• 제목/요약/키워드: $S_N1$ mechanism

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Ferromagnetic resonance of Hensler $Ni_2$MnGa thin films

  • M. D. Huang;Lee, N. N.;Lee, Y. P.;J. Y. Rhee;J. Dubowik
    • 한국진공학회지
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    • 제12권S1호
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    • pp.116-119
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    • 2003
  • $Ni_2$MnGa films, deposited on mica and glass substrates, were studied by ferromagnetic resonance (FMR) technology. The temperature-dependent resonance field was measured and a martensitic phase transformation (MT) was found between 310 and 340 K, exhibiting an abnormality on the curve. The easy axis is found to be in the film plane. The line width increases as a whole with decreasing temperature, which is discussed in terms of the motional narrowing mechanism. The resonance field was also measured as a function of orientation and the results were fitted, exhibiting a good consistence.

Kinetics of Reactions Between Substituted Benzyl Chlorides and Anilines in MeOH-MeCN Mixtures

  • Lee, Ik-choon;Sohn, Se-Chul;Lee, Byung-Choon;Song, Ho-Bong
    • Bulletin of the Korean Chemical Society
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    • 제4권5호
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    • pp.208-211
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    • 1983
  • Kinetic studies of nucleophilic substitution reactions of para-substituted benzylchlorides with anilines were conducted in a range of MeOH-MeCN mixtures at $55.1^{\circ}C$. Hammett ${\rho}_C$, ${\rho}_N$ values and Bronsted ${\beta}$ values were determined, in other to examine the transition state variations caused by changes in nucleophiles, substituents and solvents properties (${\pi}^{\ast}$ and ${\alpha}$). Applications of potential energy surface (PES) and quantum mechanical (QM) models of transitheion state characterization lead us to conclude that the reaction proceeds via the dissociative $S_N2$ mechanism.

Role of HIV Vpr as a Regulator of Apoptosis and an Effector on Bystander Cells

  • Moon, Ho Suck;Yang, Joo-Sung
    • Molecules and Cells
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    • 제21권1호
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    • pp.7-20
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    • 2006
  • The major event in human immunodeficiency virus type 1 (HIV-1) infection is the death of many cells related to host immune response. The demise of these cells is normally explained by cell suicide mechanism, apoptosis. Interestingly, the decrease in the number of immune cells, such as non-CD4+ cells as well as CD4+ T cells, in HIV infection usually occurs in uninfected bystander cells, not in directly infected cells. It has, therefore, been suggested that several soluble factors, including viral protein R (Vpr), are released from the infected cells and induce the death of bystander cells. Some studies show that Vpr interacts directly with adenine nucleotide translocator (ANT) to induce mitochondrial membrane permeabilization (MMP). The MMP results in release of some apoptogenic factors such as cytochrome-c (cyt-c) and apoptosis-inducing factor (AIF). Vpr also has indirect effect on mitochondria through enhancing the level of caspase-9 transcription and suppressing nuclear factor-kappa B (NF-${\kappa}B$). The involvement of p53 in Vpr-induced apoptosis remains to be studied. On the other hand, low level of Vpr expression has anti-apoptotic effect, whereas it's high level of expression induces apoptosis. Extracellular Vpr also exhibits cytotoxicity to uninfected bystander cells through apoptotic or necrotic mechanism. The facts that Vpr has cytotoxic effect on both infected cells and bystander cells, and that it exhibits both proand anti-apoptotic activity may explain its role in viral survival and disease progression.

분자 궤도론에 의한 반응성 계산 (I) Benzene과 Maleic Anhydride 간의 광화학 반응 (Determination of Reactivities by Molecular Orbital Theory (I) Theoretical Treatment on the Photochemical Reaction of Benzene and Maleic Anhydride)

  • 황보명환;이익춘
    • 대한화학회지
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    • 제13권4호
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    • pp.273-280
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    • 1969
  • Maleic Anhydride의 분자궤도를 다음의 파라미터를 사용하여 계산하였다. $h_{o}$=1, $h_{o}$=2, $k_{c=o}$ =0.8 ${\delta}_{{\alpha}_n}=2{\times}(0.3)^n$ 얻어진 분자궤도들로부터 Benzene과 Maleic Anhydride(MA)의 광화학적반응의 작용 에너지를 구하였다. 작용에너지에는 상수항이 포함될 수 있으며 이항이 작용 에너지에 크게 기여함을 보였고 이 반응의 메카니즘은 계산된 작용에너지로 잘 설명됨을 밝혔다. 또한 MA의 두번 째 첨가반응이 광화학적으로 가능하며 MA-Benzene의 부가 생성물은 잘 알려진 입체 화학적 구조를 가져야함을 증명하였다.

