• 제목/요약/키워드: $S_N1$ mechanism

검색결과 719건 처리시간 0.027초

Pyridinolysis of 2,4-Dinitrophenyl Phenyl Thionocarbonate: Effect of Changing Electrophilic Center from C=O to C=S on Reactivity and Mechanism

  • Son, Min-Ji;Kim, Song-I;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • 제32권4호
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    • pp.1165-1169
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    • 2011
  • Second-order rate constants ($k_N$) have been measured spectrophotometrically for nucleophilic substitution reactions of 2,4-dinitrophenyl phenyl thionocarbonate 4 with a series of Z-substituted pyridines in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The Br${\o}$nsted-type plot for the reactions of 4 exhibits downward curvature (i.e., ${\beta}_1$ = 0.21 and ${\beta}_2$ = 1.04), indicating that the reactions proceed through a stepwise mechanism with a change in rate-determining step. It has been found that 4 is less reactive than its oxygen analogue, 2,4-dinitrophenyl phenyl carbonate 3, although the thionocarbonate is expected to be more electrophilic than its oxygen analogue. The $pK_a$ at the center of the Br${\o}$nsted curvature, defined as $pK_a^o$, has been analyzed to be 6.6 for the reactions of 4 and 8.5 for those of 3. Dissection of $k_N$ into the microscopic rate constants $k_1$ and $k_2/k_{-1}$ ratio has revealed that the reactions of 4 result in smaller $k_1$ values but larger $k_2/k_{-1}$ ratios than the corresponding reactions of 3. The larger $k_2/k_{-1}$ ratios have been concluded to be responsible for the smaller $pK_a^o$ found for the reactions of 4.

흰쥐 대동맥에서 Trazodone의 혈관이완 작용기전 (Mechanism of the relaxant action of Trazodone in isolated rat aorta)

  • 김상진;김정곤;김진상
    • 대한수의학회지
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    • 제43권4호
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    • pp.587-595
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    • 2003
  • The aim of this study was to investigate trazodone's effect on vasorelaxation and blood pressure lowering and to examine its underlying mechanism of action in isolated thoracic aorta and anesthesized rats. Precontracted aortic rings with high KCl were relaxed with trazodone, at concentrations of $50{\mu}M$ or greater. However, precontracted rings with phenylephrine (PE) were relaxed with trazodone, at concentrations of $0.03{\mu}M$ or greater, in a concentration-dependent manner. These relaxant effects of trazodone on endothelium intact rat aortic rings were significantly greater than those on denuded rings. The trazodone-induced relaxations were suppressed by nitric oxide synthase (NOS) inhibitors, N(G)-nitro-L-arginine (L-NNA) and N(omega)-nitro-L-arginine methyl ester (L-NAME), guanylate cyclase inhibitors, methylene blue and 1H-[1,2,4]oxadiazolo[4,3-a]quinoxalin-1-one (ODQ), a $Ca^{2+}$-activated $K^+$ channel blocker, tetrabutylammonium (TBA), a $Ca^{2+}$ channel blocker, nifedipine, $Na^+$ channel blockers, lidocaine and procaine, and removal of extracellular $Na^+$, but not by aminoguanidine, 2-nitro-4-carboxyphenyl-n, n-diphenylcarbamate (NCDC), indomethacin, glibenclamide and clotrimazole. In vivo, infusion of trazodone elicited significant decrease in arterial blood pressure. Trazodone-induced decrease in blood pressure was markedly inhibited by pretreatment of intravenous injection of saponin, L-NNA, methylene blue, TBA, lidocaine or nifedipine. These findings suggest that the endothelium-dependent relaxation and decrease in blood pressure induced by trazodone is mediated by release of NO from the endothelium, activation of TBA-sensitive $Ca^{2+}$-activated $K^+$ channels or inhibition of $Ca^{2+}$ entry through voltage-gated channel.

n-6/n-3 지방산 비율이 고지혈증 랫드의 지질대사 분할에 미치는 영향 (Effect of n-6/n-3 fatty acid ratio on metabolic partitioning in hyperlipidemic rats)

