• Title/Summary/Keyword: V-T mechanism

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Thermodynamic Properties of the Solute Transfer from the Aqueous Acetonitrile Mobile Phase to the Stationary Phase Monitored by HPLC

  • Jeong, Won Jo;Kim, Ji Yeon;Gu, Yun Mo
    • Bulletin of the Korean Chemical Society
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    • v.21 no.1
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    • pp.105-109
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    • 2000
  • High-performance liquid chromatography is suitable for getting thermodynamic information about solute-solvent interactions. We used a squalane impregnated $C_{18}$ phase as a presumably bulk-like stationary phase to secure a simple partition mechanism for solute retention in reversed phase liquid chromatographic system. We measured retention data of some selected solutes (benzene, toluene, ethylbenzene, propylbenzene, butylbenzene, phenol, benzylalcohol, phenethylalcohol, benzylacetone, acetophenone, benzonitrile, benzylcyanide) at 25, 30, 35, 40, 45, and 50 $^{\circ}C$ in 30/70, 40/60, 50/50, 60/40 and 70/30 (v/v%) acetonitrile/water eluents. The van't Hoff plots were nicely linear, thus we calculated dependable thermodynamic values such as enthalpies and entropies of solute transfer from the mobile phase to the stationary phase based on more than four retention measurements on different days (or weeks). We found that the cavity formation effect was the major factor in solute distribution between the mobile and stationary phases in the system studied here. Our data were com-pared with some relevant literature data.

Kinetics and mechanism of hydrolysis of insecticidal buprofezin (살충제 buprofezin의 가수분해 반응 메카니즘)

  • Sung, Nack-Do;Yu, Seong-Jae;Choi, Kyung-Sub;Kwon, Ki-Sung
    • The Korean Journal of Pesticide Science
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    • v.2 no.1
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    • pp.46-52
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    • 1998
  • The hydrolysis rate of insecticidal buprofezin(IUPAC : tert-butylimino-3-isopropyl-5-phenylperhydro-1,3,5-thiadiazin-4-one) in the range of pH 2.0 and 12.0 have been examined in 15%(v/v) aqueous dioxane at $45^{\circ}C$. The hydrolysis mechanism of buprofezin is proposed from the pH-effect, solvent effect(${\ell}{\gg}m$), thermodynamic parameter(${\Delta}H^{\neq}$=11.12 $Kcal{\cdot}mol^{-1}$ &, ${\Delta}S^{\neq}=5.0e.u.$), rate equation and hydrolysis product, l-isopropyl-3-phenyl urea. General acid catalyzed hydrolysis and specific acid catalyzed($k_{H3O+}$) hydrolysis through $A-S_{E}2$ and A-2(or $A_{AC}2$) reaction mechanism with orbital-control reaction proceed below pH 8.0 and above pH 9.0, the nucleophilic addition-elimination, $Ad_{N}-E$ mechanism via tetrahedral($sp^{3}$) intermediate is initiation by general base catalyzed($k_{H2O}$) reaction. Buprofezin was more stable in alkaline ($k=10^{-8}sec.^{-1}$) than acid solutions from the sigmoid pH-rate profile. And the half-life($t=\frac{1}{2}$) of hydrolysis reaction in neutral aqueous solution(pH 7.0) at $45^{\circ}C$ was about 3 months.

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Branched N-glycans and their implications for cell adhesion, signaling and clinical applications for cancer biomarkers and in therapeutics

  • Taniguchi, Naoyuki;Korekane, Hiroaki
    • BMB Reports
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    • v.44 no.12
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    • pp.772-781
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    • 2011
  • Branched N-glycans are produced by a series of glycosyltransferases including N-acetylglucosaminyltransferases and fucosyltransferases and their corresponding genes. Glycans on specific glycoproteins, which are attached via the action of glycosyltransferases, play key roles in cell adhesion and signaling. Examples of this are adhesion molecules or signaling molecules such as integrin and E-cadherin, as well as membrane receptors such as the EGF and TGF-${\beta}$ receptors. These molecules also play pivotal roles in the underlying mechanism of a variety of disease such as cancer metastasis, diabetes, and chronic obstructive pulmonary disease (COPD). Alterations in the structures of branched N-glycans are also hall marks and are useful for cancer biomarkers and therapeutics against cancer. This mini-review describes some of our recent studies on a functional glycomics approach to the study of branched N-glycans produced by N-acetylglucosaminyltransferases III, IV, V and IX (Vb) (GnT-III, GnT-IV, V and IX (Vb)) and fucosyltransferase 8 (Fut8) and their pathophysiological significance, with emphasis on the importance of a systems glycobiology approach as a future perspective for glycobiology.