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A Mechanistic Study on the Nucleophilic Addition Reactions of Benzylamines to the Activated Olefins

  • Oh, Hyuck-Keun
    • Bulletin of the Korean Chemical Society
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    • 제29권6호
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    • pp.1195-1198
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    • 2008
  • Kinetic studies of the additions of benzylamines to a noncyclic dicarbonyl group activated olefin, methyl $\alpha$-acetyl-$\beta$ -phenylacrylates (MAP), in acetonitrile at 30.0 ${^{\circ}C}$ are reported. The rates are lower than those for the cyclic dicarbonyl group activated olefins. The addition occurs in a single step with concurrent formation of the $C_\alpha$ -N and $C_\beta$ -H bonds through a four-center hydrogen bonded transition state. The kinetic isotope effects ($k_H/k_D$ > 1.0) measured with deuterated benzylamines ($XC_6H_4CH_2ND_2$) increase with a stronger electron acceptor substituent ($\delta\sigma$ X > 0) which is the same trend as those found for other dicarbonyl group activated series (1-4). The sign and magnitude of the cross-interaction constant, ρXY, is comparable to those for the normal bond formation processes in the $S_N2$ and addition reactions. The relatively low ${\Delta}H^\neq$ and large negative ${\Delta}S^\neq$ values are also consistent with the mechanism proposed.

카보닐 탄소원자 친핵 치환반응. 제2보. Methyl chloroformate의 티오 치환제들의 구조와 반응성에 관한 CNDO/2 계산 (Nucleophilic Substitution at a Carbonyl Carbon Atom. Part II. CNDO/2 Studies on Conformation and Reactivity of the Thio-Analogues of the Thio-Analogues of Methyl Chloroformate)

  • 이익춘
    • 대한화학회지
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    • 제16권6호
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    • pp.334-340
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    • 1972
  • 메틸 클로로 티올, 메틸클로로 티오노 및 메틸 클로로 디티오 훠메이트에 대하여 CNDO/2 계산을 실시하였다. 결과로 이들 화합물은 trans형이 안정한 것임을 밝혔다. 또 유황 원자는 산소원자에 비하여 그 고립쌍 전자들을 ${\pi}$-결합 형성에 사용하려는 경향이 적고 티올 훠메이트의 경우는 메틸기의 hyperconjugation에 의하여 안정화됨을 알았다. 가용매 반응성의 순서는 양이온의 안정도와 일치하며 이것은 알려진 $S_N1$형 반응 메카니즘과 부합된다.

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합곡(合谷)(L14)의 자침(刺鍼)과 자석외첩(磁石外貼)이 천추(天樞)(S25) 부분(部分) 영역(領域)의 온도변화(溫度變化)에 미치는 영향(影響) 비교(比較) (Comparison study of effects of magnetic therapy at Hap-Kok(LI4 ) on the thermal change of Chun-Choo(ST25) in man)

  • 백태호;박령준
    • 대한의료기공학회지
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    • 제5권1호
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    • pp.22-39
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    • 2001
  • This study is designed to compare the effect of a needle with the magnet on body. We took the skin temperature of the belly with digital infrared thermographic imaging while we sticked needle and apply magnets on L14. We made experiments on 40 healthy male volunteers for one month. We classified control group not acupuncture or magnet adhering(CON). acupuncture group on left and right L14(LA). and the permanent magnet group adhering to left and right(LM). And LM is divided into S-polar permanent magnet group(LMS) and N-polar permanent magnet group adhering to left and right L14(LMN). When we observed that temperature changed with time, the skin temperature of th belly in CON descended significantly but LM, LMS and LMN is not changed significantly. As mentioned above. we observed that the needles on L14 affected the change of temperature on the belly, and conjectured that the appliance of magnets had the same results. If the mechanism depends on the meridian of body and energy. we suppose that the appliance of magnets and needles has same effects.

