Ab initio molecular dynamics simulation of aqueous solution of nitric oxide in different formal oxidation states

Venâncio, Mateus F.; Rocha, Willian R.

doi:10.1016/j.cplett.2015.08.020

Cited by 4 publications

(8 citation statements)

References 61 publications

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“…The theoretical results presented in this work, in conjunction with our previous ab initio molecular dynamics study, 39 give us support to propose the processes shown in Figure 3, which can be involved in the reduction of NO to HNO in aqueous solution. NO is involved in equilibrium with the radical anion HONO •− which opens two possible pathways for the reduction of NO, as shown in Figure 3.…”

Section: ■ Theoretical Detailssupporting

confidence: 83%

“…We have recently shown by ab initio molecular dynamics that 2 NO in aqueous solution is involved in a reversible equilibrium, starting around 700 fs, generating the radical anion species HONO •– , according to Scheme . This radical anion species can trap one electron and, therefore, be involved in a competitive reduction process with 2 NO, as shown in Scheme , opening up a new pathway for the reduction of 2 NO to 3 NO – .…”

Section: Results and Discussionmentioning

confidence: 99%

“…The hybrid meta-GGA functional TPSSh provides good results, as was also obtained for transition metal compounds. 38 We have recently shown 39 by ab initio molecular dynamics that 2 NO in aqueous solution is involved in a reversible equilibrium, starting around 700 fs, generating the radical anion species HONO •− , according to Scheme 1. This radical anion species can trap one electron and, therefore, be involved in a competitive reduction process with 2 NO, as shown in Scheme 2, opening up a new pathway for the reduction of 2 NO to The solvent surface area (SASA) of HNO (152.60 Å 2 ) was computed using the molecular surface module of MarvinView package.…”

Section: ■ Theoretical Detailsmentioning

confidence: 99%

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Solvation and Proton-Coupled Electron Transfer Reduction Potential of ²NO^• to ¹HNO in Aqueous Solution: A Theoretical Investigation

2017

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In this work, quantum mechanical calculations and Monte Carlo statistical mechanical simulations were carried out to investigate the solvation properties of HNO in aqueous solution and to evaluate the proton-coupled one electron reduction potential of NO toHNO, which is essential missing information to understand the fate of NO in the biological medium. Our results showed that theHNO molecule acts mainly as a hydrogen bond donor in aqueous solution with an average energy of -5.5 ± 1.3 kcal/mol. The solvation free energy of HNO in aqueous solution, computed using three approaches based on the linear response theory, revealed that the current prediction of the hydration free energy of HNO is, at least, 2 times underestimated. We proposed two pathways for the production of HNO through reduction of NO. The first pathway is the direct reduction of NO through proton-coupled electron transfer to produce HNO, and the second path is the reduction of the radical anion HONO, which is involved in equilibrium with NO in aqueous solution. We have shown that both pathways are viable processes under physiological conditions, having reduction potentials of E°' = -0.161 V and E°' ≈ 1 V for the first and second pathways, respectively. The results shows that both processes can be promoted by well-known biological reductants such as NADH, ascorbate, vitamin E (tocopherol), cysteine, and glutathione, for which the reduction potential at physiological pH is around -0.3 to -0.5 V. The computed reduction potential of NO through the radical anion HONO can also explain the recent experimental findings on the formation of HNO through the reduction of NO, promoted by HS, vitamin C, and aromatic alcohols. Therefore, these results contribute to shed some light into the question of whether and how HNO is produced in vivo and also for the understanding of the biochemical and physiological effects of NO.

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Section: ■ Theoretical Detailssupporting

confidence: 83%

Section: Results and Discussionmentioning

confidence: 99%

Section: ■ Theoretical Detailsmentioning

confidence: 99%

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Solvation and Proton-Coupled Electron Transfer Reduction Potential of ²NO^• to ¹HNO in Aqueous Solution: A Theoretical Investigation

2017

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“…That is, the reactant and products have different spin states and thus the reaction may proceed through surface crossings, which usually requires more sophisticated theoretical treatment to include these nonadiabatic effects . The released NO molecule can also react with the solvent water molecules generating different NO species as we demonstrated recently . Therefore, to investigate this reaction mechanism, we must include explicit solvent water molecules at least up to the first solvation shell.…”

Section: Resultsmentioning

confidence: 99%

“…Additionally, multiconfigurational spin-corrected calculations revealed that the ground state of the complex has a significant contribution to the Ru III NO 0 electronic configuration, in contrast to the proposed Ru II NO + configuration. Aiming at understanding the fate of the released NO species in solution, we have recently employed ab initio molecular dynamics simulations to investigate the early chemical events involved in the dynamics of NO (NO • ), nitrosonium cation (NO + ), and nitroxide anion (NO – ) in aqueous solution . We showed that NO + ion is very reactive in aqueous solution having a lifetime of ∼4 × 10 –13 s, which is shorter than the value of 3 × 10 –10 s predicted experimentally.…”

Section: Introductionmentioning

confidence: 90%

Formation and Release of NO from Ruthenium Nitrosyl Ammine Complexes [Ru(NH₃)₅(NO)]^2+/3+ in Aqueous Solution: A Theoretical Investigation

