• Title/Summary/Keyword: Acid dissociation constants

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Kinetic Studies on the Reaction of Thiocyanate with Di-$\mu$-oxobis-(aquaoxalatooxomolybdate (V)) in Acid Media (산성수용매에서 이-$\mu$-옥소비스-(아쿠아옥살라토옥소몰리브덴 (V)) 산이온과 티오시안산이온의 반응)

  • Chang-Su Kim;Chang-Yong Kwon;Moon-Pyoung Yi;Chann-Woo Kim
    • Journal of the Korean Chemical Society
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    • v.29 no.6
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    • pp.623-628
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    • 1985
  • Rate constants for complexing with thiocyanate after ring opening of molybdenum-oxalate in acid media were obtained spectrophotometrically at 460nm. The acid-assisted dissociation of molybdenum-oxalate and the reaction of thiocyanate with oxalatooxomolybdenum (V) complex in acid media were investigated with thiocyanate and hydrogen ion concentration. The kinetic data indicate that molybdenum-oxalate is protonated to a limited extent in acid media and the protonated complex is responsible for an increase in rate for the reaction of thiocyanate with oxalatooxomolybdenum (V) complex. Replacement of an oxalate ligand in acid media has been interpreted in terms of dissociative mechanism involving bond-breaking of the oxygen trans to the yl oxygen.

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GTPase Activity Analysis of eRF3 in Euplotes octocarinatus

  • Song, Li;Dong, Jun-Li;Zhao, Ya-Qin;Chai, Bao-Feng;Liang, Ai-Hua
    • Journal of Microbiology and Biotechnology
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    • v.20 no.9
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    • pp.1283-1287
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    • 2010
  • In eukaryotes, eRF3 participates in translation termination and belongs to the superfamily of GTPases. In this work, the dissociation constants for nucleosides bound to Euplotes octocarinatus eRF3 in the presence and absence of eRF1a were determined using fluorescence spectra methods. Furthermore, a GTP hydrolyzing assay of eRF3 was carried out using an HPLC method, and the kinetic parameters for GTP hydrolysis by eRF3 were determined. Consistent with data from humans, the results showed that eRF1a promoted the binding of GTP to eRF3 and the GTP hydrolyzing activity of eRF3. However, in contrast to the lack of GTP binding in the absence of eRF1 in human eRF3, the E. octocarinatus eRF3 was able to bind GTP by itself. The nucleotide binding affinity of the E. octocarinatus eRF3 also differed from the human data. A structure model and amino acid sequence alignment of potential G domains indicated that these differences may be due to valine 317 and glutamate 452 displacing the conserved glycine and lysine involved in GTP binding.

Formation and Dissociation Kinetics of Zinc(II) Complexes of Tetraaza-Crown-Alkanoic Acids (Zinc(Ⅱ) Tetraaza-Crown-Allkanoic Acids 착물의 형성 및 해리 반응속도론)

  • Choi, Ki Young;Kim, Dong Won;Kim, Chang Suk;Park, Byung Bin;Choi, Suk Nam;Hong, Choon Pyo;Ryu, Hae Il
    • Journal of the Korean Chemical Society
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    • v.44 no.5
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    • pp.403-409
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    • 2000
  • The formation and dissociation rates of $Zn^{2+}$ Complexes with l,4,7,10-tetraaza-13,16-diox-acyclooctadecane-N,N',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 stopped-flow and conventional spectrophotometry. Observations were made at 25.0$\pm$0.1 $^{\circ}C$ and at an ionic strength of 0.10 M NaClO$_4$. The formation reactions of $Zn^{2+}$ ion with 1 and 2 took place by the rapid formation of an intermediate complex (ZnH$_3L^+$) in which the $Zn^{2+}$ ion is incompletely coor-dinated. This might then lead to be a final product in the rate-determining step.ln the pH range 4.76-5.76, the diprotonated (H2L2-) form is the kinetically active species despite of its low concentration. The stability con-stants (log$K_{(ZnH$_3$3$L^+$)}$) and specific water-assisted rate constants (koH) of intermediate complexes have been deter-mined from the kinetic data. The dissociation reactions of $Zn^{2+}$ 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 con-tributions. The effect of buffer and $Cu^{2+}$ concentration on the dissociation rate has also been investigated. The ligand effect on t dissociation rate of $Zn^{2+}$ complexes is discussed in terms of the side-pendant armsand the chelate ring sizes of the ligands.

