• Title/Summary/Keyword: p-$\Delta$ effect

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The Effect of Pressure on the Solvolysis of Benzylchlorides. p-Methoxybenzyl Chloride in Ethanol-Water Mixtures (염화벤질류의 가용매분해반응에 대한 압력의 영향. 에탄올-물 혼합용매내에서 p-메톡시 염화벤질의 분해반응)

  • Oh Cheun Kwun;Jin Burm Kyong;Kee Joon Choi
    • Journal of the Korean Chemical Society
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    • v.30 no.3
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    • pp.301-306
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    • 1986
  • The rate constants for the solvolysis reactions of p-methoxybenzylchloride in ethanol-water mixtures were determined at 2$^{\circ}$ and 10$^{\circ}C$ up to 1600bar. Rates of reaction were increased with increasing temperature and pressure, and decreased with increasing solvent composition of ethanol mole fraction. From the rate constants, the values of the activation parameters (${{\Delta}V_o}^{\neq},\;{\Delta}{\beta}^{\neq},\;{\Delta}H^{\neq},\;and\;{\Delta}S^{\neq}$) were evaluated. The values of ${{\Delta}V_o}^{\neq}$ and ${\Delta}{\beta}^{\neq}$ exhibit the extremum behavior at about 0.30 mole fraction of ethanol. This behavior is discussed in terms of solvent structure variation. From these results, it could be postulated that the reaction proceeds through $S_N1$ mechanism.

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The Effect of 15% Carbamide Peroxide on the Surface Roughness and Staining of Esthetic Restoratives (15% Carbamide Peroxide가 심미수복재의 표면조도와 착색에 미치는 영향)

  • Kim, Soo-Hwa;Choi, Hye-Sook;Roh, Jj-Yeon;Kim, Kwang-Mahn
    • Journal of dental hygiene science
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    • v.13 no.2
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    • pp.165-173
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    • 2013
  • The purpose of this study was to evaluate the surface change after 15% carbamide peroxide home bleaching to various restorative materials (composite resin [CR], resin modified glass ionomer [RMGI] and glass ionomer [GI]) and to observe the effect of surface condition of the materials on re-staining. Three esthetic restorative materials (Filtek Z250, 3M, USA; Fuji II LC, GC, Japan; Fuji II, GC, Japan) were used in this study. Twenty specimens per material group were made and divided into two groups (bleached and control). The specimens were immersed in coffee after applying bleaching agent. The color change and surface roughness were measured before and after bleaching and after immersion in coffee. The data were analyzed with SPSS 18.0. The results were as follows: 1. The color of all experiment groups was significantly changed after bleaching (p<0.05). RMGI was the greatest value of ${\Delta}E^*$ and ${\Delta}L^*$. GI and CR groups were in ordering (p<0.05). The ${\Delta}a^*$ value was decreased GI, RMGI and CR. RMGI was only significantly decreased in ${\Delta}b^*$ value (p<0.05). 2. The surface roughness before and after bleaching was significantly different on CR, RMGI and GI (p<0.05). 3. After staining with coffee, the value of ${\Delta}E^*$ was increased in GI, RMGI and CR, furthermore GI and RMGI showed significant difference in the bleaching groups (p<0.05). The ${\Delta}L^*$ value of GI and RMGI was significantly decreased. 4. The change of surface roughness after staining was not significantly different in all groups (p>0.05). The maintenance of color stability in esthetic restorations is one of the most important properties. Tooth whitening is for the aesthetic. Therefore, dental professionals should notice to patients about re-staining after tooth whitening. They should give an instruction that how to prevent and which kinds of agents could be stained.

The Effect of Pressure on the Reaction of p-Substituted Benzoyl Chlorides with Pyridine (염화벤조일류와 피리딘과의 반응에 대한 압력의 영향)

  • Young Cheul Kim;Jin Burm Kyong;Se Kyong Kim;Deog Ja Koo
    • Journal of the Korean Chemical Society
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    • v.36 no.2
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    • pp.180-184
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    • 1992
  • Kinetic studies for the reaction of pyridine with substituted benzoyl chlorides were conducted under various pressures (1-1000 bar) in acetonitrile. From rate constants, the activation parameters (${\Delta}V^{\neq}$, ${\Delta}{\beta}^{\neq}$,${\Delta}H^{\neq}$, ${\Delta}S^{\neq}$ and ${\Delta}G^{\neq}$) were evaluated. Rates of these reaction increased with an increase in the pressure. The activation volume, the activation compressibility coefficient and the activation entropy were negative. From substituents effect and these results, it was found that these reactions proceed through $S_N2$ mechanism, but the structure of transition state was slightly changed with substituents and pressure.

