• Title/Summary/Keyword: Complex formation constant

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Determination of Complex Formation Constant of Sodium-Selective Ionophores in Solvent Polymeric Membranes (용매 고분자막 상에 고정된 나트륨 이온선택성 물질의 착물형성상수 결정)

  • Kang, Tae Young;Kim, Sung Bae;Oh, Hyon Joon;Han, Sang Hyun;Cha, Geun Sig;Nam, Hakhyun
    • Analytical Science and Technology
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    • v.13 no.4
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    • pp.466-473
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    • 2000
  • The complex formation constants (${\beta}_{MLn}$) of potassium and various sodium-selective neutral carriers in solvent polymeric membranes have been determined using solvent polymeric membrane-based optodes and ion-selective electrodes (ISEs). Two different types of PVC-based membranes containing the H^+selective chromoionophore (ETH 5294) with and without a sodium ionophore (4-tert-bntylcalix[4]arenetetraacetic acid tetraethyl ester, ETH 2120, bis[(12-crown-4)methyl] dodecylmethylmalonate or monensin methyl ester) were prepared and their optical responses to either the changes in alkali metal cation (e.g., sodium and potassium) concentrations at a fixed pH (0.05 M Tris-HCl, pH 7.2) or varying pH at a fixed alkali metal cation concentration (0.1 M) were measured. The same type of membranes were also mounted in conventional electrode body and their potentiometric responses to varying pH at a fixed alkali metal cation concentration (0.1 M) were measured. The complex formation constants of the ligand could be calculated from the calibration plots of the relative absorbance vs. the activity ratios of cation and proton ($a_{M^+}/a_{H^+}$) and of the emf vs. pH. It was confirmed that the ratio values of the complex formation constants for the primary and interfering ions are closely related to the experimental selectivity coefficients of ISEs.

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Kinetic and Equilibrium Studies on Complex Formation Between Ni(II) and D-Penicillamine in Aqueous Media (Ni(II)와 D-Penicillamine과의 착물형성반응에 대한 속도론적 및 평형에 관한 연구)

  • Yong-Kyu Kim;Sung-Nak Choi
    • Journal of the Korean Chemical Society
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    • v.30 no.5
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    • pp.475-482
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    • 1986
  • Rates and equilibriurn of complex formation between $Ni^{2+}$ and D-penicillamine have been investigated in aqueous solutions. Kinetic study on the complex formation were performed in the pH range of 8∼9 by the use of pressure-jump technique. D-Penicillamine coordinates to the nickel(II) ion utilizing sulfur and nitrogen as donor atoms in the high pH condition (pH 9.2). However, in the pH range of 8.25∼9.07, the stepwise stability constant becomes drastically reduced and the undissociated mercapto group does not participate in bonding. The rate-determining step of the complexation reaction is found to be the release of a water molecule from the inner-coordination sphere of $Ni^{2+}$ ion.

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The Study on the Physicochemical Properties of Fluid under High Pressure (Ⅱ). The Effect of Pressure and Temperature on the Hexamethyl Benzene-Iodine Charge Transfer Complex in n-Hexane

  • Kwun Oh Cheun;Kim Jeong Rim
    • Bulletin of the Korean Chemical Society
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    • v.6 no.4
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    • pp.186-191
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    • 1985
  • The effect of pressure and temperature on the stabilities of the charge transfer complexes of hexamethyl benzene with iodine in n-hexane has been investigated by UV-spectrophotometric measurements. In this experiment the absorption spectra of mixed solutions of hexamethyl benzene and iodine in n-hexane were measured at 25, 40 and $60^{\circ}C$ under 1,200, 600, 1200 and 1600 bar. The equilibrium constant of the complex formation was increased with pressure while being decreased with temperature raising. Changes of volume, enthalpy, free energy and entropy for the formation of the complexes were obtained from the equilibrium constants. The red shift at higher pressure, the blue shift at higher temperature and the relation between pressure and oscillator strength were discussed by means of thermodynamic functions. In comparison with the results in the previous studies, it can be seen that the pressure dependence of oscillator strength has a extremum behavior in durene as the variation of ${\Delta}H$ or ${\Delta}S$ with the number of methyl groups of polymethyl benzene near atmospheric pressure in the previous study. The shift or deformation of the potential in the ground state and in the excited state of the complexes formed between polymethyl benzene and iodine was considered from the correlation between the differences of the electron transfer energies and the differences of free energies of the complex formation for the pressure variation.

