• Title/Summary/Keyword: constant-sign

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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.

Kinetics and Mechanism of the Addition of Benzylamines to Benzylidene Meldrum's Acids in Acetonitrile

  • Oh, Hyuck-Keun;Kim, Tae-Soo;Lee, Hai-Whang;Lee, Ik-Choon
    • Bulletin of the Korean Chemical Society
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    • v.24 no.2
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    • pp.193-196
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    • 2003
  • Nucleophilic addition reactions of benzylamines $(XC_6H_4CH_2NH_2)$ to benzylidene Meldrum's acids (BMA; $YC_6H_4CH=C(COO)_2C(CH_3)_2$) have been investigated in acetonitrile at 20.0 ℃. The rates of addition are greatly enhanced due to the abnormally high acidity of Meldrum's acid. The magnitudes of the Hammett $({\rho}_X\;and\;{\rho}_Y)$ and Bronsted $({\rho}_X$)$ coefficients are rather small suggesting an early transition state. The sign and magnitude of the cross-interaction constant, ${\rho}_{XY}$ (= -0.33), and kinetic isotope effects $(k_H/k_D\;{\stackrel}{~}{=}\;1.5-1.7)$ involving deuterated benzylamine nucleophilies $(XC_6H_4CH_2ND_2)$ are indicative of hydrogen-bonded cyclic transition state. The activation parameters, ${\Delta}H^{\neq}\;{\stackrel}{~}{=}\;4\;kcal\;mol^{-1}\;and\;{\Delta}S^{\neq}\;{\stackrel}{~}{=}\;-37\;e.u.$, are also in line with the proposed mechanism.

Electrochemical Properties of Polypyrrole-Glucose Oxidase Enzyme Electrode with Different Dopants (Polypyrrole-Glucose Oxidase 효소전극의 배위자 크기에 따른 전기화학적 특성)

  • 김현철;구할본
    • Journal of the Korean Institute of Electrical and Electronic Material Engineers
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    • v.15 no.2
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    • pp.141-146
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    • 2002
  • We synthesized polypyrrole (PPy) by electrolysis of the pyrrole monomer solution containing support electrolyte, KCl and/or p-toluene sulfonic acid sodium salt (p-TS). The electrochemical behavior, was investigated using cyclic voltammetry and AC impedance. In the case of using electrolyte p-TS, the oxidation potential of the PPy was about -02 V vs Ag/AgCl reference electrode, while the potential was about 0 V for using electrolyte KCl. The falloff of the oxidation potential gave a sign of an improvement in the electron hopoing mechanism on the backbone. The AC impedance plot gave a hint of betterment of mass transport. PPy doped with p-TS improved in mass transport or diffusion. That was because the PPy doped with p-TS was more porous than PPy with KCl. We attained an effect of good kinetic parameters, in the case of PP-GOx enzyme electrodes doped with p-TS, which were determined by 58 mmol dm$\^$-3/ for apparent Michaelis constant and by 581 ㎂ for maximum current respectively.

Kinetic Studies on the Nucleophilic Addition Reactons of Vinylic β-Diketones

  • Oh, Hyuck-Keun;Lee, Jae-Myon
    • Bulletin of the Korean Chemical Society
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    • v.23 no.10
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    • pp.1459-1462
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    • 2002
  • The kinetics of the addition of X-substituted benzylamines (BA) to Y-substituted Benzylideneacetylacetones (BAA) have been investigated in acetonitrile at $25.0^{\circ}C$. The reaction is studied under pseudo-first-order conditions by keeping a large excess of BA over BAA. The addition of BA to BAA occurs in a single step in which the addition of BA to $C_\alpha$ of BAA and proton transfer from BA to $C_\beta$ of BAA take place concurrently with a four-membered cyclic transition state structure. The magnitude of the Hammett ($p_X$) and Bronsted ($\beta_x$) coefficients are rather small suggesting an early tansition state (TS). The sign and magnitude of the cross-interaction constant, $p_{XY}$ (= -0.49), is comparatible to those found in the normal bond formation processes in the $S_N2$ and addition reactions. The normal kinetic isotope effect ($K_H/K_D$ > 1.0) and relatively low $\Delta$H^{${\neq}$}$ and large negative $\Delta$S^{${\neq}$}$ values are also consistent with the mechanism proposed.

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.

Relation between Huggins Constant and Compatibility of Binary Polymer Mixtures in the Aqueous Ternary Systems

  • Isamu Inamura;Makoto Kittaka;Tatsuya Aikou;Kazuhiko Akiyama;Tomoyuki Matsuyama;Masatsugu Hiroto;Hirade, Ken-ichi;Yuji Jinbo
    • Macromolecular Research
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    • v.12 no.2
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    • pp.246-250
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    • 2004
  • We have classified a number of aqueous ternary systems containing two different polymers into three types by focusing on the deviation of the Huggins constant k'from the additivity line. Systems of type I have negative deviations of k'; the repulsive interaction between the two different polymers dominates. In systems of type II, k' almost follows the additivity relation; the repulsive and attractive interactions between the two different polymers are balancing. Type III systems have positive deviations of k'; the attractive interactions are relatively dominant. This classification of systems is supported by the fact that the positive and negative deviations of k' from the additivity line also correspond to the sign of interaction parameter between polymer 2 and 3, Δb$\_$23/. Furthermore, we have verified the relatively high compatibility between dextran and poly(vinyl alcohol) by determining the binodal concentration of a liquid-liquid phase separation for a water/dextran/poly(vinyl alcohol) system, which is classified as type III. Thus, we found that the compositional dependence of k' closely relates to the compatibility of binary polymer mixtures in aqueous ternary systems.

