• Bulletin of the Korean Chemical Society
• /
• v.35 no.5
• /
• pp.1440-1448
• /
• 2014

Co(II)-tetrasulfonated phthalocyanine (CoTSP) is known to be aggregated to dimer at high concentration levels in water. A study on the aggregation of CoTSP using multivariate curve resolution analysis of the visible absorbance spectra over a concentration range of 30, 40 and 50 ${\mu}M$ in the presence of dimethyl sulfoxide (DMSO), dimethyl formamide (DMF), acetonitrile (AN) and ethanol (EtOH) in the concentration range of 0 to 3.57 M is conducted. A hard modeling-based multivariate curve resolution method was applied to determine the dissociation constants of the CoTSP aggregates at various temperatures ranging from 25, 45 and $65^{\circ}C$ and in the presence of various co-solvents. Dissociation constant for aggregation was increased and then decrease by temperature and concentration of phthalocyanine, respectively. Utilizing the vant Hoff relation, the enthalpy and entropy of the dissociation equilibriums were calculated. For the dissociation of both aggregates, the enthalpy and entropy changes were positive and negative, respectively. Molecular dynamics simulation of cosolvent effect on CoTSP aggregation was done to confirm spectroscopy results. Results of radial distribution function (RDF), root mean square deviation (RMSD) and distance curves confirmed more effect of polar solvent to decrease monomer formation.

• BMB Reports
• /
• v.42 no.6
• /
• pp.367-372
• /
• 2009

In this study, we showed that WAX9D, a nonspecific lipid-transfer protein found in broccoli, binds palmitate (C16) and stearate (C18) with dissociation constants of 0.56 ${\mu}M$ and 0.52 ${\mu}M$, respectively. WAX9D was fused to thioredoxin protein by genetic manipulation to enhance its solubility. The data revealed strong interaction of Trx-WAX9D with palmitate and stearate. The dissociation constants of Trx-WAX9D for palmitate and stearate were 1.1 ${\mu}M$ and 6.4 ${\mu}M$, respectively. The calculated number of binding sites for palmitate and stearate was 2.5 to 2.7, indicating that Trx-WAX9D can bind three molecules of fatty acids. Additionally, Trx-WAX9D was shown to inhibit the apoptotic effect of palmitate in endothelial cells. Our data using Trx-WAX9D provide insight into the broad spectrum of its biological applications with specific palmitate binding.

• Journal of the Korean Chemical Society
• /
• v.20 no.4
• /
• pp.270-276
• /
• 1976

The absorption spectra and the dissociation constants of various sulfophthaleins have been measured in the presence of a cationic surfactant. In the presence of 2.0 ${\times}$ 10-3 M zephiramine and an ionic strength of 0.05 at 25${\pm}1^{\circ}C$ the absorption maxima of the basic forms are shifted to red by 6${\sim}$21 nm and their molar absorptivities are increased, while the absorption maxima of the yellow forms are shifted to blue by 4${\sim}$20 nm and their molar absorptivities are decreased. The decreases in pKa values are of the order of ranging -1.38${\sim}$0.37. The characteristic of the observed changes has been explained by the assumption that the dye molecule adsorbed on micellar surface forms a stable coplanar structure easily and then the conjugation in the dye molecule is elevated.

• Analytical Science and Technology
• /
• v.6 no.5
• /
• pp.443-451
• /
• 1993

Pentaethylenehexaamine(penten) was reacted with a chloromethylated polystyrene resin on the purpose of the synthesis of polyamine chelating resin, $(P)_c$-penten. The stepwise dissociation constants of the synthesized polyamine chelating resin and the stability constants with metal ions were determined by Bjerrum's method. These stability constants were compared with those of the free penten. The adsorptivities and eluting tendencies of several metal ions on the chelating resin were studied.

• Bulletin of the Korean Chemical Society
• /
• v.12 no.6
• /
• pp.629-632
• /
• 1991

The rate constants for the formation and dissociation of nickel(II) and cobalt(II) complexes with mandelate have been determined by the pressure-jump relaxation study. The forward and reverse rate constants for the mandelate complex formation reactions were obtained to be $k_f=3.60{\times}10^4\;M^{-1}s^{-1}$ and $k_r=1.73{\times}10^2\;s^{-1}$ for the nickel(II), and $k_f=1.75{\times}10^5\;M^{-1}s{-1}$ and $2.33{\times}10^3\;s^{-1}$ for the cobalt(II) in aqueous solution of zero ionic strength ($(\mu{\to}0)\;at\;25^{\circ}C$. The results were interpreted by the use of the multistep complex formation mechanism. The rate constants evaluated for each individual steps in the multistep mechanism draw a conclusion that the rate of the reaction would be controlled by the chelate ring closure step in concert with the solvent exchange step in the nickel(II) complexation, while solely by the chelate ring closure step for the cobalt(II) complex.