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Enzymatic Characteristics of steroid $\Delta^1$-dehydrogenase from Arthrobacter simplex

  • Lee, Mi-Kyung;Bae, Moo
    • Journal of Microbiology and Biotechnology
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    • v.4 no.2
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    • pp.119-125
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    • 1994
  • Steroid $\Delta^1$-dehydrogenase purified from hydrocortisone-induced cells of Arthrobacter simplex converted various 3-ketosteroids into their corresponding $\Delta^1$-dehydrogenated products. The transformation efficiencies depend upon the chemical structure of the steroids, especially length of the side chain at 17 position and hydroxyl groups at 11 and 17 positions. The Km values for androstenedione, the most favorable substrate examined, and hydrocortisone were 74 ${\mu}M$ and 294 ${\mu}M$, respectively. The optimum temperature and pH of the enzyme reaction were 35$^{\circ}C$ and pH 9, respectively, and the enzyme was relatively stable at the range from 20 to 35$^{\circ}C$ and from pH 5 to 10 after one hour of incubation. The enzyme activity was markedly inhibited in the presence of $Cu^{2+},\;Fe^{3+},\;Hg^{2+},\;Mo^{6+}$ ions, and somewhat inhibited by $Zn^{2+}$ and $Fe^{2+}$. $\alpha,\alpha'$-Dipyridyl that inhibits 9$\alpha$-hydroxylase and accumulates 1,4-androstadiene-3,17-dione from sterols revealed no inhibitory effect on this enzyme. EGTA showed inhibitory effect. $\beta$-Estradiol competitively inhibited the enzyme activity. Chemical modifications of the enzyme were attempted with several reagents. p-Hydroxymer-curibenzoate showed inhibition of the enzyme activity and protection of the substrate. This suggests that cysteine residue may be involved in the active site of the enzyme.

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Nonlinear Inelastic Analysis of 3-Dimensional Steel Structures Using Fiber Elements (화이버 요소를 이용한 3차원 강구조물의 비선형 비탄성 해석)

  • Kim, Seung-Eock;Oh, Jung-Ryul
    • Journal of the Computational Structural Engineering Institute of Korea
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    • v.19 no.4 s.74
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    • pp.347-356
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    • 2006
  • In this paper, practical nonlinear inelastic analysis method of 3-dimensional steel structures accounting for gradual yielding with fibers on a section is developed. Geometric nonlinearities of member(p-$\delta$) and frame(p-$\Delta$) are accounted for by using stability functions. Residual stresses are considered by assigning initial stresses to the fiber on the section. The elastic core in a section is investigated at every loading step to determine the axial and bending stiffness reduction. The strain reversal effect is captured by investigating the stress change of each fiber. The proposed analysis proves to be useful in applying for practical analysis and design of three-dimensional steel frames.

The Effect of Pressure on the Solvolysis of Benzylchlorides(Ⅰ). p-Methylbenzyl Chloride in Ethanol-Water Mixtures

  • Kwun, Oh-Cheun;Kyong, Jin-Burm
    • Bulletin of the Korean Chemical Society
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    • v.6 no.5
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    • pp.259-263
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    • 1985
  • Rate Constants for the solvolysis of p-methylbenzyl chloride in various ethanol-water mixtures were studied at 30 and $40^{\circ}C$ under various pressures up to 1600 bar. The rates of reaction were increased with increasing temperature and pressure, and decreased with increasing solvent composition of ethanol mole fraction. From the rate constants, the values of the activation parameters (${\Delta}V^{\neq},{\Delta}{\beta}^{\neq},{\Delta}H^{\neq}\;and\;{\Delta}S^{\neq}$) were evaluated. The values of ${\Delta}V^{\neq}\;and\;{\Delta}{\beta}^{\neq}$ exhibit the extremum behavior at about 0.30 mole fraction of ethanol. This behavior is discussed in terms of solvent structure variation (electrostriction). From the relation between the reaction rate and the dielectric constant of solvent or the number of water molecule participated in the transition state, it could be postulated that the reaction proceeds through $S_N1$ mechanism.

Thermodynamic Properties of Lanthanides Complexes with Benzoylformate Anion (Lanthanides-Benzoylformate 착물 형성에 관한 열역학적 연구)

  • Young-Inn Kim;Sun-Geum Park
    • Journal of the Korean Chemical Society
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    • v.37 no.4
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    • pp.442-447
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    • 1993
  • The thermodynamic parameters (${\Delta}$G, ${\Delta}$H and ${\Delta}$S) of lanthanides(III)-benzoylformate complexes in aqueous solution have been determined in the ionic medium of 0.1M $NaClO_4$ at 25$^{\circ}C$, using pH and enthalpy titration method. The stability constants of the lanthanide(III)-benzoylformate complexes (1 : 1) agree well with the general relationships for the bidentate ligands (e.g., log${\beta}_1$ vs. p$K_a$). Thermodynamic evidences show that the oxygen atom in ketone group is coordinated along with the carboxylate group. It is ascribed to the increasing charge density on the oxygen atom in ketone group due to the conjugation effect in the benzoylformate ligand. Thermodynamic results also indicate that the complexes are stabilized by the enthalpy effect caused by the ionic interaction of metal-oxygen bond as well as the entropy effect.