Alternative Mechanism of Aspirin in Anti-Thrombotic Therapy: Inhibition of Thrombin Activatable Fibrinolysis Inhibitor

  • An, Seong-Soo A.;Greenfield, Robert S.
    • Bulletin of the Korean Chemical Society
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    • 제33권9호
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    • pp.3048-3054
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    • 2012
  • The use of aspirin is widely recommended for the prevention of heart attacks owing to its ability to inhibit platelet activation by irreversibly blocking cyclooxygenase 1. However, aspirin also affects the fibrinolytic and hemostatic pathways by mechanisms that are not well understood, causing severe hemorrhagic complications. Here, we investigated the ability of aspirin and aspirin metabolites to inhibit thrombin-activatable fibrinolysis inhibitor (TAFI), the major inhibitor of plasma fibrinolysis. TAFI is activated via proteolytic cleavage by the thrombin-thrombomodulin complex to TAFIa, a carboxypeptidase B-like enzyme. TAFIa modulates fibrinolysis by removing the C-terminal arginine and lysine residues from partially degraded fibrin, which in turn inhibits the binding of plasminogen to fibrin clots. Aspirin and its major metabolites, salicylic acid, gentisic acid, and salicyluric acid, inhibit TAFIa carboxypeptidase activity. Salicyluric acid effectively blocks activation of TAFI by thrombin-thrombomodulin; however, salicylates do not inhibit carboxypeptidase N or pancreatic carboxypeptidase B. Aspirin and other salicylates accelerated the dissolution of fibrin clots and reduced thrombus formation in an in vitro model of fibrinolysis. Inhibition of TAFI represents a novel hemostatic mechanism that contributes to aspirin's therapy-associated antithrombotic activity and hemorrhagic complications.

Kinetics and Mechanism of the Addition of Benzylamines to α-Cyano-β-phenylacrylamides in Acetonitrile

  • Oh, Hyuck-Keun;Ku, Myoung-Hwa;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • 제26권6호
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    • pp.935-938
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    • 2005
  • Nucleophilic addition reactions of benzylamines (BA; $XC_6H_4CH_2NH_2$) to $\alpha-cyano-\beta$-phenylacrylamides (CPA; $YC_6H_4CH=C(CN)CONH_2$) have been investigated in acetonitrile at 25.0 ${^{\circ}C}$. The rate is first order with respect to BA and CPA and no base catalysis is observed. The addition of BA to CPA occurs in a single step in which the addition of BA to $C_{\beta}$ of CPA and proton transfer from BA to $C_{\alpha}$ of CPA take place concurrently with a four-membered cyclic transition state structure. The magnitude of the Hammett ($\rho_X$) and Bronsted ($\beta_X$) coefficients are rather small suggesting an early tansition state (TS). The sign and magnitude of the crossinteraction constant, $\rho_XY$ (= −D0.26), is comparable to those found in the normal bond formation processes in the $S_N2$ and addition reactions. The normal kinetic isotope effect ($k_H/k_D\;{\gt}$ 1.0) and relatively low ${\Delta}H^{\neq}$ and large negative ${\Delta}S^{\neq}$ values are also consistent with the mechanism proposed.

Transition-State Variation in the Solvolyses of para-Substiuted Phenyl Chloroformates in Alcohol-Water Mixtures

  • 구인선;양기율;강금덕;이익춘
    • Bulletin of the Korean Chemical Society
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    • 제19권9호
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    • pp.968-973
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    • 1998
  • Solvolyses of para-substituted phenyl chloroformates in water, $D_2O,\;CH_3OD$, 50% $D_2O-CH_3OD$, and in aqueous binary mixtures of acetone, ethanol, methanol are investigated at 25.0 ℃. Product selectivities are reported for a wide range of ethanol-water and methanol-water solvent compositions. These data are interpreted using the Grunwald-Winstein relationship, Hammett equation, and quantum mechanical model. Grunwald-Winstein plots of the first-order rate constants for phenyl chloroformates with $Y_{Cl}$ (based on 1-adamantyl chloride) show marked dispersions into three separate curves for the three aqueous mixtures with a small m value and a rate maximum for aqueous alcohol solvents. To account for these results, third-order rate constants, $k_{ww},\;k_{aw},\;k_{wa}$, and $k_{aa}$ were calculated from the observed $k_{ww}\;and\;k_{aa}$ values together with $k_{aw}\;and\;k_{wa}$ calculated from the computer fit. The kinetic solvent isotope effects determined in water and methanol are consistent with the proposed mechanism of the general base catalyzed carbonyl addition-elimination for para-substituted phenyl chloroformates solvolyses based on mass law and stoichiometric salvation effect studies. This study has shown that the quantum mechanical model predicts transition state variation correctly for $S_N2\;like\;S_AN$ reaction mechanism of para-substituted phenyl chloroformates.