Effect of Number and Location of Amine Groups on the Thermodynamic Parameters on the Acridine Derivatives to DNA

  • Kwon, Ji Hye;Park, Hee-Jin;Chitrapriya, Nataraj;Han, Sung Wook;Lee, Gil Jun;Lee, Dong Jin;Cho, Tae-Sub
    • Bulletin of the Korean Chemical Society
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    • v.34 no.3
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    • pp.810-814
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    • 2013
  • The thermodynamic parameters for the intercalative interaction of structurally related well known intercalators, 9-aminoacridine (9AA) and proflavine (PF) were determined by means of fluorescence quenching study. The fluorescence intensity of 9AA decreased upon intercalation to DNA, poly[$d(A-T)_2$] and poly[$d(G-C)_2$]. A van't Hoff plot was constructed from the temperature-dependence of slope of the ratio of the fluorophore in the absence and presence of a quencher molecule with respect to the quencher concentration, which is known as a Stern-Volmer plot. Consequently, the thermodynamic parameters, enthalpy and entropy change, for complex formation was calculated from the slope and y-intercept of the van't Hoff plot. The detailed thermodynamic profile has been elucidated the exothermic nature of complex formation. The complex formation of 9AA with DNA, poly[$d(A-T)_2$] and poly[$d(G-C)_2$] was energetically favorable with a similar negative Gibb's free energy. On the other hand, the entropy change appeared to be unfavorable for 9AA-poly[$d(G-C)_2$] complex formation, which was in contrast to that observed with native DNA and poly[$d(A-T)_2$] cases. The equilibrium constant for the intercalation of PF to poly[$d(G-C)_2$] was larger than that to DNA, and was the largest among sets tested despite the most unfavorable entropy change, which was compensated for by the largest favorable enthalpy. The favorable hydrogen bond contribution to the formation of the complexes was revealed from the analyzed thermodynamic data.

Determination of inclusion complex formation constants for the β-CD and [Cu(Dien)(sub-Py)]2+ ion by the spectrophotometric methods (분광 광도법에 의한 β-CD와 [Cu(Dien)(sub-Py)]2+이온간의 복합체 형성 상수 결정)

  • Kim, Chang Suk;Oh, Ju Young
    • Analytical Science and Technology
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    • v.20 no.5
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    • pp.406-412
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    • 2007
  • The formation of inclusion complexes between ${\beta}$-cyclodextrin and diethylenetriamine substituted-pyridine copper(II) perchlorate; [Cu(dien)(sub-py)] $(ClO_4)_2$, were studied by spectrophotometric methods. On account of charge-transfer band(MLCT) and $^2T_2{\rightarrow}^2E$, the two high peaks were observed as an inclusion complex for the [${\beta}$-CD]$[Cu(dien)(p-Cl-py)]^{2+}$ in the ultraviolet region of the spectrum. The ${\beta}$-CD and $[Cu(dien)(sub-py)]^{2+}$ ion formed a 1:1 complex, and the formation constants were decreased with the increasing temperatures, due to weak binding energy between ${\beta}$-CD and $[Cu(dien)(sub-py)]^{2+}$ ion. This reaction was controlled by enthalpy. In a correlation of the Hammett substituent constants and formation constants for the reaction, formation constants were increased by strong binding energy in the inclusion complexes when electron donating groups were substituted in pyridine ring.

Drug-biomacromolecule interaction 1

  • Kim, Chong-Kook;Ahn, Hae-Young
    • Archives of Pharmacal Research
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    • v.4 no.2
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    • pp.99-107
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    • 1981
  • To investigate the protein binding characteristics of ibuprofenlysine, the effects of drub conentration, pH, ionic strength and protein concentration on the binding of drug to protein concentration on the binding of drug to protein were studied by fluorescence probe method. The conformational change of protein was investigated by circular dichroism (CD) measurement. As the concentration of drug increases, the association constant decreases. These may be due to complex formation of the probe and drug, or the interaction of the protein-probe complex and drug. The association constant for ibuprofenlysine increased with increasing protein concentration. These finding suggest a sharing of one ibuprofenlysine molecule by more than one protein molecule in the binding. The binding between ibuprofenlysine and protein was dependent on pH and ionic strength. It seems that both hydrophobic binding and some electrostatic forces are involved in the binding of ibuprofenlysing to protein.

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Effect of sequence variations within DNA melting region on the rate of formation of open complexes at $\lambdaP_{R}$ promoter ($\lambdaP_{R}$ 프로모터 열린복합체 형성에 미치는 DNA melting 부위 염기서열의 영향)