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Analysis of Plastic Hinge on Pile-Bent Structure with Varying Diameters (변단면 단일 현장타설말뚝의 소성힌지 영향분석)

  • Ahn, Sangyong;Jeong, Sangseom;Kim, Jaeyoung
    • KSCE Journal of Civil and Environmental Engineering Research
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    • v.30 no.3C
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    • pp.149-158
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    • 2010
  • In this study, the behavior of Pile-Bent structure with varying diameters subjected to lateral loads were evaluated by a load transfer approach. An analytical method based on the beam-column model and nonlinear load transfer curve method was proposed to consider material non-linearity (elastic, yielding) and P-${\Delta}$ effect. For an effective analysis of behavior Pile-Bent structure, the bending moment and fracture lateral load of material were evaluated. And special attention was given to lateral behavior of Pile-Bent structures depending on reinforcing effect of materials and ground conditions. Based on the parametric study, it is shown that the maximum bending moment is located within a depth (plastic hinge) approximately 1~3D (D: pile diameter) below ground surface when material non-linearity and P-${\Delta}$ effect are considered. And distribution of the lateral deflections and bending moments on a pile are highly influenced by the effect of yielding. It is also found that this method considering material yielding behavior and P-${\Delta}$ effect can be effectively used to perform the preliminary design of Pile-bent structures.

The Effect of Pressure on the Solvolysis of Benzylchlorides (II). p-Chlorobenzyl Chloride in Ethanol-Water Mixtures (염화벤질류의 가용매분해반응에 대한 압력의 영향 (제 2 보). 에탄올-물 혼합용매내에서 p-클로로 염화벤질의 분해반응)

  • Oh Cheun Kwun;Jin Burm Kyong
    • Journal of the Korean Chemical Society
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    • v.30 no.2
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    • pp.188-194
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    • 1986
  • The rate constants for the solvolysis reactions of p-chlorobenzyl chloride in ethanol-water mixtures were determinded at 30${\circ}\;and\;40{\circ}$C up to 1,600bar. Rates of reaction were increased with increasing temperature and pressure, and decreased with increasing solvent composition of ethanol mole fraction. The plots of ln k against pressure are fitted to a second-order function in P, and values of ${\Delta}V^{\neq}\;and\;${\Delta}{\beta}^{\neq}$ are obtained. The values of ${\Delta}V^{\neq}\;and\;${\Delta}{\beta}^{\neq}$ extremum behavior at about 0.20 mole fraction of ethanol. This behavior is discussed in terms of solvent structure variation. From the relation between the plots of ln k versus the solvent parameter, q ≡ (D-1)/(2D+1), or the logarithmic molar water concentration, In $C_w$, it could be estimated that the reaction proceeds through $S_N1(2)$ mechanism.

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Pharmacokinetic and Pharmacodynamic Characterization of Gliclazide in Healthy Volunteers

  • Kim, Ho-Soon;Yun, Min-Hyuk;Kwon, Kwang-Il
    • Archives of Pharmacal Research
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    • v.26 no.7
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    • pp.564-568
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    • 2003
  • Pharmacokinetic and pharmacodynamic properties of gliclazide were studied after an oral administration of gliclazide tablets in healthy volunteers. After an overnight fasting, gliclazide tablet was orally administered to 11 volunteers; Additional 10 volunteers were used as a control group (i.e., no gliclazide administration). Blood samples were collected, and the concentration determined for gliclazide and glucose up to 24 after the administration. Standard pharmacokinetic analysis was carried out for gliclazide. Pharmacodynamic activity of the drug was expressed by increase of glucose concentration ($\Delta$PG), by area under the increase of glucose concentration-time curve ($AUC_{$\Delta$PG}$) or by the difference in increase of glucose concentration ($D_{$\Delta$PG}$) at each time between groups with and without gliclazide administration. Pharmacokinetic analysis revealed that $C_{max}, T_{max}$, CL/F (apparent clearance), V/F (apparent volume of distribution) and half-life of gliclazide were $4.69\pm1.38 mg/L, 3.45\pm1.11 h, 1.26\pm0.35 L/h, 17.78\pm5.27 L, and 9.99\pm2.15 h$, respectively. When compared with the no drug administration group, gliclazide decreased significantly the $AUC_{$\Delta$PG}$ s at 1, 1.5, 2, 2.5, 3 and 4 h (p<0.05). The $\Delta$PGs were positively correlated with $AUC_{gliclazide}$ at 1 and 1.5 h (p<0.05), and the correlation coefficient was maximum at 1 h (r = 0.642) and gradually decreased at 4 h after the administration. The $AUC_{$\Delta$PG}$s were positively correlated with $AUC_{gliclazide}$ at 1, 2, 3 and 4 h (p<0.05), and the maximum correlation coefficient was obtained at 2 h (r=0.642) after the administration. The $D_{$\Delta$PG}$ reached the maximum at 1 h, remained constant from 1 h to 3 h, and decreased afterwards. Therefore, these observations indicated that maximum hypoglycemic effect of gliclazide was reached at approximately at 1.5 h after the administration and the effect decreased, probably because of the homeostasis mechanism, in health volunteers.