Thermodynamic Measurements

Salomon, Mark; Garnsey, R.; Prue, J. E.; Criss, Cecil M.

doi:10.1007/978-1-4684-1959-7_2

Cited by 9 publications

(14 citation statements)

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“…We have decided to use methanol for this purpose. The Δ t X ° ( X = G , H , S ) of cations from MeOH to any other solvent (e.g., EtOH) were obtained by combining the corresponding functions of transfer from water: The data, based on Ph 4 AsPh 4 B convention, were taken from refs and . Transfer thermodynamic parameters for M L + were calculated using the following expression: Such analysis resulted, for example, in the thermodynamic cycle shown in Scheme , which explains differences in standard reaction Gibbs energies for the binding of Na + in MeOH and EtOH.…”

Section: Discussionmentioning

confidence: 99%

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Solvation Effect on Complexation of Alkali Metal Cations by a Calix[4]arene Ketone Derivative

et al. 2017

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The medium effect on the complexation of alkali metal cations with a calix[4]arene ketone derivative (L) was systematically examined in methanol, ethanol, N-methylformamide, N,N-dimethylformamide, dimethyl sulfoxide, and acetonitrile. In all solvents the binding of Na cation by L was rather efficient, whereas the complexation of other alkali metal cations was observed only in methanol and acetonitrile. Complexation reactions were enthalpically controlled, while ligand dissolution was endothermic in all cases. A notable influence of the solvent on NaL complex stability could be mainly attributed to the differences in complexation entropies. The higher NaL stability in comparison to complexes with other alkali metal cations in acetonitrile was predominantly due to a more favorable complexation enthalpy. The H NMR investigations revealed a relatively low affinity of the calixarene sodium complex for inclusion of the solvent molecule in the calixarene hydrophobic cavity, with the exception of acetonitrile. Differences in complex stabilities in the explored solvents, apart from N,N-dimethylformamide and acetonitrile, could be mostly explained by taking into account solely the cation and complex solvation. A considerable solvent effect on the complexation equilibria was proven to be due to an interesting interplay between the transfer enthalpies and entropies of the reactants and the complexes formed.

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Section: Discussionmentioning

confidence: 99%

“…The transfer of Na + from MeOH to NMF is favorable in terms of both enthalpy and entropy (Δ t H ° (Na + , MeOH → NMF) = −9 kJ mol –1 ; Δ t S ° (Na + , MeOH → NMF) = 21 J K –1 mol –1 , Schemes S5 and S6). , …”

Section: Discussionmentioning

confidence: 99%

Solvation Effect on Complexation of Alkali Metal Cations by a Calix[4]arene Ketone Derivative

et al. 2017

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“…Previous studies (9,22) indicated apparent deviation of the concentrations of adenine nucleotides in the ascites tumor cell from the adenylate kinase equilibrium when the energy state of the cell is high, although in all other metabolic states total adenine nucleotides appear to be in equilibrium (9,10,22 Table 2. The extent of deviation of the mass action ratios from the corresponding equilibrium values increased from 3.5-fold to 11-fold when the MgATP or total ATP levels were nearly doubled by incubation of the cells with adenosine, Pi, and Mg2+.…”

Section: Resultsmentioning

confidence: 99%

Noninvasive ³¹ P NMR probes of free Mg ²⁺ , MgATP, and MgADP in intact Ehrlich ascites tumor cells

Gupta

Yushok

1980

Proc. Natl. Acad. Sci. U.S.A.

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MATERIALS AND METHODSEhrlich ascites tumor cells of the hypotetraploid fast clone strain were propagated in female white Swiss mice of the ICR strain by intraperitoneal injection of the ascites tumor fluid and were prepared for in vitro incubation as described (9). The tumor cells were washed three times with cold isotonic salt solution containing 147 mM NaCl, 5.9 mM KCI, 1.5 mM MgSO4, 3mM glucose, 0.6 mM Pi, 30 mM Hepes, pH 7.4 at 37°C, and amino acids required for protein synthesis. The cells were then incubated in the same medium for 30 min at 37°C in a shaker bath and were concentrated by refrigerated centrifugation immediately prior to use in the NMR experiment. Other supplementary additions were made as indicated in Results. The NMR sample was initially saturated with 02 by bubbling pure gaseous 02 through the cell suspension and was then maintained at 10°C with cooled nitrogen so that the cells metabolized slowly, did not alter the pH of the suspension, and remained viable. The cells in the NMR tube were kept aerobic by periodic resuspension in oxygenated buffer. Noncellular control experiments with ATP and MgATP were done at pH 7.2 in 20 mM 2-[bis(2-hydroxyethyl)amino]-2-(hydroxymethyl)-1,3-propanediol (Bistris) buffer containing 0.14 M KCI and 10 mM NaCl to simulate intracellular pH and ionic strength. Phos- 2487The publication costs of this article were defrayed in part by page charge payment. This article must therefore be hereby marked "advertisement" in accordance with 18 U. S. C. §1734 solely to indicate this fact.