Rodrigues

Rocha

2016

J. Phys. Chem. B

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In this article, density functional theory in conjunction with Monte Carlo statistical mechanical simulation was used to investigate the electronic structure, reduction potential, solvation, and solvent effects on the electronic spectra of nitrosyl ammine complexes using [Ru(NH)(NO)] as model compounds. In addition, ligand exchange reactions with solvent water molecules were also investigated. It is shown that the complexes are involved in strong hydrogen bonds in aqueous solution, with mean average energies of -13.5 ± 0.4 and -22.4 ± 0.4 kcal mol for Ru(II) and Ru(III), respectively. Interestingly, for all the complexes studied, the NO ligand is not involved in hydrogen bonding interactions in aqueous solution. These strong hydrogen bonds are responsible for the high stability of these complexes in aqueous solution, showing formation constants K greater than 10. The complex [Ru(NH)(NO)] can easily be reduced by biological reducing agents in both the singlet and triplet states; however, the reduction is easier in the triplet state, which has a positive reduction potential of 1.70 V. The formation of [Ru(NH)(NO)] in its most stable singlet state may take place through at least two singlet-triplet surface crossings leading to nonadiabatic effects. The existence of the minimum-energy crossing points makes the release of NO from the triplet state more favorable, with an activation energy almost seven times lower (∼6 kcal mol).

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Nature of the bond, reduction potential, and solvation properties of ruthenium nitrosyl complexes of the type trans‐[Ru(NH₃)₄(L)(NO)]^2+/3+ and [Ru(salen)(L)(NO)]^2+/3+ in different charge and spin states

Rodrigues

Rocha

2020

Int J of Quantum Chemistry

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In this work, we present a systematic study of the nature of the RuNO bond, reduction potential, and behavior in the solution of several ruthenium nitrosyl complexes of the type trans‐[Ru(NH3)4(L)(NO)]2+/3+ (L = Cl, H2O, NH3, OH, py = pyridine, POEt3 = triethylphosphite, TVP = trivinyl phosphite) and [Ru(salen)(L)(NO)]2+/3+ (L = Cl, H2O) in different charge and spin states. We employed density functional theory, complete active space self‐consistent field, the quantum theory of atoms in molecules, charge decomposition analysis, and Monte Carlo statistical simulation in aqueous solution to investigate how the different ligands on the coordination sphere of the ruthenium atom can affect the nature of the RuNO bond and, therefore, its reactivity, reduction potential, and solvation properties. The nature of the RuNO bond varies significantly between the singlet, doublet, and triplet electronic states of these complexes, in part due to the change in the coordination mode of the NO ligand and also due to the electron correlation effects along the RuNO bond that changes drastically. For all complexes studied, the RuNO bond shows some intriguing characteristics, such as large kinetic energy density and considerable amount of electron localization between the atoms, besides high multiconfigurational character, with a significant contribution from the RuIIINO0 configuration. In addition, for all the complexes investigated, the NO ligand does not interact with the solvent through hydrogen bonds, making this group accessible for chemical reactions in solution. Another important finding was that some of the RuIIINO compounds can be reduced by biological reducing agents in the singlet ground state, while all of them have high reduction potentials in the triplet excited state, making them suitable candidates for the photorelease of nitric oxide.

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Ab initio molecular dynamics simulation of aqueous solution of nitric oxide in different formal oxidation states

Cited by 4 publications

References 61 publications

Solvation and Proton-Coupled Electron Transfer Reduction Potential of ²NO^• to ¹HNO in Aqueous Solution: A Theoretical Investigation

Solvation and Proton-Coupled Electron Transfer Reduction Potential of ²NO^• to ¹HNO in Aqueous Solution: A Theoretical Investigation

Formation and Release of NO from Ruthenium Nitrosyl Ammine Complexes [Ru(NH₃)₅(NO)]^2+/3+ in Aqueous Solution: A Theoretical Investigation

Nature of the bond, reduction potential, and solvation properties of ruthenium nitrosyl complexes of the type trans‐[Ru(NH₃)₄(L)(NO)]^2+/3+ and [Ru(salen)(L)(NO)]^2+/3+ in different charge and spin states

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Ab initio molecular dynamics simulation of aqueous solution of nitric oxide in different formal oxidation states

Cited by 4 publications

References 61 publications

Solvation and Proton-Coupled Electron Transfer Reduction Potential of 2NO• to 1HNO in Aqueous Solution: A Theoretical Investigation

Solvation and Proton-Coupled Electron Transfer Reduction Potential of 2NO• to 1HNO in Aqueous Solution: A Theoretical Investigation

Formation and Release of NO from Ruthenium Nitrosyl Ammine Complexes [Ru(NH3)5(NO)]2+/3+ in Aqueous Solution: A Theoretical Investigation

Nature of the bond, reduction potential, and solvation properties of ruthenium nitrosyl complexes of the type trans‐[Ru(NH3)4(L)(NO)]2+/3+ and [Ru(salen)(L)(NO)]2+/3+ in different charge and spin states

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Solvation and Proton-Coupled Electron Transfer Reduction Potential of ²NO^• to ¹HNO in Aqueous Solution: A Theoretical Investigation

Solvation and Proton-Coupled Electron Transfer Reduction Potential of ²NO^• to ¹HNO in Aqueous Solution: A Theoretical Investigation

Formation and Release of NO from Ruthenium Nitrosyl Ammine Complexes [Ru(NH₃)₅(NO)]^2+/3+ in Aqueous Solution: A Theoretical Investigation

Nature of the bond, reduction potential, and solvation properties of ruthenium nitrosyl complexes of the type trans‐[Ru(NH₃)₄(L)(NO)]^2+/3+ and [Ru(salen)(L)(NO)]^2+/3+ in different charge and spin states