Preprint of "Guanidinium Like-Charge Ion Pairing and Oligoarginine Aggregation in Water by NMR, Cryo-Electron Microscopy, and Molecular Dynamics"
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| Format: | Recurso digital |
| Langue: | anglais |
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2025
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| _version_ | 1866901921052229632 |
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| author | Vazdar, Mario Paušová, Šárka Bouzek, Karel |
| author_facet | Vazdar, Mario Paušová, Šárka Bouzek, Karel |
| contents | <p>Like-charge pairing is a physical manifestation of the unique solvation properties of certain ion pairs in water.<br>Water's high dielectric constant and related charge screening capability significantly influence the interaction between like-charged ions, with the possibility to transform it, in exceptional cases, from repulsion to attraction.<br>Guanidinium cations (Gdm+) represent a quintessential example of such like-charge pairing due to their specific geometry and electronic structure. In this work, we present experimental validation and quantification of Gdm+ - Gdm+ contact ion pairing in water utilizing nuclear magnetic resonance (NMR) spectroscopy complemented by molecular dynamics (MD) simulations and density functional theory (DFT) calculations. The observed Gdm+ - Gdm+ interaction is attractive albeit weak, about -0.5~kJ/mol, which aligns with theoretical estimation from MD simulations. We contrast the behavior of Gdm+ with that of NH4+ cations, which exhibit no contact ion pairing in water. DFT calculations predict that the NMR chemical shift of Gdm+ dimers is smaller than that of monomers, in agreement with NMR titration curves that display a nonlinear Langmuir-like behavior. Additionally, we conducted cryo-electron microscopy on nona-arginines R9, which, unlike nona-lysines K9, exhibit aggregation in water. These results point to like charge pairing of the guanidinium side chain groups, as corroborated also by MD simulations and free energy calculations of aqueous solutions of these peptides.</p> |
| format | Recurso digital |
| id | zenodo_https___doi_org_10_5281_zenodo_15744735 |
| institution | Zenodo |
| language | eng |
| publishDate | 2025 |
| publisher | Zenodo |
| record_format | zenodo |
| spellingShingle | Preprint of "Guanidinium Like-Charge Ion Pairing and Oligoarginine Aggregation in Water by NMR, Cryo-Electron Microscopy, and Molecular Dynamics" Vazdar, Mario Paušová, Šárka Bouzek, Karel VZ4 VSCHT 214 021 quanidinium peptide oligomers hydration quasi-aromaticity DFT calculation molecular dynamics binding constant chemical shift <p>Like-charge pairing is a physical manifestation of the unique solvation properties of certain ion pairs in water.<br>Water's high dielectric constant and related charge screening capability significantly influence the interaction between like-charged ions, with the possibility to transform it, in exceptional cases, from repulsion to attraction.<br>Guanidinium cations (Gdm+) represent a quintessential example of such like-charge pairing due to their specific geometry and electronic structure. In this work, we present experimental validation and quantification of Gdm+ - Gdm+ contact ion pairing in water utilizing nuclear magnetic resonance (NMR) spectroscopy complemented by molecular dynamics (MD) simulations and density functional theory (DFT) calculations. The observed Gdm+ - Gdm+ interaction is attractive albeit weak, about -0.5~kJ/mol, which aligns with theoretical estimation from MD simulations. We contrast the behavior of Gdm+ with that of NH4+ cations, which exhibit no contact ion pairing in water. DFT calculations predict that the NMR chemical shift of Gdm+ dimers is smaller than that of monomers, in agreement with NMR titration curves that display a nonlinear Langmuir-like behavior. Additionally, we conducted cryo-electron microscopy on nona-arginines R9, which, unlike nona-lysines K9, exhibit aggregation in water. These results point to like charge pairing of the guanidinium side chain groups, as corroborated also by MD simulations and free energy calculations of aqueous solutions of these peptides.</p> |
| title | Preprint of "Guanidinium Like-Charge Ion Pairing and Oligoarginine Aggregation in Water by NMR, Cryo-Electron Microscopy, and Molecular Dynamics" |
| topic | VZ4 VSCHT 214 021 quanidinium peptide oligomers hydration quasi-aromaticity DFT calculation molecular dynamics binding constant chemical shift |
| url | https://doi.org/10.5281/zenodo.15744735 |