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Synthesis, Tautomeric Structure, Dyeing Characteristics, and Antimicrobial Activity of Novel 4-(2-Arylazophenyl)-3-(2-hydroxyphenyl)-1-phenyl-2-pyrazolin-5-ones

  • Metwally, M.A.;Bondock, S.A.;El-Desouky, S.I.;Abdou, M.M.
    • Journal of the Korean Chemical Society
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    • v.56 no.1
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    • pp.82-91
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    • 2012
  • Novel azopyrazolin-5-one dyes 4a-f were synthesized by the regioselective reaction of phenylhydrazine with 2,3,4-chromantrione-3-arylhydrazones 2a-f. The acid dissociation constants $pK_a$ for the series prepared were determined and correlated by the Hammett equation. The results of such correlation together with the spectral data indicated that the studied compounds exist predominantly in the hydrazone keto structure, (D) as the Z-configuration. The dyes were applied to polyester fabrics, affording orange-yellow shades and assessments of their dyeing performance are considered. Further, the compounds 4a-f were screened for their antimicrobial activity against various microorganisms.

Studies on Enzymatic Characteristic′s of Adenylate Kinase from Baker′s Yeast (제빵효모 Adenylate Kinase의 효소학적 특성에 관하여)

  • ;Takahisa Ohta;Hiroshi Sakai
    • Microbiology and Biotechnology Letters
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    • v.12 no.4
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    • pp.277-283
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    • 1984
  • In the forward reaction (ADP formation) of the adenylate kinase from baker's yeast, dissociation constants from binary complexes are higher by a factor of about 4 times then those from at ternary complexes. In the reverse reaction, dissociation constants from the binary complexes are 2 times higher then those from the ternary complexes. The enzyme showed activities against various nucleotide triphospate in following orders; ATP 100, UTP 18, ITP 9 and GTP 5, of the necleotide monophosphate. only dAMP showed 33% activity of that AMP as phosphate acceptor. Divalent cations were required in enzyme reaction in following orders; $Mg^{2+}$ 100, Co$^{2+}$ 57, Mn$^{2+}$ 54, $Ca^{2+}$ 51, Ni$^{2+}$ 10 and Sn$^{2+}$ 6. AMP, as a substrate inhibitor, competitively inhibited the adenylate kinase at pH 7.2 or 8.0. Inhibition constants of the enzyme showed greater dependence on the pH of the reaction mixture, which was the lower Ki values under higher pH. Adenosine pentaphospho adenosine was competive inhibitor to the enzyme against all substrate, and it showed the same Ki values, 2.9mM. Further, PEP was competive inhibitor with respect to AMP and non-competive inhibitor with respect to MgATP. Adenylate kinase from bakers yeast was similar to mitochondrial type of animal in the contents of aianine, leucine and asparagine or asparatic acid differing from muscle type enzyme. Based on the results and observation, characteristic of yeast adenylate kinase resembled the adenylate kinase of mitochondrial type from animals. Further, difference of characteristics in adenylate kinasa depending upon the workers might be due to the difference of strain used.

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The Synthesis of Surfactant of N-Alkyl Nicotinates (N-알킬 니코틴산염류(酸鹽類) 계면활성제(界面活性劑)의 합성(合成))

  • Nam, Ki-Dae;Jeong, No-Hee;Lee, Chang-Seoup;Lee, Seung-Yeol
    • Journal of the Korean Applied Science and Technology
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    • v.7 no.2
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    • pp.11-18
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    • 1990
  • N-alkyl carboxy pyridinium chlorides such as N-lauryl carboxy-pyridinium chloride, N-myristyl carboxy pyridinium chloride, N-cetyl carboxy pyridinium chloride and N-stearyl carboxy pyridinium chloride were synthesized by the reaction of nicotinic acid and isonicotinic acid with long chain alkyl chlorides, and N-alkyl pyrinium carboxylates such as N-lauryl pyridinium carboxylate, N-myristyl pyridinium carboxylate. N-cetyl pyridinium carboxylate and N-stearyl pyridinium carboxylate were prepared from N-alkyl carboxy pyridinium chlorides. These reaction products could be separated by both column chromatogrphy, and paper chromatography, and there dissociation constants of N-alkyl pyridinium carboxylates were found to pKa $1.0{\times}10^{13}{\sim}6,31{\times}10^{14}$.

Kinetic Studies on the Oxidation Reaction of Malonic Acid by Ceric Ion (세륨(Ⅳ)에 의한 말론산의 산화반응에 관한 반응속도론적 연구)

  • Kim, Wang Gi
    • Journal of the Korean Chemical Society
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    • v.38 no.10
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    • pp.705-709
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    • 1994
  • The kinetics of the oxidation reaction of malonic acid by ceric ion in 1 M sulfuric acid solution at $20^{\circ}C$ have been investigated by spectrophotometric method. The reaction rate at a large excess of malonic acid was found to be pseudo-first order. The observed pseudo-first order rate constants, $k_{obs}$, are dependent on the concentration of malonic acid, [MA], of which relationship has been found to be $k_{obs}$ = (0.592[MA])/(1+14.5[MA]$^2$). A mechanism for the reaction has been suggested on the basis of the above rate equation. The rate determining step may be the electron transfer reaction between enolate type malonate anion, which is formed by the acid dissociation reaction of malonic acid, and Ce(IV). The rate depression in the range of high concentration of MA has been explained by the formation of 1 : 2 chelate between Ce(IV) and malonate. According to the mechanism, the pH dependence of the rate, which was studied by Sengupta et al., has also been explained.

