• Title/Summary/Keyword: $S_N1$ mechanism

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Wear Characteristics of Atomic Force Microscope Tip

  • Chung, Koo-Hyun;Kim, Dae-Eun
    • International Journal of Precision Engineering and Manufacturing
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    • v.5 no.2
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    • pp.39-45
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    • 2004
  • Atomic Force Microscope (AFM) has been widely used in micro/nano-scale studies and applications for the last few decades. In this work, wear characteristics of silicon-based AFM tip was investigated. AFM tip shape was observed using a high resolution SEM and the wear coefficient was approximately calculated based on Archard's wear equation. It was shown that the wear coefficient of Si and ${Si}_3$$N_4$ tips were in the range of ${10}^{-1}$~${10}^{-3}$and ${10}^{-3}$~${10}^{-4}$, respectively. Also, the effect of relative humidity and sliding distance on adhesion-induced tip wear was investigated. It was found that the tip wear has more severe for harder counter surface materials. Finally, the probable wear mechanism was analyzed from the adhesive and abrasive interaction point of view.

Ferromagnetic resonance of Hensler $Ni_2$MnGa thin films

  • M. D. Huang;Lee, N. N.;Lee, Y. P.;J. Y. Rhee;J. Dubowik
    • Journal of the Korean Vacuum Society
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    • v.12 no.S1
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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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    • v.4 no.5
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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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    • v.21 no.1
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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.

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

  • Myung-Hwan Whangbo;Ikchoon Lee
    • Journal of the Korean Chemical Society
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    • v.13 no.4
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    • pp.273-280
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    • 1969
  • The MO's of maleic anhydride are calculated using the parameter values, $h_{o}$.= 1, $h_{o}$:= 2, $k_{c=o}$= 1, $k_{c-o}$= 0.8, and ${\delta}_{{\alpha}_n}=2{\times}(0.3)^n$. With these MO's the interaction energies of the photochemical reaction of maleic anhydride (MA) with benzene are calculated using intermolecular orbital theory. It is shown that there are cases where the interaction energy includes a constant term and this term takes a great role in the photochemical interaction energy, and that with the calculated interaction energies the reaction mechanism is quite well explained. And it is proved that the photochemical reaction is possible for the second addition step of MA to benzene, and that the MA-benzene adduct should have the well-known stereochemical structure.

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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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    • v.29 no.6
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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.

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 (카보닐 탄소원자 친핵 치환반응. 제2보. Methyl chloroformate의 티오 치환제들의 구조와 반응성에 관한 CNDO/2 계산)

  • Lee Ikchoon
    • Journal of the Korean Chemical Society
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    • v.16 no.6
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    • pp.334-340
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    • 1972
  • CNDO/2 calculations have been carried out on methyl chloro-thiol-, methyl chloro-thiono-, and methyl chloro-dithio-formates. Results show that the trans is the stable configuration for these compounds. It was found that sulfur atom has much less tendency to use its lone pair electrons for ${\pi}$ bond formation compared with oxygen, and that thiolformates are stabilized by hyperconjugation of methyl hydrogens. The order of solvolytic reactivity was found to follow the order of cation stability, which is consistent with the $S_N1$ mechanism proposed for these compounds.

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Comparison study of effects of magnetic therapy at Hap-Kok(LI4 ) on the thermal change of Chun-Choo(ST25) in man (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))

  • Baek Tae-Ho;Park Ryoung-Jun
    • Journal of Korean Medical Ki-Gong Academy
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    • v.5 no.1
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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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    • v.33 no.9
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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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    • v.26 no.6
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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.