Dust Collection Characteristics of Multi-layer Multi-stage Porous Plate System with Polarization Charge to Impaction Effect (임팩션 효과에 편극전하 방식을 부가한 다층 다단 다공성 플레이트 시스템의 집진특성)

  • Kim, Bo-Bae;Kim, Il-Kyu;Yoa, Seok-Jun
    • Journal of Korean Society of Environmental Engineers
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    • v.33 no.8
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    • pp.598-605
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    • 2011
  • The main object of this study is to investigate the Dust Collection Characteristics of multi-layer multi-stage porous plate system with polarization charging mechanism, experimentally. The experiment is carried to analyze the characteristics of pressure drop and collection efficiency for the present system with the experimental parameters such as applied voltage, inlet velocity, inlet concentration and stage number, etc. In results, the pressure drop becomes 18 to $134mmH_2O$, with increment of stage number (1 to 5) at inlet velocity $v_{in}$ = 3.11 m/s ($v_t$ = 18 m/s) and inlet concentration 3 g/m3 for inflow current. In case of both applied voltage 0 kV and non-inflow current, the collection efficiency of 5 stage is 92.5% at $v_{in}$ = 2.58 m/s ($v_t$ = 15 m/s), while it is estimated that the collection efficiency becomes about 6% higher than that of 0 kV and non-inflow as 98.5% at $v_{in}$ = 2.58 m/s for both alternating polarization charge (applied voltage 2.5 kV) and inflow current system.

The Measurements of Thermodynamic Properties for the Solute Transfer in RPLC with a $C_{18}$ Stationary Phase ($C_{18}$ 정지상으로 구성된 역상 액체 크로마토그래피에서 용질전이의 열역학적 특성측정)

  • Cheong, Won Jo;Kang, Young Ryul;Kang, Gyoung Won;Keum, Young Ik
    • Journal of the Korean Chemical Society
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    • v.43 no.6
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    • pp.656-662
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    • 1999
  • We have obtained retention data of benzene, toluene, ethylbenzene, phenol, and acetophenone at 25, 30, 35, 40, 45 and 50 $^{\circ}C$ in 30/70, 40/60, 50/50, 60/40, 70/30, and 80/20 (v/v %) methanol/water eluents using a $C_18$ phase with a high ligand density. We drew van't Hoff plots from the data, and computed enthalpies and entropies of solute transfer from the mobile to the stationary phase. The cavity formation effect was found the major factor that governs the solute distribution between the mobile and stationary phases. The hydrophobic effect became significant in highly aqueous mobile phases. We also concluded that the Shodex C18-5B stationary phase was a polymer-like phase with a high ligand density, and followed a partially adsorption-like mechanism.

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Forward-Mode $Na^+-Ca^{2+}$ Exchange during Depolarization in the Rat Ventricular Myocytes with High EGTA

  • Kim, Eun-Gi;Ko, Chang-Mann
    • The Korean Journal of Physiology and Pharmacology
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    • v.5 no.6
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    • pp.487-494
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    • 2001
  • During depolarization, extrusion of $Ca^{2+}$ from sarcoplasmic reticulum through forward-mode $Na^+-Ca^{2+}$ exchange was studied in the rat ventricular myocytes patch-clamped in whole-cell configuration. In order to confine the $Ca^{2+}$ responses in a micro-domain by limiting the $Ca^{2+}$ diffusion time, rat ventricular myocytes were dialyzed with high (14 mM) EGTA. $K^+$ current was suppressed by substituting KCl with 105 mM CsCl and 20 mM TEA in the pipette filling solution and by omitting KCl in the external Tyrode solution. $Cl^-$ current was suppressed by adding 0.1 mM DIDS in the external Tyrode solution. During stimulation roughly mimicking action potential, the initial outward current was converted into inward current, $47{\pm}1%$ of which was suppressed by 0.1 mM $CdCl_2.$ 10 mM caffeine increased the remaining inward current after $CdCl_2$ in a cAMP-dependent manner. This caffeine-induced inward current was blocked by $1\;{\mu}M$ ryanodine, $10\;{\mu}M$ thapsigargin, 5 mM $NiCl_2,$ or by $Na^+\;and\;Ca^{2+}$ omission, but not by $0.1\;{\mu}M$ isoproterenol. The $I{\sim}V$ relationship of the caffeine-induced current elicited inward current from -45 mV to +3 mV with the peak at -25 mV. Taken together, it is concluded that, during activation of the rat ventricular myocyte, forward-mode $Na^+-Ca^{2+}$ exchange extrudes a fraction of $Ca^{2+}$ released from sarcoplasmic reticulum mainly by voltage-sensitive release mechanism in a micro-domain in the t-tubule, which is functionally separable from global $Ca^{2+}{_i}$ by EGTA.

