• Title/Summary/Keyword: basicity

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Cyclic Oligopyrroles as Sensors for Absolute Configuration Determination of Carboxylic Acids

  • Lintuluoto Juha M.;Nakayama Kana;Setsune Jun-Ichiro
    • Proceedings of the Polymer Society of Korea Conference
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    • 2006.10a
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    • pp.241-241
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    • 2006
  • Absolute configuration of carboxylic acids, including amino acids can be determined by circular dichroism (CD) exciton chirality method. This method employs cyclic oligopyrroles able to form stable complexes with carboxylic acids. Addition of carboxylic acids to the oligopyrroles induce CD spectrum at the macrocycle absorption region and in which the sign of the $1^{st}$ Cotton effect is determined solely by the absolute configuration of the carboxylic acid. The basicity of the pyrrole nitrogen can be controlled by macrocycle substitution thus yielding more sensitive chirality sensors.

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Characterization of DNA/Poly(ethylene imine) Electrolyte Membranes

  • Park, Jin-Kyoung;Won, Jong-Ok;Kim, Chan-Kyung
    • Macromolecular Research
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    • v.15 no.6
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    • pp.581-586
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    • 2007
  • Cast DNA/polyethyleneimine (PEI) blend membranes containing different amounts of DNA were prepared using acid-base interaction and characterized with the aim of understanding the polymer electrolyte membrane properties. Two different molecular weights of PEI were used to provide the mechanical strength, while DNA, a polyelectrolyte, was used for the proton transport channel. Proton conductivity was observed for the DNA/PEI membrane and reached approximately $3.0{\times}10^{-3}S/cm$ for a DNA loading of 16 wt% at $80^{\circ}C$. The proton transport phenomena of the DNA/PEI complexes were investigated in terms of the complexation energy using the density functional theory method. In the case of DNA/PEI, a cisoid-type complex was more favorable for both the formation of the complex and the dissociation of hydrogen from the phosphate. Since the main requirement for proton transport in the polymer matrix is to dissociate the hydrogen from its ionic sites, this suggests the significant role played by the basicity of the matrix.

Study of 8-Hydroxyquinoline Derivatives. The Acid Dissociation Constants of 5-Acetyl-8-Hydroxyquinoline (8-Hydroxyquinoline 誘導體에 關한 硏究 5-Acetyl-8-Hydroxyquinoline의 酸解離定數)

  • Lee, Dong-Hyung
    • Journal of the Korean Chemical Society
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    • v.9 no.1
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    • pp.33-36
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    • 1965
  • Acid dissociation constants of 5-acetyl-8-hydroxyquinoline have been determined by spectrophotometric and potentiometric methods at $25^{\circ}C$. $pK_1$, $pK_2$ values obtained by potentiometric method were 4.56, 8.20 respectively and $pK_1$ obtained by spectrophotometric method was 4.21. pK values were lower than those of 8-hydroxyquinoline. The lower basicity of 5-acetyl-8-hydroxyquinoline compared with 8-hydroxyquinoline was considered as the result of the electronic attraction of the acetyl group with aromatic ring.

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Studies of 8-Hydroxyquinoline Derivatives (Part I) Synthesis of 7-Nitroso-8-Hydroxyquinoline-5-Sulfonate and its Acid Dissociation Constants (8-Hydroxyquinoline 誘導體에 關한 硏究 (第 1 報) 7-Nitroso-8-Hydroxyquinoline-5-Sulfonate 의 合成과 그 酸解離定數)

  • Lee, Dong-Hyung
    • Journal of the Korean Chemical Society
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    • v.9 no.1
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    • pp.37-40
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    • 1965
  • 7-Nitro-8-hydoxyquinoline-5-sulfonate (NHQS) have been synthesized from 8-hydroxyquinoline-5-sulfonic acid by nitrosation in alkaline medium at temperature below $10^{\circ}C$ and the acid dissociation constants of NHQS have been determined by spectrophotometric and potentiometric methods. Almost same values are obtained by both methods but the values are lower than the corresponding 8-hydroxyquinoline. The lower basicity of NHQS is considered as the effect of electron withdrawing groups, especially adjacent nitroso group.

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Gas Phase Proton Affinity, Basicity, and pKa Values for Nitrogen Containing Heterocyclic Aromatic Compounds

  • Hwang, Sun-Gu;Jang, Yun-Hee;Chung, Doo-Soo
    • Bulletin of the Korean Chemical Society
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    • v.26 no.4
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    • pp.585-588
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    • 2005
  • Bipyridine and its derivatives have been widely used as the ligands in transition metal complexes. The proton affinities of pyridine derivatives were calculated using an ab initio quantum mechanical method (B3LYP with various double zeta and triple zeta basis sets) in combination with the Poisson-Boltzmann continuum solvation model. Van der Waals radii of the atoms in the heterocyclic rings for the solvation energy calculation were set to values determined to reproduce the $pK_a$ values of guanine and oxoguanine derivatives and that of chlorine was optimized to reproduce the experimental values of relating compounds. The $pK_a$ values for the heterocyclic ring compounds were in agreement with the experimental values with a mean unsigned error of 0.45 $pK_a$ units.