• Analytical Science and Technology
• /
• v.10 no.4
• /
• pp.256-263
• /
• 1997

The new naphthol-containing hexadentate ligands, 1,12-bis (2-naphthol)- 2,5,8,11-tetraazadodecane 4HCl (nptr) and 1,14-bis(2-naphthol)- 2,6,9,13- tetraazatetradodecane .4HCl (npptr) were synthesized and characterized by elemental analysis, IR, NMR, and mass spectrometry. Acid dissociation constants and stability constants of Co(II), Ni(II). Cu(II), and Zn(II) complexes were determined at $25.0^{\circ}C$ and ionic strength ($\mu$)=0.10M($KNO_3$) by potentiometry. The relationship between basicity and stability constants of ligands containing aliphatic amines and 2-naphthol were studied.

• Molecules and Cells
• /
• v.24 no.1
• /
• pp.119-124
• /
• 2007

TLR4 together with CD14 and MD-2 forms a pattern recognition receptor that plays an initiating role in the innate immune response to Gram-negative bacteria. Here, we employed the surface plasmon resonance technique to investigate the kinetics of binding of LPS to recombinant CD14, MD-2 and TLR4 proteins produced in insect cells. The dissociation constants ($K_D$) of LPS for immobilized CD14 and MD-2 were $8.7{\mu}m$, and $2.3{\mu}m$, respectively. The association rate constant ($K_{on}$) of LPS for MD-2 was $5.61{\times}10^3M^{-1}S^{-1}$, and the dissociation rate constant ($K_{off}$) was $1.28{\times}10^2S^{-1}$, revealing slow association and fast dissociation with an affinity constant $K_D$ of $2.33{\times}10^6M$ at $25^{\circ}C$. These affinities are consistent with the current view that CD14 conveys LPS to the TLR4/MD-2 complex.

• Bulletin of the Korean Chemical Society
• /
• v.6 no.5
• /
• pp.266-269
• /
• 1985

The dissociation constants(K) of m-chloroanilinium ion in water-ethanol mixture, where the volume percentage of water is 89.5%, were evaluated by UV-spectroscopic method at $20{\sim}50^{\circ}C$, up to 1500 bars with changing ionic strength from 0.04 to 0.10 mol $kg^{-1}$ by use of acetate buffer. K values enhance with increasing ionic strength and temperature, but decrease with elevating pressure. From K values, we obtained the partial molar volume change and some other thermodynamic parameters. From the values of enthalpy, entropy and isoequilibrium temperature (649 K), we concluded that the dissociation of m-chloroanilinium ion mentioned above is controlled by enthalpy.

• Journal of the Korean Chemical Society
• /
• v.30 no.4
• /
• pp.335-450
• /
• 1986

The thermodynamic dissociation constants of $[Co(en)]_3Cl_3\;and\;[Co(NH_3)_6Cl_3$ in aqueous solutions at $25{\circ}$ and at the pressure from 1 bar to 2000 bars were measured by conductometric method. The dissociation constants were increased with pressure elevation because of volume decreasing by the formation of charged ions during dissociation reaction. That is, the $pK^T$ values of $[Co(en)]_3Cl_3$ were 2.16 for I bar, 2.08 for 500 bars, 2,08 for 1000 bars, 2.05 for 1500 bars and 2.03 for 2000 bars, respectively and those of $[Co(NH_3)_6Cl_3$ were 2.02 for 1 bar 1.96 for 500 bars, 1.90 for 1000 bars, 1. 88 for 1500 bars and 1. 87 for 2000 bars, respectively. Comparing and analyzing the values of Stokes' radii and $K^T$, the formation of ion pair compound was affected by not only the electrostatic interaction, but also the Interal Conjugate Base(ICB), which was increased by the elevation of the pressure.

• Journal of the Korean Chemical Society
• /
• v.13 no.1
• /
• pp.5-8
• /
• 1969

Acid dissociation constants and chelate stability constants of 8-hydroxyquinoline-5-sulfonic acid have been determined for divalent metal ions. Co (Ⅱ), Ni (Ⅱ) and Zn (Ⅱ) by means of the Calvin-Bjerrum technique at the various temperatures. The standard free energy changes for the reactions at $20^{\circ}$, $30^{\circ}$, $40^{\circ}$and $50^{\circ}C$ were calculated, and the corresponding values of ${\Delta}H^{\circ}$ and ${\Delta}S^{\circ}$ applying over this temperature range are reported. The results are interpreted on the basis of current theories of metal chelate formation in aqueous solution.