Binding of divalent cations to acetate: molecular simulations guided by Raman spectroscopy
| Autor: | Hector Martinez-Seara, Elise Duboué-Dijon, Denilson Mendes de Oliveira, Dor Ben-Amotz, Jérôme Hénin, Vladimír Palivec, Pavel Jungwirth, Samual R. Zukowski |
|---|---|
| Přispěvatelé: | Laboratoire de biochimie théorique [Paris] (LBT (UPR_9080)), Université Paris Diderot - Paris 7 (UPD7)-Centre National de la Recherche Scientifique (CNRS)-Institut de biologie physico-chimique (IBPC (FR_550)), Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), ANR-11-LABX-0011,DYNAMO,Dynamique des membranes transductrices d'énergie : biogénèse et organisation supramoléculaire.(2011), ANR-11-EQPX-0008,CACSICE,Centre d'analyse de systèmes complexes dans les environnements complexes(2011) |
| Rok vydání: | 2020 |
| Předmět: |
inorganic chemicals
Ab initio General Physics and Astronomy Infrared spectroscopy 010402 general chemistry 01 natural sciences Divalent Metal Molecular dynamics chemistry.chemical_compound symbols.namesake 0103 physical sciences Carboxylate Physical and Theoretical Chemistry chemistry.chemical_classification 010304 chemical physics Chemistry Ion pairing Binding constant 0104 chemical sciences [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry Crystallography visual_art Raman spectroscopy visual_art.visual_art_medium symbols Molecular simulations |
| Zdroj: | Physical Chemistry Chemical Physics Physical Chemistry Chemical Physics, Royal Society of Chemistry, 2020, ⟨10.1039/D0CP02987D⟩ |
| ISSN: | 1463-9084 1463-9076 |
| DOI: | 10.1039/D0CP02987D⟩ |
| Popis: | In spite of the biological importance of the binding of Zn2+, Ca2+, and Mg2+ to the carboxylate group, cation-acetate binding affinities and binding modes remain actively debated. Here, we report the first use of Raman multivariate curve resolution (Raman-MCR) vibrational spectroscopy to obtain self-consistent free and bound metal acetate spectra and one-to-one binding constants, without the need to invoke any a priori assumptions regarding the shapes of the corresponding vibrational bands. The experimental results, combined with classical molecular dynamics simulations with a force field effectively accounting for electronic polarization via charge scaling and ab initio simulations, indicate that the measured binding constants pertain to direct (as opposed to water separated) ion pairing. The resulting binding constants do not scale with cation size, as the binding constant to Zn2+ is significantly larger than that to either Mg2+ or Ca2+, although Zn2+ and Mg2+ have similar radii that are about 25% smaller than Ca2+. Remaining uncertainties in the metal acetate binding free energies are linked to fundamental ambiguities associated with identifying the range of structures pertaining to non-covalently bound species. |
| Databáze: | OpenAIRE |
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