Kinetics and Mechanism of Pyridinolysis of Aryl Dithiocyclopentanecarboxylates in Acetonitrile

  • Oh, Hyuck-Keun
    • Bulletin of the Korean Chemical Society
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    • v.31 no.8
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    • pp.2357-2360
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    • 2010
  • Kinetic studies on the pyridinolysis of aryl dithiocyclopentanecarboxyaltes 2 were carried out at $60.0^{\circ}C$ in acetonitrile. In the aminolysis of 2, the $\beta_X$ values were 0.5 - 0.8 with anilines, and there was no breakpoint. However, in the pyridinolysis of 2, biphasic Bronsted plots were obtained, with a change in slope from a large value ($\beta_X{\cong}0.7$) to a small value ($\beta_X{\cong}0.4$) at $pK_{a}^0$ = 5.2. This was attributed to a change in the rate-limiting step from breakdown to the formation of a zwitterionic tetrahedral intermediate, $T^{\pm}$, in the reaction path, with an increase in the basicity of the pyridine nucleophile. An obvious change in the cross-interaction constant ${\rho}_{XZ}$ from a large positive ($\rho_{XZ}$ = +1.02) value to a small negative value (${\rho}_{XZ}$ = -0.17) supports the proposed mechanistic change.

Effects of Hydrothermal Conditions on the Morphology of Hematite Particles (Hematite 입자형상에 미치는 수열반응조건의 영향)

  • 변태봉;손진군
    • Journal of the Korean Ceramic Society
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    • v.31 no.2
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    • pp.117-128
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    • 1994
  • Hematite particles were obtained by hydrothermal reaction of ferric hydroxide in the presence of small amount of citric acid which is acted as crystal growth controller. The effects of hydrothermal reaction condition son the morphology and crystal structure of powder were investigated using X-ray, TEM and FT-IR. Ellipsoidal or rectangular hematite particles were formed in the range of pH 10.75~11.75 as initial basicity of reactants and 3$\times$10-5 ~9$\times$10-5 mol as citric acid content. Crystallization of hematite was inhibited in the range of pH9. 0~10.5 and above citric acid content of $1.5\times$10-4 mol. Hematite particle length and aspect ratio were decreased gradually with increasing of citric acid content. Hematite particles formed at 14$0^{\circ}C$ exhibited particle properties with the length of 0.7 ${\mu}{\textrm}{m}$ and aspect ratio of 8. Hematite particles having a good acicular-type were not obtained above 22$0^{\circ}C$.

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The Response Characteristic of Hydrogen-responsive Glass Electrode in Methanol, N, N-dimethylformamide and Acetonitrile (Methanol, N,N-dimethylformamide 및 Acetonitrile 속에서 유리전극의 pH 응답성)

  • Su Chan Moon
    • Journal of the Korean Chemical Society
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    • v.16 no.3
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    • pp.149-156
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    • 1972
  • The responsive characteristics of hydrogen-responsive glass electrode in various buffer solutions of methanol, N,N-dimethylformamide and acetonitrile were examined. The potentials were attained more rapidly with an electrode stored in the same solvent medium than that stored in water before use. However, the time to be required for a stable potential increased with the basicity of buffer solution, and it was not provide a constant potential in the strong basic solution of these solvent. Even in acidic solution, the potential was varied according to the past usage of the electrode.

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Application of Two Centre Huckel Method for Basicity of the Polydentate Amine Ligands (여러자리 아민리간드의 염기도에 대한 이중심 Huckel 법의 응용)

  • Kim, Ja Hong;Lee Kae Soo
    • Journal of the Korean Chemical Society
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    • v.22 no.5
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    • pp.317-319
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    • 1978
  • The change of the electron densities of polydentate amine ligands in the reaction of protonation are discussed on the basis of the calculation by Two Center Huckel method. From results, such as ${\Delta}E_{\sigma}$, $q_N,\;q_H$ , and observed pKb, it is concluded that the stabilities of polydentate amine ligands are in the order of trien > en > gly > dien.

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Interactions between Dimethylsulfoxide and Some Organic Molecules (Dimethylsulfoxide와 몇 가지 유기분자와의 상호작용)

  • Si-Joong Kim;Doo-Soon Shin
    • Journal of the Korean Chemical Society
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    • v.15 no.6
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    • pp.352-358
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    • 1971
  • The interaction between dimethylsulfoxide molecules and some organic molecules, i.e.nitrobenzene, m-dinitrobenzene, o-dinitrobenzene, 1,3,5-trinitrobenzene, m-xylene, mesitylene, bibenzyl, biphenyl, o-phenanthrene, naphthalene, has been studied. The organic molecules exhibit negative deviation from Raoult's law due to the formation of the charge transfer complexes with dimethylsulfoxide. The stability constants of the complexes were determined spectrophotometrically, and also some thermodynamic functions were calculated. The binding energies of the complexes appear in the range of -1 ∼ -4 kcal/mole. The stability depends on the polarity and basicity of the solvent used.

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