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“…The values of the free energies of transfer of ions from one solvent to another are reliable in view of the compensation of the ~d-/0 and TZarS O terms, where the structural contributions of unknown magnitudes largely cancel out [5].…”

Section: ~Go(ion) = Ago(neut) + Ago(el)(ion)mentioning

confidence: 99%

“…Though a number of theoretical and semi-empirical extrathermodynamic methods have been attempted to divide the free energies of transfer into single-ion contributions, all the methods have some inherent limitations and the results obtained are usually divergent [1][2][3][4][5].…”

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Enthalpy and entropy of transfer of hydrogen ion from water to mixed solvents

Chakraborty

Lahiri

1984

Journal of Thermal Analysis

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Attempts have been made to determine the enthalpy and entropy of transfer of H -t-ion from water to mixed solvents using the calorimetric data of earlier experiments. The results are in qualitative agreement with the facts that ~HO(H +) passes through an exothermic maximum and T~,S 0 passes through a minimum at about 20 to 30 wt% of organic solvent indicating the initial structure formation and the ultimate breakdown of the solvent structure with the addition of organic solvent.The importance and use of the free energies of transfer [~G~ or medium effects of the H + ion in different mixed or non-aqueous solvents are well-known. The medium effect of the H + ion is a quantitative measure of the differences in ion-solvent interactions which are the controlling factors in dilute solutions where ion-ion interactions are absent. Moreover, medium effects of H + ions in different solvents would measure the relative basicities of the solvents directly.Measurements of the medium effects of electroneutral combinations are relatively simple, but the thermodynamics provide no method to divide them into single-ion contributions. Though a number of theoretical and semi-empirical extrathermodynamic methods have been attempted to divide the free energies of transfer into single-ion contributions, all the methods have some inherent limitations and the results obtained are usually divergent [1][2][3][4][5].However, it has been widely admitted that the free energy of transfer of ions can be regarded as composed of a neutral part and an electrostatic part, i.e. ~GO(ion) = AGO(neut) + AGO(el)(ion)The values of the free energies of transfer of ions from one solvent to another are reliable in view of the compensation of the ~d-/0 and TZarS O terms, where the structural contributions of unknown magnitudes largely cancel out [5].However, the separation of ~d-/0 into single-ion contributions is difficult, as the enthalpies of solvation are mainly dependent on complex structural contributions arising from the making or breaking of bonds. Considerable disagreements (as high as 50 Kcal) in the single-ion enthalpy values in water have been reported [5]. Consistent results are not given by methods such as [6]

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Thermodynamic Measurements

Cited by 9 publications

References 384 publications

Solvation Effect on Complexation of Alkali Metal Cations by a Calix[4]arene Ketone Derivative

Solvation Effect on Complexation of Alkali Metal Cations by a Calix[4]arene Ketone Derivative

Noninvasive ³¹ P NMR probes of free Mg ²⁺ , MgATP, and MgADP in intact Ehrlich ascites tumor cells

Enthalpy and entropy of transfer of hydrogen ion from water to mixed solvents

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Thermodynamic Measurements

Cited by 9 publications

References 384 publications

Solvation Effect on Complexation of Alkali Metal Cations by a Calix[4]arene Ketone Derivative

Solvation Effect on Complexation of Alkali Metal Cations by a Calix[4]arene Ketone Derivative

Noninvasive 31 P NMR probes of free Mg 2+ , MgATP, and MgADP in intact Ehrlich ascites tumor cells

Enthalpy and entropy of transfer of hydrogen ion from water to mixed solvents

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Noninvasive ³¹ P NMR probes of free Mg ²⁺ , MgATP, and MgADP in intact Ehrlich ascites tumor cells