scholarly journals Thermodynamics of porphyrin dimerization in aqueous solutions

1984 ◽  
Vol 219 (2) ◽  
pp. 445-450 ◽  
Author(s):  
R Margalit ◽  
M Rotenberg
Keyword(s):  
Aqueous Solution ◽  
Aqueous Solutions ◽  
Equilibrium Constants ◽  
Enthalpy Change ◽  
Aggregation Process ◽  
Neutral Ph ◽  
Similar Temperature ◽  
Increasing Temperature ◽  
Phosphate Buffered Saline ◽  
Hydrophobic Bonding

The dimerization equilibrium of deuteroporphyrin IX and of mesoporphyrin IX in aqueous solutions were studied by fluorimetric techniques over the 0.01-1 microM concentration range, where dimerization is the dominant aggregation process. Deuteroporphyrin IX was studied at several temperatures over the range 22-37 degrees C, and mesoporphyrin at 25 and 37 degrees C. The magnitudes determined for the dimerization equilibrium constants (25 degrees C, neutral pH, phosphate-buffered saline) are 2.3 × 10(6)M-1 and 5.4 × 10(6)M-1 for the deutero and meso derivatives respectively. The meso, deutero and haemato species tested show a similar temperature effect, namely dimerization decreasing with increasing temperature, indicating the involvement of a negative enthalpy change. Van't Hoff isochore of the dimerization constants determined for deuteroporphyrin IX was linear within the temperature range of 22-37 degrees C, allowing the calculation of the thermodynamic parameters. For deuteroporphyrin dimerization, those were found to be delta G0 = −36. 4kJ X mol-1; delta H0 = −46. 0kJ X mol-1 and delta S0 = −32.2J X K-1 X mol-1 (at neutral pH, 25 degrees C, phosphate-buffered saline), showing the process to be enthalpy-driven. Similar trends have been found for porphyrin species other than those studied here. Our data fit with a hypothesis giving a major role to the solvent in driving porphyrins to aggregate in aqueous solution. The magnitudes and directions of the energetic changes fit better with the expectation of the ‘ solvophobic force’ theory predicting enthalpy-driven association, than with the classic hydrophobic bonding, predicting the association to be entropy-driven.

THE DISSOCIATION OF α- AND β-LIPOVITELLIN IN AQUEOUS SOLUTION: PART I. EFFECT OF pH, TEMPERATURE, AND OTHER FACTORS

1962 ◽  
Vol 40 (3) ◽  
pp. 363-372 ◽  
Author(s):  
R. W. Burley ◽  
W. H. Cook
Keyword(s):  
Aqueous Solution ◽  
Ionic Strength ◽  
Aqueous Solutions ◽  
Thermodynamic Data ◽  
Equilibrium Constants ◽  
Effect Of Ph ◽  
Reversible Dissociation ◽  
Lipoprotein Concentration ◽  
Irreversible Aggregation ◽  
Increasing Temperature

The effect of pH, temperature, ionic strength, and lipoprotein concentration on the reversible dissociation of α- and β-lipovitellin in aqueous solutions above pH 6 has been examined by ultracentrifugal measurements. Under otherwise similar conditions α- and β-lipovitellin are 50% dissociated at pH 10.5 and 7.8, respectively. Both lipovitellins undergo an irreversible aggregation above about pH 11; β-lipovitellin is sometimes converted to a non-dissociable form upon aging. Dissociation of both lipovitellins decreases with increasing ionic strength and increasing temperature. Although the ultracentrifugal method has limitations, provisional equilibrium constants and thermodynamic data were obtained from it that are comparable with those obtained for certain protein systems.

THE DISSOCIATION OF α- AND β-LIPOVITELLIN IN AQUEOUS SOLUTION: PART I. EFFECT OF pH, TEMPERATURE, AND OTHER FACTORS

1962 ◽  
Vol 40 (1) ◽  
pp. 363-372 ◽  
Author(s):  
R. W. Burley ◽  
W. H. Cook
Keyword(s):  
Aqueous Solution ◽  
Ionic Strength ◽  
Aqueous Solutions ◽  
Thermodynamic Data ◽  
Equilibrium Constants ◽  
Effect Of Ph ◽  
Reversible Dissociation ◽  
Lipoprotein Concentration ◽  
Irreversible Aggregation ◽  
Increasing Temperature