  • 이승형;엄경환;박병성
    • 한국응용과학기술학회지
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    • 제35권3호
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    • pp.643-653
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    • 2018
  • 본 연구는 고지혈증 모델동물 랫드에서 n-6/n-3가 서로 다른 식이를 급여하였을 때 혈액지질의 대사적 분할에 미치는 작용 메카니즘을 생체 모니터링 기법으로 구명하였다. 총 glycerolipids의 간에서 대사된 cholesteryl $^{14}C$-oleate 비율은 n-6/n-3 비율 4:1, 15:1, 30:1, 대조군 순서로 낮았다(p<0.05). 인지질 분비량은 대조군과 비교할 때 n-6/n-3 비율 4:1, 15:1, 30:1 순서로 높았다(p<0.05). 중성지방 분비량은 대조군과 비교할 때 n-6/n-3 비율 4:1, 15:1, 30:1 순서로 특히, 4:1 처리군에서 낮았다(p<0.05). 총 glycerolipid에 대한 인지질의 분할 비율은 n-6/n-3 비율 4:1, 15:1, 30:1, 대조군 순서로 높았다(p<0.05). 간으로부터 중성지방 분할 비율(%)은 대조군 82.25%와 비교할 때 n-6/n-3 비율 4:1, 15:1, 30:1에서 각각 72.99, 75.93, 78.12%로써 n-6/n-3 비율이 증가할수록 높아졌다(p<0.05). 인지질 분할 비율(%)은 대조군 11.04%와 비교할 때 n-6/n-3 비율 4:1, 15:1, 30:1에서 각 25.15, 18.87, 18.15%로써 n-6/n-3 비율이 증가할수록 낮아졌다(p<0.05).

Arachidonic Acid Activates $K^+$-$Cl^-$-cotransport in HepG2 Human Hepatoblastoma Cells

  • Lee, Yong-Soo
    • The Korean Journal of Physiology and Pharmacology
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    • 제13권5호
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    • pp.401-408
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    • 2009
  • $K^+$-$Cl^-$-cotransport (KCC) has been reported to have various cellular functions, including proliferation and apoptosis of human cancer cells. However, the signal transduction pathways that control the activity of KCC are currently not well understood. In this study we investigated the possible role of phospholipase $A_2$ ($PLA_2$)-arachidonic acid (AA) signal in the regulatory mechanism of KCC activity. Exogenous application of AA significantly induced $K^+$ efflux in a dose-dependent manner, which was completely blocked by R-(+)-[2-n-butyl-6,7 -dichloro-2-cyclopentyl-2,3-dihydro-1-oxo-1Hinden-5-yl]oxy]acetic acid (DIOA), a specific KCC inhibitor. N-Ethylmaleimide (NEM), a KCC activatorinduced $K^+$ efflux was significantly suppressed by bromoenol lactone (BEL), an inhibitor of the calciumindependent $PLA_2$ ($iPLA_2$), whereas it was not significantly altered by arachidonyl trifluoromethylketone ($AACOCF_3$) and p-bromophenacyl bromide (BPB), inhibitors of the calcium-dependent cytosolic $PLA_2$ ($cPLA_2$) and the secretory $PLA_2$ ($sPLA_2$), respectively. NEM increased AA liberation in a doseand time-dependent manner, which was markedly prevented only by BEL. In addition, the NEM-induced ROS generation was significantly reduced by DPI and BEL, whereas $AACOCF_3$ and BPB did not have an influence. The NEM-induced KCC activation and ROS production was not significantly affected by treatment with indomethacin (Indo) and nordihydroguaiaretic acid (NDGA), selective inhibitors of cyclooxygenase (COX) and lipoxygenase (LOX), respectively. Treatment with 5,8,11,14-eicosatetraynoic acid (ETYA), a non-metabolizable analogue of AA, markedly produced ROS and activated the KCC. Collectively, these results suggest that $iPLA_2$-AA signal may be essentially involved in the mechanism of ROS-mediated KCC activation in HepG2 cells.

