate that BPA can act either estrogenic or anti-estrogenic effects.

Lyα Radiative Transfer and The Wouthuysen-Field effect

  • 선광일;김창구
    • 천문학회보
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    • 제42권2호
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    • pp.43.1-43.1
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    • 2017
  • A three-dimensional (3D) $Ly{\alpha}$ radiative transfer code is developed to study the Wouthuysen-Field effect, which couples the 21 cm spin temperature of neutral hydrogen and the $Ly{\alpha}$ radiation field, and the escape fraction of $Ly{\alpha}$ from galaxies. The Monte Carlo code is capable of treating arbitrary 3D distributions of $Ly{\alpha}$ source, neutral hydrogen and dust densities, gas temperature, and velocity field. It is demonstrated that the resonance-line profile at the center approaches to the Boltzmann distribution with the gas temperature. A plane-parallel ISM model, which is appropriate for the neutral ISM of our Galaxy, is used to calculate the $Ly{\alpha}$ radiation field strength as a function of height above the galactic plane. We also use a two-phase, clumpy medium model which is composed of the cold and warm neutral media (WNM). It is found that the $Ly{\alpha}$ radiation field is strong enough to thermalize the 21 cm spin temperature in the WNM to the gas kinetic temperature. The escape fraction of $Ly{\alpha}$ is found to be a few percent, which is consistent with the $Ly{\alpha}$ observations of our Galaxy and external galaxies.

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고형상의 모델시스템에 있어서 리놀레산의 산화에 미치는 리폭시게나아제, 카로틴, 토코페롤 및 수분활성의 영향 (Effect of Lipoxygenase, ${\beta}-Carotene$, ${\alpha}-Tocopherol$ and Water Activity on the Oxidation of Linoleic Acid in Starch-Solid Model System)

  • 김혜경;최홍식;송영옥
    • 한국식품영양과학회지
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    • 제21권1호
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    • pp.23-28
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    • 1992
  • 고형상의 모델시스템에서 리놀레산의 산화에 영향을 미치는 여러가지 인자들 즉 리폭시게나아제, 수분활성도, ${\beta}$-카로틴, ${\alpha}$-토코페롤등에 대해 관찰하여 다음과 같은 결과를 얻었다. 리폭시게나아제에 의한 리놀레산의 산화반응은 aw 0.72에서 aw 0.25에 보다 잘 일어났다. 그러나 이 시스템에 ${\beta}$-카로틴이나 ${\alpha}$-토코페롤을 반응시키게 되면 리놀레산의 산화를 크게 저해하였으며 ${\beta}$-카로틴보다는 ${\alpha}$-토코페롤이 지질과 산화 과정에서 항산화작용이 더 컸다. 즉, 유사한 조건에서 ${\beta}$-카로틴은 24시간의 유도기간을 보여 준 반면 ${\alpha}$-토코페롤은 72시간까지도 유도기간이 지속되었다. ${\beta}$-카로틴의 항산화작용은 수분활성도의 영향을 크게 받았으며 수분활성도가 높을수록 항산화 작용이 뛰어났고 또한 ${\beta}$-카로틴의 농도가 높을수록 CDA 생성이 적었다.

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$\gamma$-알루미나부터 $\alpha$-알루미나 분말 제조에 있어 Seeding과 알루미나 졸이 미치는 영향 (Effect of $\alpha-Al_2O_3$ Seeds and Alumina Sol on $\alpha$-Alumina Powder Derived from $\gamma-Al_2O_3$)

  • 임경란;장진욱;임창섭;홍국선
    • 한국세라믹학회지
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    • 제32권4호
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    • pp.482-488
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    • 1995
  • The phase transformation temperature from $\theta$- to $\alpha$-alumina was lowered from 1214$^{\circ}C$ to 114$0^{\circ}C$ in DSC by treating ${\gamma}$-alumina obtained by calcination of boehmite at $700^{\circ}C$ for 2hrswith $\alpha$-Al2O3 seeds (d50=0.36${\mu}{\textrm}{m}$) and 3wt% of the alumina sol. $\alpha$-Al2O3 seeds seemed to lower to the transformation temperature and the alumina sol suppressed the high temperature agglormeration. The effect was increased as the amount of the sol was increased, which was supported by TEM and particle size distribution. For an example, spherical ${\gamma}$-alumina powder with d50=0.54${\mu}{\textrm}{m}$ was prepared by treating the ${\gamma}$-alumina with 9 wt% of the alumina sol and 3wt% of the $\alpha$-Al2O3. It sintered to 99% of the theoretical density at 150$0^{\circ}C$ for 2hrs. and it had relatively homogeneous microstructure with 2~3${\mu}{\textrm}{m}$ sized grains.

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