  • 정현채;노정혜
    • Korean Journal of Microbiology
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    • v.28 no.1
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    • pp.19-26
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    • 1990
  • To examine the effects of sequence variations near the transcriptional start site on the rate of formation of the open complexes at bacteriophage $\lambda P_{R}$ promoter, two mutant promoters were created by site-specific mutagenesis using synthetic oligonucleotides. Mutant I coatains changes at positions -3 and -4 from TT to CC, thus having a 6-bp long G/C stretch between -10 region and transciptional start site (+1). Mutant II has changes at positions -5 and -6 from GG to AA, thereby having a 9-bp long A/T stretch between positions -11 and -3. Selective filter binding assays were performed to measure the rate of formation of the open complexes between the wild-type or two mutant $P_{R}$ promoters on 664 bp fragments and E. coli RNA polymerase at two temperatures. At 37.deg.C, the wild-type and two mutants showed similar rates for the formation of open complex. The second order rate constant $k_{a}$ and $\tau _{int}$, as determined from the .tau.-plot analysis, were $(6.0\pm0.4)\times10^{6}M^{-1}sec^{-1}$ and $11\pm5$sec, respectively. At 18.deg.C, however, the wild-type and two mutant promoters showed differences in the kinetic parameters. k for the wild-type promoter was (2.2$\pm$0.1)\times 10^{6}M^{-1}sec^{-1}$ and $\tau _{int}$ was 76$\pm$sec. Mutant I and II exhibited differences mainly in the rate of isomerization ($\tau_{int,I}=91\pm$10 sec, int,II=34$\pm$ sec), whereas the second order rate constant $k_{a}$ was similar to the wild type value. This result implies that at $18^{\circ}C$, the isomerization rate is determined by both protein conformational change and DNA melting, which are separable kinetically according to the 3-step mechanism of Roe et al.(1984,1985), and that the base changes affected mainly the rate of DNA melting as predicted.lting as predicted.

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Studies on 1-Isonicotinoyl-2-furfurylidene hydrazine-Cu(II) Complex Compound. (1-Isonicotinoyl-2-furfurylidene Hydrazine-Cu(II) 착화합물에 관한 분석화학적연구)

  • 백남호;최윤수
    • YAKHAK HOEJI
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    • v.9 no.1_2
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    • pp.18-22
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    • 1965
  • A new organic reagent, 1-isonicotinoyl-2-furfurylidene hydrazine was synthesized from isonicotinic acid hydrazide and furfural, gives precipitate with copper(II), mercury(II) and argent(I), whereas, it gives a water soluble yellow complex with iron(III). Copper complex of the reagent is soluble in EtOH MtOH, pyridine, dioxane and dimethylformamide with green yellow coloration. The complex has a maximum absorption at 385 m.$\mu$ and molar ratio of copper; reagent was estimated as 1:1 by continuous variation method, slop method and chelate titration method. Molar extinction coefficient (9600) and apparant formation constant of this complex was spectrophotometrically determined. K=1.7 * $10^{7}$ (Babko's method) K=2.1 * $10^{7}$ (Anderson's method). This reagent reacted with copper so sensitive that it would be available for determination of Cu (II).

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Determination of Stability Constants Using Electrochemical Methods for the Complex Formation of Platinum and Palladium with Polyelectrolytes

  • Park, Joon Seo;Chung, Koo Soon
    • Analytical Science and Technology
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    • v.8 no.4
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    • pp.691-698
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    • 1995
  • The complexation of platinum and palladium with synthetic polyelectrolytes was studied. The successive and overall stability constants of Pd(II) with PEI and 2PVP were obtained by potentiometric titration. Because of the slow equilibrium time, the potentiometric titrations were performed using the home-made automatic titrator in order to analyze the complexations according to the modified Bjerrum method. The complex formation constant of Pt(IV) with 2PVP, measured by differential pulse polarography, was calculated from the peak currents that were obtained in non-complexing media and in solution containing 2PVP.

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Preparation and Evaluation of Inclusion Complex of Lansoprazole with 2-HP-β-Cyclodextrin and Meglumine (2-HP-β-시클로덱스트린과 메글루민을 이용한 란소프라졸의 포접화합물 제조 및 평가)

  • Lee, Jung-Woo;Kim, Jung-Su;Chang, Hye-Jin;Lee, Gye-Won;Jee, Ung-Kil
    • Journal of Pharmaceutical Investigation
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    • v.34 no.4
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    • pp.269-274
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    • 2004
  • To enhance the solubility and stability of lansoprazole (LAN), new proton pump inhibitor, we were prepared various molar ratio of inclusion complex with $2-hydroxypropyl-{\beta}-cyclodextrin$ (HPCD) and organic alkali agent, meglumine (MEG). Inclusion complex formation of LAN with HPCD was investigated by Differential Scanning Calorimetry and X-ray diffractometry. The aqueous solubilities of inclusion complexes, and the stabilities of 1:4 and 1:5 inclusion complexes in aqueous solutions containing different concentrations of MEG were examined. The stability of 1:5 LAN-HPCD inclusion complex containing MEG, which was equaled to amount of LAN, was performed in 0.9% NaCl and 5% dextrose solution. The formation of inclusion complex of LAN with HPCD was $A_L$ type and the molar ratio of complex was 1:1. The stability constant was $41.557\;M^{-1}$. As molar ratio of LAN to HPCD was increased, solubility of inclusion complex was increased. 1:5 LAN-HPCD inclusion complex was more stable than 1:4 LAN-HPCD inclusion complex. And as contained MEG amount in LAN solution was increased, stability of 1:4 and 1:5 LAN-HPCD inclusion complexes was improved. Also stability of 1:5 LAN-HPCD-MEG inclusion complex in 0.9% NaCl solution and 5% dextrose solution was similar to it in water at room temperature, but it was unstable at $40^{\circ}C$.