Benzyl Benzenesulfonate와 피리딘과의 고압반응에 대한 반응속도론적 연구 (Kinetics for the Reaction of Benzyl Benzenesulfonate with Pyridine in Acetone Under High Pressure)

  • 황정의;여수동;지종기
    • 대한화학회지
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    • 제24권2호
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    • pp.150-154
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    • 1980
  • Benzyl benzenesulfonate와 피리딘의 반응속도를 아세톤 용매중에서 20∼$40^{\circ}C$ 및 1∼2000 bars에서 전기전도도법으로 측정하였다. 반응속도는 온도 및 압력이 증가함에 따라 증가하였다. 이 반응의 활성화엔탈피$({\Delta}H^{\neq})$, 엔트로피$({\Delta}S^{\neq})$ 그리고 활성화부피$({\Delta}V^{\neq})$를 구하였다. 이 반응에서 압력변화에 대한 $({\Delta}H^{\neq})$$({\Delta}S^{\neq})$사이에 등속관계가 성립하였으며 등속온도는 $342^{\circ}K$였다. 이상의 결과로 본 반응은 전이상태에서 $C{\cdots}N$ 결합형성이 주로 반응속도를 결정하는 $S_N2$ 반응 메카니즘으로 진행된다는 것을 알았다.

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N-nitroso-N-methylurethane으로 유도된 급성 폐손상에서 호중구에 의한 산화성 스트레스의 역할 (Neutrophilic Respiratory Burst Contributes to Acute Lung Leak in Rats Given N-nitroso-N-methylurethane)

  • 김성은;김덕영;나보경;이영만
    • Applied Microscopy
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    • 제33권1호
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    • pp.1-16
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    • 2003
  • 급성호흡곤란증후군 (acute respiratory distress syndrome)을 포함한 급성폐손상의 기전을 산화성스트레스와 연관하여 알아보기 위하여 본 연구를 시행하였다. N-nitroso-N-methylurethane (NNNMU)은 실험동물에 있어서 사람에서 보이는 ARDS와 유사한 병리학적인 소견을 보이므로 ARDS의 모델로 사용된다. 본 연구에서는 흰쥐에서 NNNMU로 급성폐손상을 유도한 뒤 이를 Lung weight/Body weight ratio, 폐포세척액(BAL)내의 단백함량을 측정하여 확인하고, 동시에 호중구의 침윤에 의한 산소기형성, 이에 따른 산화성스트레스를 확인하기 위하여 BAL 내의 호중구수의 산정 및 폐장의 MPO 활성도를 측정하였다. 동시에 광학현미경, 전자현미경 및 세포화학적 전자현미경법을 이용하여 호중구에 의한 급성폐손상, 호중구의 침윤 및 미세구조의 변화 및 산소기의 생성을 확인하였다. 대조군에 비하여 NNNMU를 투여한 흰쥐에서는 BAL 내의 단백질이 증가하고 BAL 내의 호중구의 증가, 폐장의 MPO 활성도의 증가로 호중구의 침윤이 증가함을 관찰하였다. 광학현미경상 호중구의 침윤, 폐포내 호중구의 유입 및 vascular cuffing 등이 관찰되었다. 전자현미경 소견상 제2형 폐포세포는 산화성 스트레스의 전형적 소견을 보이고 조직의 손상은 호중구에 의한 손상으로 생각되었으며 세포화학적 전자현미경법으로 산소기의 생성이 증가됨을 확인하였다. 이러한 결과들을 종합할 때 NNNMU에 의한 급성폐손상은 호중구의 산소기 생성에 의한 산화성스트레스에 의한 것으로 생각되었다.