The effect of pH, temperature, ionic strength, and lipoprotein concentration on the reversible dissociation of α- and β-lipovitellin in aqueous solutions above pH 6 has been examined by ultracentrifugal measurements. Under otherwise similar conditions α- and β-lipovitellin are 50% dissociated at pH 10.5 and 7.8, respectively. Both lipovitellins undergo an irreversible aggregation above about pH 11; β-lipovitellin is sometimes converted to a non-dissociable form upon aging. Dissociation of both lipovitellins decreases with increasing ionic strength and increasing temperature. Although the ultracentrifugal method has limitations, provisional equilibrium constants and thermodynamic data were obtained from it that are comparable with those obtained for certain protein systems.

scholarly journals Rates and equilibrium constants for the covalent hydration of 5-bromo-2(1H)-pyrimidinone in aqueous solution

1986 ◽  
Vol 64 (6) ◽  
pp. 1267-1272 ◽  
Author(s):  
Oswald S. Tee ◽  
Jana Pika ◽  
M. Judith Kornblatt ◽  
Michael Trani
Keyword(s):  
Aqueous Solution ◽  
Aqueous Solutions ◽  
Title Compound ◽  
Equilibrium Constants ◽  
Kinetic Studies ◽  
Kinetics Of

The kinetics of bromination of the title compound (1) have been measured in aqueous solutions of pH 0–6. The change in the order of reaction which occurs around pH 2.5 is explained by 1 reacting via its covalent hydrate, 3. Furthermore, there is sufficient 3 present at equilibrium that the kinetics of its equilibration with 1 were also measured. From these two studies the extent of covalent hydration of 1 is estimated to be 5%.Kinetic studies of the bromination of the dimethyl cation 5 and of its equilibration with the pseudobase 6 were also carried out for the purposes of comparison.The present results for 1, 3, 5, and 6 are compared to earlier results for 2-pyrimidinone and analogous derivatives.

Tautomeric equilibria and pKa values for 'sulfurous acid' in aqueous solution: a thermodynamic analysis

1979 ◽  
Vol 57 (4) ◽  
pp. 454-457 ◽  
Author(s):  
J. Peter Guthrie
Keyword(s):  
Aqueous Solution ◽  
Free Energy ◽  
Aqueous Solutions ◽  
Equilibrium Constants ◽  
Acid Solutions ◽  
Sulfurous Acid ◽  
Free Energy Of Formation ◽  
Dilute Aqueous Solutions ◽  
Sulfite Ion ◽  
Energy Of Formation

The free energy of formation of dimethyl sulfite in aqueous solution can be calculated as −91.45 ± 0.79 kcal/mol; this calculation required measurement of the solubility of dimethyl sulfite. From this value and the pKa of SO(OH)2, using previously reported methods, the free energy of formation of SO(OH)2 can be calculated to be −129.26 ± 0.89 kcal/mol. Comparison of this value with the value obtained from the free energy of formation of 'sulfurous acid' solutions, calculated from the free energy of formation of sulfite ion and the apparent pKa, values, permits evaluation of the free energy of covalent hydration of SO2 as 1.6 + 1.0 kcal/mol, in agreement with earlier qualitative spectroscopic observations. From the apparent pKa and the anticipated pKa values for the tautomers (SO(OH)2, pK1 = 2.3; HSO2(OH), pK1 = −2.6) it is possible to calculate the free energy change for tautomerization of SO(OH)2 to H—SO2(OH) as +4.5 ± 1.2 kcal/mol. All equilibrium constants required for Scheme 1, describing the species present in dilute aqueous solutions of SO2, have been calculated. In agreement with previous Raman studies the major tautomer of 'bisulfite ion' is calculated to be H—SO3−.

Pulse radiolysis of nitric oxide in aqueous solution

1970 ◽  
Vol 48 (2) ◽  
pp. 393-394 ◽  
Author(s):  
W. A. Seddon ◽  
M. J. Young
Keyword(s):  
Nitric Oxide ◽  
Aqueous Solution ◽  
Steady State ◽  
Aqueous Solutions ◽  
Pulse Radiolysis ◽  
Hydrated Electron ◽  
Neutral Ph

Pulse radiolysis of aqueous solutions of nitric oxide at neutral pH shows that the reaction initiated by the hydrated electron, e−(aq), proceeds via NO− and a new transient thought to be (N2O2)−, and not HNO as indicated previously by steady state radiolysis.

scholarly journals Thermodynamics of the Adsorption of Cobalt on Lead Dioxide from Aqueous Solution