Dimming Control of the LED Luminaire Emergency Exit Sign Operation using a Hybrid Super Capacitor of DC-DC Convertor (하이브리드 슈퍼커패시터 DC-DC 컨버터를 이용한 LED 비상 유도등 동작 디밍 제어)

  • Hwang, Lark-Hoon;Kim, Jin-Sun;Na, Yong-Ju
    • Journal of Advanced Navigation Technology
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    • v.21 no.3
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    • pp.220-229
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    • 2017
  • In this paper, To take advantage a variety of DC power as the boost DC-DC converter design specifications through the inductor L and capacitor C through PSPICE to calculate the best estimate of the value. Boost DC-DC converter with a switch device using IRF840 and reverse recovery time Schottky diodes with excellent with constant current controller using D10SC6M and resistance can be configured to considering the Power LED Module was driven by the production. Converter's switching frequency is 50 kHz, the first Duty Rate was made to increase gradually depending on the value of the detection were, 10 % in the output voltage. As a result, the simulated Boost Power LED driver characteristics is in comparison with the design specifications, 5% or less as the error was approximated. Finally, when input 15 V were offered, a stable output 24 V were obtained. and Dimming Control through the adjustment of brightness and current consumption were possible.

Characteristic of VSI Driven by Source Synchronous Type for the Utility Interactive using a Photovoltaic Generation for the LED Luminaire Emergency Exit Sign Operation (LED 비상 유도등 동작을 위한 태양광발전 계통연계 전원동기 방식의 전압형 인버터 구동 특성)

  • Hwang, Lark-Hoon;Na, Yong-Ju
    • Journal of Advanced Navigation Technology
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    • v.22 no.5
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    • pp.420-428
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    • 2018
  • In this paper, represented uninterruptible power supply (UPS) equipment maintaining constant output voltage, the proposes a photovoltaic system constructed with a step up boosting chopper and single phase pulse width modulation (PWM) voltage source inverter. as power source disconnection, voltage variation and output current variation with load variation. This system is driven by being synchronized voltage fed inverter and AC source, and in the steady state of power source charge battery connected to DC side with solar cell using a Photovoltaic that it was so called constant voltage charge. It can be results of saving electric power, and through a normal operation of energy storage system (ESS), the system operated the LED a calling on signal changes at the airport in an efficient manner. In addition, better output waveform was generated because of PWM method, and it was proved to test by experiment maintained constant output voltage regardless of AC source disconnection, load variation, and voltage variation of AC power source.

Dynamic Control of Random Constant Spreading Worm using Depth Distribution Characteristics

  • No, Byung-Gyu;Park, Doo-Soon;Hong, Min;Lee, Hwa-Min;Park, Yoon-Sok
    • Journal of Information Processing Systems
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    • v.5 no.1
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    • pp.33-40
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    • 2009
  • Ever since the network-based malicious code commonly known as a 'worm' surfaced in the early part of the 1980's, its prevalence has grown more and more. The RCS (Random Constant Spreading) worm has become a dominant, malicious virus in recent computer networking circles. The worm retards the availability of an overall network by exhausting resources such as CPU capacity, network peripherals and transfer bandwidth, causing damage to an uninfected system as well as an infected system. The generation and spreading cycle of these worms progress rapidly. The existing studies to counter malicious code have studied the Microscopic Model for detecting worm generation based on some specific pattern or sign of attack, thus preventing its spread by countering the worm directly on detection. However, due to zero-day threat actualization, rapid spreading of the RCS worm and reduction of survival time, securing a security model to ensure the survivability of the network became an urgent problem that the existing solution-oriented security measures did not address. This paper analyzes the recently studied efficient dynamic network. Essentially, this paper suggests a model that dynamically controls the RCS worm using the characteristics of Power-Law and depth distribution of the delivery node, which is commonly seen in preferential growth networks. Moreover, we suggest a model that dynamically controls the spread of the worm using information about the depth distribution of delivery. We also verified via simulation that the load for each node was minimized at an optimal depth to effectively restrain the spread of the worm.

Drug-Biomacromolecule Interaction (XIII)-Effect of ionic Strength, pH and Temperature on Binding of Cephalothin to Bovine Serum Albumin- (약물과 생체고분자 간의 상호작용(제 13보)-세파로친과 소혈청알부민의 결합에 미치는 이온강도, pH 및 온도의 영향)

  • Kim, Chong-Kook;Lim, Yun-Su;Yang, Ji-Sun;Jeong, Eun-Ju
    • Journal of Pharmaceutical Investigation
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    • v.19 no.3
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    • pp.163-171
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    • 1989
  • To investigate the protein binding characteristics of cephalothin, the effects of ionic strength, pH and temperature on the binding of cephalothin to bovine serum albumin (BSA) were studied by UV difference spectrophotometric method. With increasing ionic strength at constant PH and temperature, association constant decreased, but the number of binding sites sites was about 2 constantly. It may be deduced that the binding process is not only due to electrostatic forces. And the increased association constant at high ionic strength is explained by conformational changes of BSA from complex to subunits. The pH effect on the affinity of interaction indicated that the binding affinity of drug is higher in the neutral region than in the alkaline region. And, at high pH value, the number of binding sites decreased from 2 to 1 because of the conformational changes of BSA in alkaline region. The decrease in binding affinity of BSA to drug with increasing temperature was characteristic of an exothermic reaction. And the negative sign of ${\Delta}G^{\circ}$ meant that the binding process occurs spontaneously under the experimental conditions. In cephalothin-BSA complex formation, since the net enthalpy change value and entropy change value are positive, it is assumed that hydrophobic bindings are predominant in this binding process.

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