• Title/Summary/Keyword: $S_N1$ mechanism

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The Study of Rates of Substitution Reaction [Pd(ONN)Cl] + Y$^-\;{\rightleftharpoons}$ [Pd(ONN)Y] + Cl$^-$ (Y = SCN$^-$, CN$^-$, N$_3^-$, Imidazole, Pyridine) ([Pd(ONN)Cl] 착물의 SCN$^-$, CN$^-$, N$_3^-$, Imidazole, Pyridine에 대한 치환반응 속도연구 (제 1 보))

  • Oh Sang-Oh;Yeo, Hwan Jin;Cho Iee Yeung
    • Journal of the Korean Chemical Society
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    • v.35 no.4
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    • pp.362-367
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    • 1991
  • Rates of nucleophilic substitution reaction ([Pd (ONN) Cl] + Y$^-\;{\rightleftharpoons}$ [Pd (ONN)Y] + Cl$^-$ ; Y = SCN$^-$, CN$^-$, N$_3^-$, imidazole, pyridine) have been measured in methanol by spectrophotometric method at various temperatures. A set of nucleophilic reactivity constants, n$_{Pd}^{\circ}$ has been calculated. These values show an order of nucleophilicity CN$^-$ > SCN$^-$ > N$_3^-$ > Imidazole > Pyridine. The enthalpy of activation are small positive values and the entropy of activation are large negative values. From these results, it can be inferred that the nucleophilic substitution reaction proceeds through an associative (A) mechanism.

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Glycogen Synthase Kinase-3 Interaction Domain Enhances Phosphorylation of SARS-CoV-2 Nucleocapsid Protein

  • Jun Seop, Yun;Hyeeun, Song;Nam Hee, Kim;So Young, Cha;Kyu Ho, Hwang;Jae Eun, Lee;Cheol-Hee, Jeong;Sang Hyun, Song;Seonghun, Kim;Eunae Sandra, Cho;Hyun Sil, Kim;Jong In, Yook
    • Molecules and Cells
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    • v.45 no.12
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    • pp.911-922
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    • 2022
  • A structural protein of SARS-CoV-2 (severe acute respiratory syndrome coronavirus 2), nucleocapsid (N) protein is phosphorylated by glycogen synthase kinase (GSK)-3 on the serine/arginine (SR) rich motif located in disordered regions. Although phosphorylation by GSK-3β constitutes a critical event for viral replication, the molecular mechanism underlying N phosphorylation is not well understood. In this study, we found the putative alpha-helix L/FxxxL/AxxRL motif known as the GSK-3 interacting domain (GID), found in many endogenous GSK-3β binding proteins, such as Axins, FRATs, WWOX, and GSKIP. Indeed, N interacts with GSK-3β similarly to Axin, and Leu to Glu substitution of the GID abolished the interaction, with loss of N phosphorylation. The N phosphorylation is also required for its structural loading in a virus-like particle (VLP). Compared to other coronaviruses, N of Sarbecovirus lineage including bat RaTG13 harbors a CDK1-primed phosphorylation site and Gly-rich linker for enhanced phosphorylation by GSK-3β. Furthermore, we found that the S202R mutant found in Delta and R203K/G204R mutant found in the Omicron variant allow increased abundance and hyper-phosphorylation of N. Our observations suggest that GID and mutations for increased phosphorylation in N may have contributed to the evolution of variants.

Effect of Adenosine Analogues on the Renal Function and Renin Release (가토의 신장기능과 Renin분비에 미치는 Adenosine Analogues의 영향)

  • Song, Yun-Sik;Choi, Byung-Soo;Kim, Suhn-Hee;Cho, Kyung-Woo
    • The Korean Journal of Physiology
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    • v.22 no.2
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    • pp.319-332
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    • 1988
  • The regulations of renal function and renin release are influenced by neural, humoral and physical factors. During the last decade, considerable progress has been made in the identification and characterization of these extrinsic renal control systems. Mechanisms intrinsic to the kidney are also important for renal function. These include the autoregulation of blood flow, and the local control of renin secretion. Fundamental questions regarding the mechanism of these intrinsic controls remain unanswered. Recently, endogenous renal adenosine has been claimed to influence the tubuloglomerular feedback control and renin release. Two subclasses of adenosine receptors $A_1{\;}and{\;}A_2$ have been described. The present experiment was carried out to evaluate the effects of $N_6-cyclohexyladenosine$ $(CHA,{\;}A_1{\;}selective)$ and 5'-N-ethylcarbox-amide adenosine $(NECA,{\;}A_2{\;}selective)$ on the renal function and renin release in the unanesthetized rabbit. Intra-renal arterial infusion of NECA $(0.3{\sim}10.0n{\;}mole/min/rabbit)$ or CHA $(0.03{\sim}10.0n{\;}mole/min/rabbit)$ caused a prompt and dose-dependent decrease in urine volume, glomerular filtration rate (GFR), renal plasma flow (RPF), filtration fraction (FF), electrolyte excretion and free water clearance $(CH_2O)$, the effect being much more profound with CHA than with NECA. The NECA infusion resulted in a profound decrease of systemic blood pressure, but the CHA infusion did not. Both NECA and GHA infusions caused a prompt and dose-dependent decrease in renin secretion rate, again the effect being greater with CHA than with NEGA. These results suggest that both $A_1{\;}and{\;}A_2$ adenosine receptors may be involved in the intrinsic control of renal function and renin release, and that the $A_1$ receptors plays a more important role than the $A_2$ receptor in the regulation of renal fnction.