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Kinetic Study of Macrocyclic Ligand-Metal Ion Complexes (거대고리 리간드와 금속이온과의 착물에 관한 반응속도론적 연구)

  • Moon-Hwan Cho;Jin-Ho Kim;Hyu-Bum Park;Si-Joon Kim
    • Journal of the Korean Chemical Society
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    • v.33 no.4
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    • pp.366-370
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    • 1989
  • A new macrocyclic ligand 1,15,18-triaza-3,4;12,13-dibenzo-5,8,11-cycloeicosane (NdienOdien$H_4$ = $N_3O_3$) has been synthesized and identified by element analysis, NMR and IR spectrophotometry. Stepwise protonation constants of ligand are determined by potentiometry in 95% methanol solution(I = 0.1 mol $dm^{-3}$, $Me_4$NCl). log $K_1$;log $K_2$;log $K_3$ = 9.1;8.1;3.6.The kinetics of the acid-promoted dissociation reactions of complex cations of nickel(II) and copper(III) with NdienOdien and NdienOen macrocyclic ligands having, respectively, 17 and 20 ring members, have been studied spectrophotometrically in HCl$O_4$ NaCl$O_4$ aqueous solutions. From the temperature effect on kinetic constant ($k_{obs}$), the parameters of activation(${\Delta}H^{\neq}$, ${\Delta}S^{\neq}$) of dissociation reaction for $ML^{2+}$ with $H^+$ ion have been determined. We have proposed the possible mechanism of the reaction from the data obtained.

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Studies of Magnesium-Eriochrome Black T Complex in Acetonitrile (Acetonitrile에서의 Mg-EBT$^-$ 착물에 관한 연구)

  • Doo Won Park;Won Hyung Choi;Heung Lark Lee
    • Journal of the Korean Chemical Society
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    • v.17 no.4
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    • pp.256-261
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    • 1973
  • Complex formation of magnesium-Eriochrome Black T at constant ionic strength and hydrogen ion concentration have been studied spectrophotometrically in acetonitrile solution. The measured pH values were calibrated with standard buffer solutions by using a glass electrode Ag/0.1M $AgNO_3$ reference electrode couple. The results are as follows;$E_{glass}=716+59.1\;logA_{H+}[mv]$+(in mv. vs. Ag reference electrode for picric acid $-10^{-3}M$ tetramethylammonium picrate buffer), and $E_{glass}=1,193+59.1\;logA_{H+}[mv]$(in mv. vs. Ag reference electrode for 1,3-diphenylguanidine $-3{\times}10^{-3}M $ 1,3-diphenylguanidine perchlorate buffer). The acid dissociation exponent of ligand, $ pK_{H,EBT-}$was found to be 9.1. The conditional formation constants of $MgEBT^{-}$complex by log-ratio method were 3.97 (when m = 2) and 5.02 (when m = 1) as $log K_n$, respectively, for the reaction of $H_mEBT^{(3-m)-} + Mg^{2+} {\leftrightarrow}MgEBT^{-} + mH^{+}$. The present study showed that$MgEBT^{-}$ has the composition of 1:1 which agrees with the result of Schwarzenbach et al. in aqueous solution.

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Working partial pressure of $CO_2$ gas in aqueous solution

  • Kim Dong-Su
    • Resources Recycling
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    • v.14 no.4 s.66
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    • pp.47-52
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    • 2005
  • Carbonate species in aqueous solution play an important role in the determination of chemical properties of water in relation with alkalinity, buffer capacity, biological productivity, and so on. These compounds also have reactive characteristics such as interphasal reactions between solid, liquid, and gas phases. In the absence of solid materials, the total amount and relative abundance of each carbonate species are directly influenced by the partial pressure of $CO_2$ gas in the atmosphere, which in turn significantly affects the properties of aquatic system. In the water/wastewater treatment process along with the wastes treatment and recycling process which occurring in aquatic environment, it is essential to figure out its characteristics for their optimization and one of its most influential features upon these processes is determined by carbonate species. To understand the fundamental aspect of the relationship between the partial pressure of $CO_2$ gas and chemical features of water, especially pH, the working partial pressure of pure $CO_2$ gas that produced by contacting the dry ice with water has been estimated based on equilibrium calculation. The equilibrium constants for the dissociation ot carbonic acid were determined using van't Hoff equation and the distribution diagram of carbonate species according to the pH has been constructed to substantiate the results of equilibrium calculation. The estimated working partial pressure of pure $CO_2$ gas was found to be a function of the concentration of carbonates in solution, which suggesting that Prior evaluation of the working partial pressure of gas is essential for a better understanding of aquatic interactions.