1995 ◽  
Vol 12 (2) ◽  
pp. 139-149 ◽  
Author(s):  
H. Ahmad ◽  
M. Afzal ◽  
M. Saleem ◽  
S.M. Hasany
Keyword(s):  
Aqueous Solution ◽  
Aqueous Solutions ◽  
Distribution Coefficient ◽  
Lead Dioxide ◽  
Optimum Conditions ◽  
Different Temperatures ◽  
Increasing Temperature

The adsorption of cobalt on lead dioxide from aqueous solutions has been optimized with respect to the shaking time, the amount of adsorbent, the pH and the concentration of adsorbate at 293 K. Under such optimum conditions, the adsorption of cobalt on lead dioxide has been studied at different temperatures and the process found to be endothermic with the distribution coefficient (KD) increasing with increasing temperature. The data fitted very well to the Langmuir, Freundlich and Dubinin–adushkevich isotherms, allowing the corresponding constants to be calculated. Values of ΔH0 and ΔS0 were calculated from the slope and intercept of the plots of In KD versus 1/T. The value of ΔG0, which decreased with increasing temperature, showed that the adsorption is more favourable at higher temperatures.

Effect of thermal history of aqueous solutions of KCl on the metastable zone width

1984 ◽  
Vol 49 (3) ◽  
pp. 559-569 ◽  
Author(s):  
Jaroslav Nývlt
Keyword(s):  
Aqueous Solution ◽  
Aqueous Solutions ◽  
Thermal History ◽  
Equilibrium Solubility ◽  
Metastable Zone Width ◽  
Zone Width ◽  
Preceding Experiment ◽  
History Of ◽  
Metastable Zone ◽  
The Given

The metastable zone width of an aqueous solution of KCI was measured as a function of the time and temperature of overheating above the equilibrium solubility temperature. It has been found that when the experiments follow close upon one another, the parameters of the preceding experiment affect the results of the experiment to follow.The results are interpreted in terms of hypotheses advanced in the literature to account for the effect of thermal history of solution. The plausibility and applicability of these hypotheses are assessed for the given cause of aqueous solution of a well soluble electrolyte.

The reactions of oligoalcohols with arsenic, arsenous, boric and germanic acids

1980 ◽  
Vol 45 (10) ◽  
pp. 2645-2655 ◽  
Author(s):  
Antonín Mikan ◽  
Miloš Bartušek
Keyword(s):  
Aqueous Solutions ◽  
Equilibrium Constants ◽  
Dilute Aqueous Solutions

The reactions of sorbitol, mannitol, adonitol, dulcitol, glucose and glycerol with H3AsO4, H3AsO3, H3BO3 and GeO2 acids in dilute aqueous solutions were studied by potentiometric neutralization titrations. The formation of the following chelates was demonstrated: As(V)L3-, As(III)L(OH)2-, HAs(III)L(OH)2, BL2-, GeL2(OH)- and GeL32- and the equilibrium constants for their formation were found. Conditions for formation of these chelates of organic oligohydroxy compounds are discussed.

scholarly journals I. Thermo-electric behaviour of aqueous solutions with mercurial electrodes

1879 ◽  
Vol 29 (196-199) ◽  
pp. 472-482 ◽  
Keyword(s):  
Aqueous Solution ◽  
Aqueous Solutions ◽  
Internal Diameter ◽  
Thermo Electric ◽  
Thin Glass ◽  
Mercury Surface

In order to investigate this subject, I devised and constructed the following apparatus :—A and B are two thin glass basins, 81 millims. internal diameter (= 5,153 sq. millims. of mercury surface), and 6·0 centims. deep; each containing a layer of mercury about 1·0 centim. deep, covered by a layer, about 3 centims. deep, of the aqueous solution to be examined.

scholarly journals Meta-studtite stability in aqueous solutions. Impact of HCO3−, H2O2 and ionizing radiation on dissolution and speciation

2021 ◽  
Author(s):  
Junyi Li ◽  
Zoltán Szabó ◽  
Mats Jonsson
Keyword(s):  
Aqueous Solution ◽  
Ionizing Radiation ◽  
Aqueous Solutions ◽  
Carbonate Complexes ◽  
C Nmr

Four different uranyl-(peroxide)-carbonate complexes were identified during studtite and meta-studtite dissolution in aqueous solution containing 10 mM HCO3− by 13C NMR.

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