Calculation of the absolute hydration enthalpy and free energy of H+ and OH−

Mejías, José A.; Lago, S.

doi:10.1063/1.1313793

Cited by 175 publications

(139 citation statements)

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“…For a discussion of protonation/deprotonation equilibria, as well as the results of the COSMO procedure, the free energy of solvation of the proton is required. We adopt the value DG (solv) (H + )=-1100 kJ mol -1 [27,28,29], but note that there is considerable experimental uncertainty in the free energy of solvation of a proton, and therefore in all of the solution results (see Discussion).…”

Section: Methodsmentioning

confidence: 99%

Computational studies of Cu(II)[peptide] binding motifs: Cu[HGGG] and Cu[HG] as models for Cu(II) binding to the prion protein octarepeat region

Pushie

Rauk

2003

J Biol Inorg Chem

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The binding of Cu(II) to the prion protein is investigated by computations at the B3LYP level of theory on models of the octarepeat domain of the prion protein. The models incorporate the functionality of the glycine (G) and histidine (H) residues which occur in the octarepeat domain, PHGGGWGQ. The copper complexes are designated Cu[HG] and Cu[HGGG]. Coordination to the metal via the imidazole ring of the histidine, the amide carbonyl groups, and the backbone nitrogen atom of the amide groups were examined, as well as several protonation/deprotonation states of each structure. EPR and CD titration experiments suggest that the octarepeat segments of the unstructured N-terminal domain of prion protein can bind Cu(II) in a 1:1 Cu-to-octarepeat ratio. The results identify the extent to which the Cu(II) facilitates peptide backbone deprotonation, and the propensity of binding in the forward (toward the C-terminus) direction from the anchoring histidine residue. A plausible mechanism is suggested for changing from amide O-atom to deprotonated amide N-atom coordination, and for assembly of the observed species in solutions of Cu[PrP] and truncated models of it. A structure is proposed which has the N2O2 coordination pattern for the minor component observed experimentally by EPR spectroscopy for the Cu[HGGG] model. The most stable neutral Cu[HGGG] structure found, with coordination environment N3O1, corresponds to that observed for Cu[HGGGW] and Cu[HGGG] both in the solid state and as the major component in solution at neutral pH.

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Section: Methodsmentioning

confidence: 99%

Computational studies of Cu(II)[peptide] binding motifs: Cu[HGGG] and Cu[HG] as models for Cu(II) binding to the prion protein octarepeat region

Pushie

Rauk

2003

J Biol Inorg Chem

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“…Due to the inherent difficulty of measuring absolute solvation free energy of an ion, the reported "experimental" ΔG sol 298 (H + ) values have a wide range from −252.6 to −264.1 kcal/mol. 87 We recently calculated ΔG sol 298 (H + ) by using a high-level, ab initio method of incorporating a hybrid supermolecule-continuum approach 88,89,90,91 based on the same SVPE procedure used in the present study. ΔG sol 298 (H + ) was predicted to be −262.4 kcal/mol 88 which was used in the present study.…”

Section: Computational Detailsmentioning

confidence: 99%

First-Principles Calculation of pK_a for Cocaine, Nicotine, Neurotransmitters, and Anilines in Aqueous Solution

Chen

2007

J. Phys. Chem. B

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The absolute pK a values of 24 representative amine compounds, including cocaine, nicotine, 10 neurotransmitters, and 12 anilines, in aqueous solution were calculated by performing first-principles electronic structure calculations that account for the solvent effects using four different solvation models, i.e. the surface and volume polarization for electrostatic interaction (SVPE) model, the standard polarizable continuum model (PCM), the integral equation formalism for the polarizable continuum model (IEFPCM), and the conductor-like screening solvation model (COSMO). Within the examined computational methods, the calculations using the SVPE model lead to the absolute pK a values with the smallest root-mean-square-deviation (RMSD) value (1.18). When the SVPE model was replaced by the PCM, IEFPCM, and COSMO, the RMSD value of the calculated absolute pK a values became 3.21, 2.72, and 3.08, respectively. All types of calculated pK a values linearly correlate with the experimental pK a values very well. With the empirical corrections using the linear correlation relationships, the theoretical pK a values are much closer to the corresponding experimental data and the RMSD values become 0.51 to 0.83. The smallest RMSD value (0.51) is also associated with the SVPE model. All of the results suggest that the first-principles electronic structure calculations using the SVPE model are a reliable approach to the pK a prediction for the amine compounds.

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“…Much work has been devoted to achieving accurate hydration enthalpies of the proton (Halliwell and Nyburg 1963;Conway 1964;Marcus 1987;Rashin and Namboodiri 1987;Atkins 1998;Bockris and Reddy 1998;Tissandier et al 1998;Mejías and Lago 2000;Coe 2001) and electron (Han and Bartels 1990;Schwarz 1991;Shiraishi et al 1994;Donald et al 2010). A few results for the hydration Gibbs energies of the proton (Tissandier et al 1998;Coe 2001) and electron (Han and Bartels 1990) are also available in literature.…”

Section: Introductionmentioning

confidence: 99%

Solvation enthalpies and Gibbs energies of the proton and electron: Influence of solvation models

Tošović¹,

Marković²,

Milenković³

et al. 2016

J Serb Soc Comp Mech

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A comprehensive examination of the solvation enthalpies and Gibbs energies of the proton and electron in twenty solvents of different polarities was carried. Eleven quantum mechanical methods were applied in conjunction with the 6-311++G(d,p) basis set and C-PCM solvation model.It was found that different methods produce consistent values for the solvation enthalpy and Gibbs energy of the proton in all solvents, while the corresponding values for the electron are mutually notably different. The fact that the Minnesota functionals often produced inconsistent solvation enthalpy and Gibbs energy values of the electron indicates their unreliable performance without the corresponding SMD solvation model, whereas other studied methods only slightly depend on solvation models.A comparison of the results of the present investigation to those obtained by employing SMD reveals that C-PCM produces slightly more negative (less positive) solvation enthalpies and Gibbs energies of the electron, and less negative values for the proton. These results are also in accord with the literature data where the IEF-PCM solvation model was used.

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Calculation of the absolute hydration enthalpy and free energy of H+ and OH−

Cited by 175 publications

References 44 publications

Computational studies of Cu(II)[peptide] binding motifs: Cu[HGGG] and Cu[HG] as models for Cu(II) binding to the prion protein octarepeat region

Computational studies of Cu(II)[peptide] binding motifs: Cu[HGGG] and Cu[HG] as models for Cu(II) binding to the prion protein octarepeat region

First-Principles Calculation of pK_a for Cocaine, Nicotine, Neurotransmitters, and Anilines in Aqueous Solution

Solvation enthalpies and Gibbs energies of the proton and electron: Influence of solvation models

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Calculation of the absolute hydration enthalpy and free energy of H+ and OH−

Cited by 175 publications

References 44 publications

Computational studies of Cu(II)[peptide] binding motifs: Cu[HGGG] and Cu[HG] as models for Cu(II) binding to the prion protein octarepeat region

Computational studies of Cu(II)[peptide] binding motifs: Cu[HGGG] and Cu[HG] as models for Cu(II) binding to the prion protein octarepeat region

First-Principles Calculation of pKa for Cocaine, Nicotine, Neurotransmitters, and Anilines in Aqueous Solution

Solvation enthalpies and Gibbs energies of the proton and electron: Influence of solvation models

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First-Principles Calculation of pK_a for Cocaine, Nicotine, Neurotransmitters, and Anilines in Aqueous Solution