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Quantifying the Strength of a Salt Bridge by Neutron Scattering and Molecular Dynamics

preprint
revised on 07.05.2019 and posted on 07.05.2019 by Philip E. Mason, Pavel Jungwirth, Elise Duboué-Dijon
The molecular structure and strength of a model salt bridge between a guanidinium cation as the charged side chain group of arginine and the carboxylic group of acetate in an aqueous solutions is characterized by a combination of neutron diffraction with isotopic substitution and molecular dynamics simulations. Being able to recover the second order difference signal, the present neutron scattering experiments provide direct information about ion pairing in the investigated solution. At the same time, these measurements serve as benchmarks for assessing the quality of the force field employed in the simulation. We show that a standard non-polarizable force field, which tends to overestimate the strength of salt bridges, does not reproduce the structural features from neutron scattering pertinent to ion pairing. In contrast, a quantitative agreement with experiment is obtained when electronic polarization effects are accounted for in a mean-field way via charge scaling. Such simulations are then used to quantify the weak character of a fully hydrated salt bridge. Finally, on top of the canonical hydrogen-bonding binding mode between guanidinium and acetate, these simulations also point to another interaction motif involving an out-of-plane hydrophobic contact of the methyl group of acetate with the guanidinium cation.

Funding

PJ thanks the Czech Science Foundation for support via an EXPRO grant no. 19-26854X. EDD acknowledges support from the EMBO and Marie Curie Actions (fellowship ALTF 952- 2015), and support by the "Initiative d’Excellence" program from the French State (Grants "DYNAMO", ANR-11-LABX-0011, and "CACSICE", ANR-11-EQPX-0008). PEM acknowledges the support of his youtube channel, thunderf00t. This work was performed using neutron beam time allocated at the Laboratoire Louis Brillouin in Saclay (proposal 2018-602), computer time allocated by the national supercomputing center IT4innovations in Ostrava (project OPEN-13-24) and MetaCentrum data storage facilities.

History

Email Address of Submitting Author

duboue-dijon@ibpc.fr

Institution

Laboratoire de Biochimie Théorique, CNRS, UPR9080

Country

France

ORCID For Submitting Author

0000-0003-0871-5177

Declaration of Conflict of Interest

None

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in The Journal of Physical Chemistry Letters

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