• Title/Summary/Keyword: Dissociation constants

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The Synthesis of 2, 3, 4-Pentanetrionetrioxime and Acid Dissociation Constants (2,3,4-Pentanetrionetrioxime의 합성과 산해리 정수)

  • Oh, Joon-Suk;Lee, Kwang-Woo;Jun, Hee-Bong
    • Journal of the Korean Chemical Society
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    • v.12 no.4
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    • pp.150-154
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    • 1968
  • 2,3,4-Pentanetrionetrioxime was synthesized from 2,4-pentanedione(or acetylacetone) and its acid dissociation constants were determined in 50%(v/v) dioxane-water solvent mixture at $20{\pm}0.1^{\circ}C$. The color reactions of the ligand with divalent metal ions, Fe(II), Ni(II), Co(II), Cu(II), and Mn(II) were studied.

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Syntheses of Tetradentate Nitrogen-Oxygen(N2O2)) Ligands with Substituents and the Determination of Stability Constants of Their Heavy(II) Metal Complexes (치환기를 가진 질소-산소(N2O2)계 네 자리 리간드의 합성과 중금속(II)이온 착화합물의 안정도상수 결정)

  • Kim, Sun-Deuk;Seol, Jong-Min
    • Journal of Environmental Science International
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    • v.21 no.4
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    • pp.421-435
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    • 2012
  • Novel $N_2O_2$ tetradentate ligands, H-3BPD and H-2BPD were synthesized. Hydrochloric acid salts of Br-3BPD, Cl-3BPD, Br-2BPD and Cl-2BPD having Br and Cl substituents at the $para$ position of the phenol hydroxyl group, were synthesized. The ligands were characterized by C. H. N atomic analysis, $^1H$ NMR, $^{13}C$ NMR, UV-visible, and mass spectra. The proton dissociation constants ($logK_n{^H}$) of the phenol hydroxyl group and secondary amine of the synthesized $N_2O_2$ ligands were shown by four step wise values. The orders of the calculated overall proton dissociation constants ($log{\beta}_p$) were Br-3BPD < Cl-3BPD < H-3BPD in case of 3BPD and Br-2BPD < Cl-2BPD < H-2BPD in case of 2BPD respectively. The order agreed well with that of $para$ Hammett substituent constants(${\delta}_p$). The stability constants($logK_{ML}$) of the complexes between the synthesized ligands and transition metal(II) ions agreed with the order of $log{\beta}_p$ of the ligands. The order of the $logK_{ML}$ value of the each transition metal (II) ion was Co(II) < Ni(II) < Cu(II) > Zn(II) > Cd(II) > Pb(II), which agreed well with that of Iriving-Williams series.

The Kinetic Characteristics of K228G Mutant Horse Liver Alcohol Dehydrogenase

  • Cho, Sun-Hyoung;Ryu, Ji-Won;Lee, Kang-Man
    • Archives of Pharmacal Research
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    • v.22 no.1
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    • pp.13-17
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    • 1999
  • The kinetic constants and the reaction mechanism of the K228G mutant horse liver alcohol dehyrogenase isoenzyme E (HLADH-E) were compared to the wild-type enzyme. All the Km and Ki constants of the mutant enzyme for NAD+, ethanol, acetaldehyde and NADH were larger than those of the wild-type enzyme. The dissociation constants for the NADH and $NAD^{+}$ (Kiq and Kia) were greatly increased by 130-and 460-fold, respectively. The product inhibition patterns suggested that the reaction mechanism of the mutant enzyme was changed to Random Bi Bi. These results could attribute to the increase in the dissociation rate of coenzyme with the substitution at Lys-228 residue.

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Synthesis of New N2O2 Tetradentate Ligands and Determination of Stability Constants of Metal Complexes for Removal of Heavy Metals (중금속 이온 분리를 위한 새로운 네 자리 N2O2계 리간드의 합성 및 착 화합물의 안정도상수 결정)

  • Kim, Sun-Deuk;Kim, Jun-Kwang;Lee, Kyung-Ho
    • Journal of Environmental Science International
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    • v.16 no.8
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    • pp.913-920
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    • 2007
  • Hydrochloride acid salts of new $N_2O_2$ tetradentate ligands containing amine and phenol N,N'-bis(2-hydroxybenzyl)-o-phenylenediamine(H-BHP), N,N'-bis(5-bromo-2-hydroxybenzyl)-o-phenylenediamine(Br-BHP), N,N'-bis(5-chloro-2-hydroxybenzyl)-o-phenylene-diamine(Cl-BHP), N,N'-bis(5-methyl-2-hydroxybenzyl)-o-phenylene-diamine (Me-BHP) and N,N'-bis(5-methoxy-2-hydroxybenzyl)-o-phenylenediamine(MeO-BHP) were synthesized. The ligands were characterized by elemental analysis, mass and NMR spectroscopy. The elemental analysis showed that the ligands were isolated as dihydrochloride salt. The potentiometry study revealed that the proton dissociation constants$(logK_n{^H})$ of ligands and stability constants $(logK_{ML})$ of transition and heavy metals complexes. The order of the stability constants of each metal ions for ligands was Br-BHP < Cl-BHP > H-BHP < MeO-BHP < Me-BHP.