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Phosphorylation of p53 at threonine 155 is required for Jab1-mediated nuclear export of p53

  • Lee, Eun-Woo;Oh, Wonkyung;Song, Hosung Paul;Kim, Won Kon
    • BMB Reports
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    • v.50 no.7
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    • pp.373-378
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    • 2017
  • The Jun activation-domain binding protein 1 (Jab1) induces p53 nuclear export and cytoplasmic degradation, but the underlying mechanism is poorly understood. Here, we show that phosphorylation at the threonine 155 residue is essential for Jab1-mediated p53 nuclear export. Jab1 stimulated phosphorylation of p53 at T155 was inhibited by curcumin, an inhibitor of COP9 signalosome (CSN)-associated kinases. The T155E mutant, which mimics phosphorylated p53, exhibited spontaneous cytoplasmic localization in the absence of Jab1. This process was prevented by leptinomycin B (LMB), but not by curcumin. The substitution of threonine 155 for valine (T155V) abrogated Jab1-mediated p53 nuclear export, indicating that phosphorylation at this site is essential for Jab1-mediated regulation of p53. Although T155E can be localized in the cytoplasm in the absence of Mdm2, the translocation of T155E was significantly enhanced by ectopic Hdm2 expression. Our data suggests that Jab1-mediated phosphorylation of p53 at Thr155 residue mediates nuclear export of p53.

NDynamic Framework for Secure VM Migration over Cloud Computing

  • Rathod, Suresh B.;Reddy, V. Krishna
    • Journal of Information Processing Systems
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    • v.13 no.3
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    • pp.476-490
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    • 2017
  • In the centralized cloud controlled environment, the decision-making and monitoring play crucial role where in the host controller (HC) manages the resources across hosts in data center (DC). HC does virtual machine (VM) and physical hosts management. The VM management includes VM creation, monitoring, and migration. If HC down, the services hosted by various hosts in DC can't be accessed outside the DC. Decentralized VM management avoids centralized failure by considering one of the hosts from DC as HC that helps in maintaining DC in running state. Each host in DC has many VM's with the threshold limit beyond which it can't provide service. To maintain threshold, the host's in DC does VM migration across various hosts. The data in migration is in the form of plaintext, the intruder can analyze packet movement and can control hosts traffic. The incorporation of security mechanism on hosts in DC helps protecting data in migration. This paper discusses an approach for dynamic HC selection, VM selection and secure VM migration over cloud environment.

Spectral and Thermal Properties of Some Uranyl Complexes of Some Schiff-Bases Derived from Glycylglycine

  • Sh. A. Sallam;M. I. Ayad
    • Journal of the Korean Chemical Society
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    • v.47 no.3
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    • pp.199-205
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    • 2003
  • Complexes of uranyl ion $UO^{+2}_2$with Schiff-bases obtained by condensing glycylglycine with salicylaldehyde; 2-hydroxy-1-naphthaldehyde, 2,3-dihydroxybenzaldehyde, and 2,4-dihydroxybenzaldehyde have been synthesized and characterized through elemental analysis, conductivity measurements, magnetic susceptibility determinations, u.v., i.r. and $^1H$ nmr spectra as well as d.t.a., t.g. and d.s.c. techniques. Structures and mechanisms of thermal decomposition are proposed.

Effect of $Ta_2O_5$ Alloying on Low Temperature Degradation of 3 mol% Y-TZP ($Ta_2O_5$ 첨가가 3 mol% Y-TZP의 저온열화에 미치는 영향)

  • 김대준;최두진
    • Journal of the Korean Ceramic Society
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    • v.29 no.8
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    • pp.630-638
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    • 1992
  • Ta2O5 alloying into 3 mol% Y2O3-stabilized tetragonal ZrO2 polycrystals (3Y-TZP) increased the degradation during aging at 265℃ and the fracture toughness; both are determined by the amount of transformed m-ZrO2. It was proposed that the mechanism underlying the t→m transformation when aged at low temperatures is attributed to the reorientation of (Zzr'V ). complexes parallel to [111] lattice direction, which is accompanied by a relaxation of TZP lattice during annealing at low temperature. A small strain which results from the reorientation gives rise to a localized mechanical instability, thus lowering the nucleation barrier so that the t→m phase transformation (degradation) proceeds. The amount of transformed m-ZrO2 during aging becomes greater as the chemical free energy change related to the transformation, ΔGo, increases with increasing the Ta2O5 alloying content.

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