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Understand the Molecular Orbital Theory on the Hydrolytic Reactivity of Herbicide Flumioxazine (제초제 Flumioxazine의 가수분해 반응성에 관한 분자 궤도론적 이해)

  • Sung, Nack-Do;Jung, Hoon-Sung
    • The Korean Journal of Pesticide Science
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    • v.8 no.4
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    • pp.265-271
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    • 2004
  • Hydrolytic reactivities of N-phenylphthalimid herbicide flumioxazine (S) were disccused using molecular orbital (MO) theoretical method. It is revealed that below pH 5.0, the protonation $(SH^+)$ to carbonyl oxygens atom $(O_{21})$ of 1,2-dicarboximino group by general acid catalysis $(k_A)$ with hydronium ion $(H_3O^+)$ proceeds via charge controled reaction. Whereas, the specific base catalysis $(k_{OH})$ with hydroxide anion via orbital controled reaction occurs above pH 8.0. We may concluded that in the range of pH $5.0\sim8.0$, the hydrolysis proceeds through nucleophilic addition elimination $(Ad_{N-E})$ reaction, these two reactions occur competitively.

Kinetic Investigation on the Reaction between Cu(II) and Excess D-penicillamine in Aqueous Media

  • Lee, Yong-Hwan;Choi, Sung-Nak;Cho, Mi-Ae;Kim, Yong-Kyu
    • Bulletin of the Korean Chemical Society
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    • v.11 no.4
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    • pp.281-286
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    • 1990
  • The kinetics and mechanism of reduction of Cu(II) with an excess D-penicillamine have been examined at pH = 6.2 and 0.60M in ionic strength. The reaction at the initial stage is biphasic with a rapid complexation process to give "red" transient complex of $[Cu(II)(pen)_2]^2$- that is partially reduced to another transient "brown" intermediate. The "brown" intermediate is finally reduced to diamagnetic "yellow" complex, $[Cu(I)(Hpen)]_n$. The final reduction process is pseudo-first order in ["brown" transient] disappearance $with {\kappa} = {{\kappa}_{3a} + {\kappa}_{3b}[pen]^{2-}},$ where ${\kappa}_{3a} = (5.0{\pm}0.8){\times}10^{-3}sec^{-1}$ and ${\kappa} = (0.14{\pm}0.02) M^{-1}sec^{-1}$ at $25^{\circ}C$. The activation parameters for the $[H_2pen]$-independent and $[H_2pen]$-dependent paths are ${\Delta}H^{\neq} = (52{\pm}5)kJmol^{-1},$ and ${\Delta}S^{\neq} = ( - 27{\pm}3)JK^{-1}mo^{l-1},$ and ${\Delta}H^{\neq} = (56{\pm}2)kJmol^{-1}$ and ${\Delta} S^{\neq} = ( - 18{\pm}0.7)JK^{-1}mol^{-1}$ respectively. The nature of "brown" intermediate is not clearly identified, but this intermediate seems to be in the mixed-valence state, judging from the kinetic and spectroscopic informations.

전자가 도핑된 $Sr_{0.9}$$La_{0.1}$Cu$O_2$초전도체의 홀 효과

  • Kim, Hyun-Jung;W. N. Kang;Kim, Kijoon H. P.;Lee, Sung-Ik;S. Karimoto
    • Progress in Superconductivity
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    • v.4 no.1
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    • pp.32-36
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    • 2002
  • We have measured the Hall effect in infinite-layer Sr/sub 0.9/La/sub 0.1/$CuO_2$ thin films grown by molecular beam epitaxy. We do not observe $T^{2}$ dependence of the cotangent of Hall angle, which is commonly observed in other cuprate High-Tc superconductors. Therefore, this result cannot be interpreted within two different scattering mechanism based on charge-spin separation theory. The mixed-state Hall effect shows no sign anomaly, implying that tile hydrodynamic contribution of vortex core is negligibly small.