Mass Spectrometric Determination of Zn2+ Binding/Dissociation Constant for Zinc Finger Peptides

  • Lee, Choong Sik;Park, Soo Jin;Lee, Jae Young;Park, Sungsu;Jo, Kyubong;Oh, Han Bin
    • Mass Spectrometry Letters
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    • v.6 no.1
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    • pp.7-12
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    • 2015
  • In the present study, we proposed a simple ESI-MS model for determining $Zn^{2+}$ binding (or dissociation) constants for zinc finger peptides (ZFPs) with a unique ${\beta}{\beta}{\alpha}$ fold consensus. The ionization efficiency (response) factors for this model, i.e., ${\alpha}$ and ${\beta}$, could be determined for ZiCo ZFP with a known $Zn^{2+}$ binding constant. We could determine the binding constants for other ZFPs assuming those with a ${\beta}{\beta}{\alpha}$ consensus conformation have the same ${\alpha}/{\beta}$ response ratio. In general, the ZPF dissociation constants exhibited $K_d$ values of $10^{-7}{\sim}10^{-9}M$, while $K_d$ values for a negative control non-specific $Zn^{2+}$ peptides were high, e.g., $5.5{\times}10^{-6}M$ and $4.3{\times}10^{-4}M$ for BBA1 and melittin, respectively.

Synthesis of new N2O2 tetradentate ligands and the substituent effect on the stability constants of the transition metal complexes (새로운 산소-질소(N2O2)계 네 자리 리간드의 합성과 전이금속 착물 안정도상수에 대한 치환기 효과)

  • Kim, Sun Deuk;Jin, Gyoung Rok
    • Analytical Science and Technology
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    • v.19 no.2
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    • pp.131-141
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    • 2006
  • Hydrobromic acid salt of a $N_2O_2$ tetradentate ligand, N,N'-bis(2-hydroxybenzyl)-ethylene-diamine ($H-BHE{\cdot}2HBr$) was synthesized. $Br-BHE{\cdot}2HBr$, $Cl-BHE{\cdot}2HBr$, $CH_3-BHE{\cdot}2HBr$ and $CH_3O-BHE{\cdot}2HBr$ having Br, Cl, $CH_3$ and $CH_3O$ substituents at 5-position of the phenol group of $H-BHE{\cdot}2HBr$ were also synthesized. $Nap-BHE{\cdot}2HBr$ having naphthalen-2-ol instead of the phenol group was also synthesized. The potentiometry study in aqueous solution revealed that the proton dissociations of the synthesized ligands occurred in four steps and the order of the calculated overall proton dissociation constants (${\log}{\beta}_p$) of each ligand was Br-BHE < Cl-BHE < H-BHE < Nap-BHE < $CH_3$-BHE < $CH_3O$-BHE. The order showed a similar trend to that of Hammett substituent constants(${\sigma}_P$). The order of the stability constants (${\log}K_{ML}$) was CO(II) < Ni(II) < Cu(II) > Zn(II) > Cd(II) > Pb(II). The order in their stability constants (${\log}K_{ML}$) of each transition metal complex agreed well with that of the overall proton dissociation constants (${\log}{\beta}_p$).

Formation and Dissociation Kinetics of Tetraaza-Crown-Alkanoic Acid Complexes of Cerium(Ⅲ)

  • 최기영;김동원;정용순;김창석;홍춘표;이용일
    • Bulletin of the Korean Chemical Society
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    • v.19 no.6
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    • pp.671-676
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    • 1998
  • The formation and dissociation rates of $Ce^{3+}$ Complexes of the 1,4,7,10-tetraaza-13,16-dioxacyclooctadecane-NN', N",N"'-tetraacetic acid (1), 1,4,7,10-tetraaza-13,16-dioxacyclooctadecane-N,N',N",N"'-tetramethylacetic acid (2), and 1,4,7,10-tetraaza-13,16-dioxacyclooctadecane-N,N',N",N"'-tetrapropionic acid (3) have been measured by the use of stopped-flow spectrophotometry. Observations were made at 25.0±0.1 ℃ and at an ionic strength of 0.10 M $NaClO_4$. The complexation of $Ce^{3+}$ ion with 1 and 2 proceeds through the formation of an intermediate complex $(CeH_3L^{2+})^*$ in which the $Ce^{3+}$ ion is incompletely coordinated. This may then lead to be a final product in the rate-determining step. Between pH 4.76 and 5.76, the diprotonated $(H_2L^{2-})$ from is revealed to be a kinetically active species despite of its low concentration. The stability constants $(logK(CeH_3L^{2+}))$ and specific water-assisted rate constants $(k_{OH})$ of intermediate complexes have been determined from the kinetic data. The dissociation reactions of $Ce^{3+}$ complexes of 1, 2, and 3 were investigated with $Cu^{2+}$, ions as a scavenger in acetate buffer. All complexes exhibit acid-independent and acid-catalyzed contributions. The effect of buffer and $Cu^{2+}$ concentration on the dissociation rate has also been investigated. The ligand effect on the dissociation rate of $Ce^{3+}$ complexes is discussed in terms of the side-pendant arms and the chelate ring sizes of the ligands.

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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