Identification of Differentially Expressed Genes in Murine Hippocampus by Modulation of Nitric Oxide in Kainic Acid-induced Neurotoxic Animal Model

  • Suh, Yo-Ahn;Kwon, O-Min;Yim, So-Young;Lee, Hee-Jae;Kim, Sung-Soo
    • The Korean Journal of Physiology and Pharmacology
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    • 제11권4호
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    • pp.149-154
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    • 2007
  • Kainic acid (KA) causes neurodegeneration, but no consensus has been reached concerning its mechanism. Nitric oxide may be a regulator of the mechanism. We identified differentially expressed genes in the hippocampus of mice treated with kainic acid, together with or without L-NAME, a nonselective nitric oxide synthase inhibitor, using a new differential display PCR method based on annealing control primers. Eight genes were identified, including clathrin light polypeptide, TATA element modulatory factor 1, neurexin III, ND4, ATPase, $H^+$ transporting, V1 subunit E isoform 1, and N-myc downstream regulated gene 2. Although the functions of these genes and their products remain to be determined, their identification provides insight into the molecular mechanism(s) involved in KA-induced neuronal cell death in the hippocampal CA3 area.

시안화 벤조일의 가용매분해반응 (Solvolysis of Benzoyl Cyanide)

  • 김정화;이익춘;손세철;엄태섭
    • 대한화학회지
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    • 제27권2호
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    • pp.95-101
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    • 1983
  • 여러가지 수용성 혼합용매와 에탄올-TFE 혼합용매에서 시안화 벤조일의 가용매분해반응에 대한 유사-1차반응속도상수를 1, 5, 10, 15, $20^{\circ}C$에서 구하였다. Kivinen polt의 n값, Grunwald-Winstein polt의 m값, Leffler 관계식의 $\beta$값, 확정된 Grunwald-Winstein식의 m 및 l값을 구하였다. More O'Ferrall polt와 양자역학적 해석 방법을 이용하여 용매 변화에 따른 전이상태 변화를 논의하였으며 본 반응은 associative $S_N2$ 반응 메카니즘으로 진행됨을 알 수 있었다.

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고체 전해질용 $CuO-P_2O_5-V_2O_5$ 유리의 결정화와 전기 전도도 (Crystallization and Electrical properties of $CuO-P_2O_5-V_2O_5$ Glass for solid state Electrolyte)

  • 손명모;이헌수;전연수;구할본;이상근
    • 한국전기전자재료학회:학술대회논문집
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    • 한국전기전자재료학회 2003년도 하계학술대회 논문집 Vol.4 No.2
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    • pp.934-937
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    • 2003
  • Glasses in the system $CuO-P_2O_5-V_2O_5$ were prepared by a press-quenching method on the copper plate. The glass-ceramics from these glasses were obtained by post-heat treatment, and the crystallization behavior and DC conductivities were determined. The conductivities of the glasses were range from $10^{-6}s.Cm^{-1}$ at room temperature, but the conductivities of the glass-ceramics were $10^{-3}s.Cm^{-1}$ increased by $10^3$ order. The crystalline product in the glass-ceramics was $CuV_2O_6$. Heat-treatment conditions influenced the crystal growth of $CuV_2O_6$ and conductivity. The linear relationship between in (${\sigma}T$) and $T^{-1}$ suggested that the electrical conduction in the present glass-ceramics would be due to a small polaron hopping(SPH) mechanism.

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Shear Resistant Mechanism into Base Components: Beam Action and Arch Action in Shear-Critical RC Members

  • Jeong, Je-Pyong;Kim, Woo
    • International Journal of Concrete Structures and Materials
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    • 제8권1호
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    • pp.1-14
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    • 2014
  • In the present paper, a behavioral model is proposed for study of the individual contributions to shear capacity in shear-critical reinforced concrete members. On the basis of the relationship between shear and bending moment (V = dM/dx) in beams subjected to combined shear and moment loads, the shear resistant mechanism is explicitly decoupled into the base components-beam action and arch action. Then the overall behavior of a beam is explained in terms of the combination of these two base components. The gross compatibility condition between the deformations associated with the two actions is formulated utilizing the truss idealization together with some approximations. From this compatibility condition, the ratio of the shear contribution by the tied arch action is determined. The performance of the model is examined by a comparison with the experimental data in literatures. The results show that the proposed model can explain beam shear behavior in consistent way with clear physical significance.