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Oxidative Addition Reaction of Mono(aryl)cyanoplatinum(Ⅱ) Complex with Two Amino Ligands with the Dihalogens

  • Ko Jaejung;Kim Moonsik;Kim Seho;Shin Yookil
    • Bulletin of the Korean Chemical Society
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    • v.13 no.2
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    • pp.135-139
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    • 1992
  • The mono(aryl)cyanoplatinum(II) complex $[Pt(CN)(C_6H_3{CH_2NMe_2}_2-26)]$, reacts with the dihalogens to yield the mono(aryl)cyanoplatinum complexes $[PtX_2(CN)(C_6H_3{CH_2NMe_2}_2-26)]$, (X = Cl, Br, I). The structural configuration of the two halogen atoms for a square planar platinum complex was studied by 1H-NMR spectroscopy and led to a mixture of trans and cis orientation. The trans orientation was found to be more stable in energy (1.33 kcal/mol) than the cis orientation by means of Extended H ckel calculations. On the base of a combination of the analysis of $^1H-NMR$, $^{13}C-NMR spectra and computational calculations it is assumed that the intermediate consists of an initial attack in the linear transition state, leading to the $S_{N}2$ type mechanism.

A Study on the Cutting Mechanism and Energy with Saw-toothed Chip (톱니형Chip의 절삭기구와 Energy에 관한 연구)

  • Kim, Hang-Young;Oh, Seok-Hyung;Seo, Nam-Seob
    • Journal of the Korean Society for Precision Engineering
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    • v.4 no.3
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    • pp.44-51
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    • 1987
  • In metal cutting various types of chips are produced in consequence of cutting conditions. Flow-type chips have been studied in most cases because they are easier to be analyzed, but the actual surfaces of chips are not smooth, but crushed. This paper deals with saw-toothed chips, special types of flow-type chips, which have deep concaves and high convexes and sharp angles on the free surface. I tried to establish the theory of saw-toothed chip mechanism through experimental observation, that is, the mathmatical model of the cutting energy and cutting mechanism through the geometrical observation of the chips by using a microscope. The results obtained are as follows: 1. The mechanism of saw-toothed chips is diffenent from that of general flow-chips. 2. In the case of saw-toothed chips, the shear angle must be measured by the hypotenuse angle and the rake angle, and the shear angle is more affected by the rake angle than by the hypotenbuse angle. 3. The friction angle is represented by .beta. = . pi. /4+ .alpha./ sub n/- .phi. which is different from Merchant's equation. 4. The pitch and the slip are greatly influenced by depth of cut, but the influence of the rake angle on it is small. 5. The normal stress and the shear stress on the shear plane decrease with the increase of the cutting depth, and they are almost independent on the variation of a rake angle. 6. The unit friction energy on the tool face, the unit shear energy on the shear plane, and the total cutting energy per unit volume decrease with the increase of rake angle and cutting depth.

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Coarsening Mechanism in Cemented Carbides and Suggestion for Suppression of Grain Growth (Cemented Carbides에서의 입성장 기구와 입성장 억제를 위한 제안)

  • Choi, K.;Choi, U.S.;Hwang, N.M.;Kim, D.Y.
    • Proceedings of the Korean Powder Metallurgy Institute Conference
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    • 2001.04a
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    • pp.14-14
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    • 2001
  • WC-Co 계의 입성장 억제는 현재 초경합금 분야에서 공학적으로 가장 중요한 이슈들 중의 하나이다 VC를 비롯한 입방정 탄화물이나 $Cr_3C_2$ 등의 여러 가지 탄화 물이 혼합되어 입성장 억제에 이용되는데 입성장 억제의 효과는 대략적으로 용해되는 탄화물의 양에 의존하고 있는 것으로 추정된다. 보다 효율적으로 입성장 억제를 실현하려면 입성장 기구를 명확히 할 필요가 있다. 최 등[1]은 VC가 WC 입자 표면 에서의 edge energy를 증가시켜서 2차원 핵생성의 에너지 장벽을 올리게 하고 이에 따라 입성장이 억제된다는 모델을 제안하였다. 이러한 모텔을 입증하기 위해서는 이론적으로만 예측이 가능한 edge energy보다 좀 더 명확한 물리적인 변수가 제시되어야 할 것이다. 여기서는 또 다른 계인 NbC- TiC-Co 계에서 NbC와 TiC의 버에 따른 입성장 거동과 입자의 형상간의 관계로부터 업성장과 edge energy 그리 고 edge energy와 입자 형상간의 관계를 알아보고 이로부터 좀 더 구체적인 의미 에서의 입성장 모텔과 입성장 억제기구를 제시하고자 한다.

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Reliability Growth Modeling in the Vehicles Developement Stage

  • Won Jung;Park, Sukhwan
    • Journal of Korea Society of Industrial Information Systems
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    • v.3 no.1
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    • pp.67-77
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    • 1998
  • Reliability growth testing used to evaluate reliability in the automobile industry have not always been able to correctly address reliability concerns with increased confidence. The demand to confirm to all product performance requirements under various operating environments has added to the complexity of accurately assessin theproduct's reliability in the required development time. In addition, it is often desired to determine the relationship of a product's reliability to cost, development time, design, manufacturability and assembly. This paper presents the methods for reliability growth modeling to evaluate and interpret reliability concerns to support the reliability analysis of automobile assemblies and systems. This reliability growth modeling process is a mechanism to help "build in" reliability during early phases in the vehicle devleopment stage.