A Study of Solvation-Shell Symmetry in Electrolyte Solutions Using Quadrupolar NMR Relaxation of the Nuclei of Monoatomic Ions

Chizhik, Vladimir I.; Podkorytov, Ivan S.; Kaikkonen, Andrei; Михайлов, В. И.

doi:10.1006/jmra.1996.0207

Cited by 6 publications

(3 citation statements)

References 7 publications

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“…8 There are several experimental techniques to study fluxional H-bonds in the condensed phase. Apart from neutron scattering 36 (also in liquid state 37 ), these are fluorescence labeling, 38 terahertz, 39 pump-probe IR, 40 as well as NMR 7,41 spectroscopies. In recent years, using solid-state NMR in combination with crystallographic techniques, fairly good correlations were observed 2,29,[42][43][44][45][46][47] for 1 H, 13 C, 15 N and 19 F NMR chemical shifts and H-bond geometry.…”

Section: Introductionmentioning

confidence: 99%

Proton transfer in a short hydrogen bond caused by solvation shell fluctuations: an ab initio MD and NMR/UV study of an (OHO)⁻ bonded system

Pylaeva

Allolio

Koeppe

et al. 2015

Phys. Chem. Chem. Phys.

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We present a joint experimental and quantum chemical study on the influence of solvent dynamics on the protonation equilibrium in a strongly hydrogen bonded phenol-acetate complex in CD2Cl2. Particular attention is given to the correlation of the proton position distribution with the internal conformation of the complex itself and with fluctuations of the aprotic solvent. Specifically, we have focused on a complex formed by 4-nitrophenol and tetraalkylammonium-acetate in CD2Cl2. Experimentally we have used combined low-temperature (1)H and (13)C NMR and UV-vis spectroscopy and showed that a very strong OHO hydrogen bond is formed with proton tautomerism (PhOH···(-)OAc and PhO(-)···HOAc forms, both strongly hydrogen bonded). Computationally, we have employed ab initio molecular dynamics (70 and 71 solvent molecules, with and without the presence of a counter-cation, respectively). We demonstrate that the relative motion of the counter-cation and the "free" carbonyl group of the acid plays the major role in the OHO bond geometry and causes proton "jumps", i.e. interconversion of PhOH···(-)OAc and PhO(-)···HOAc tautomers. Weak H-bonds between CH(CD) groups of the solvent and the oxygen atom of carbonyl stabilize the PhOH···(-)OAc type of structures. Breaking of CH···O bonds shifts the equilibrium towards PhO(-)···HOAc form.

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Section: Introductionmentioning

confidence: 99%

Proton transfer in a short hydrogen bond caused by solvation shell fluctuations: an ab initio MD and NMR/UV study of an (OHO)⁻ bonded system

Pylaeva

Allolio

Koeppe

et al. 2015

Phys. Chem. Chem. Phys.

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“…For example, neutron diffraction can give an atom-to-atom radial distribution function. 11 Among many spectroscopic techniques, fluorescence labeling, 12 terahertz, 13 pump-probe IR 14 and NMR 15 spectroscopies were used to study the structure of solvation shells. In our recent publication we have employed NMR spectroscopy to study the effects of the counterion and the solvent polarity on the cationic NHN hydrogen bonds in a series of protonated proton sponges dissolved in polar aprotic media.…”

Section: Introductionmentioning

confidence: 99%

Trimethylglycine complexes with carboxylic acids and HF: solvation by a polar aprotic solvent

Guo

Koeppe

Tolstoy

2011

Phys. Chem. Chem. Phys.

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A series of strong H-bonded complexes of trimethylglycine, also known as betaine, with acetic, chloroacetic, dichloroacetic, trifluoroacetic and hydrofluoric acids as well as the homo-conjugated cation of betaine with trifluoroacetate as the counteranion were investigated by low-temperature (120-160 K) liquid-state NMR spectroscopy using CDF(3)/CDF(2)Cl mixture as the solvent. The temperature dependencies of (1)H NMR chemical shifts are analyzed in terms of the solvent-solute interactions. The experimental data are explained assuming the combined action of two main effects. Firstly, the solvent ordering around the negatively charged OHX region of the complex (X = O, F) at low temperatures, which leads to a contraction and symmetrisation of the H-bond; this effect dominates for the homo-conjugated cation of betaine. Secondly, at low temperatures structures with a larger dipole moment are preferentially stabilized, an effect which dominates for the neutral betaine-acid complexes. The way this second contribution affects the H-bond geometry seems to depend on the proton position. For the Be(+)COO(-)···HOOCCH(3) complex (Be = (CH(3))(3)NCH(2)-) the proton displaces towards the hydrogen bond center (H-bond symmetrisation, O···O contraction). In contrast, for the Be(+)COOH···(-)OOCCF(3) complex the proton shifts further away from the center, closer to the betaine moiety (H-bond asymmetrisation, O···O elongation). Hydrogen bond geometries and their changes upon lowering the temperature were estimated using previously published H-bond correlations.

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“…Its value is different from one for ions in bulk solvent due to change in solvation shell composition upon binding. The effect of asymmetric perturbation of the solvation shell on relaxation time was considered in the work [51] in terms of duration of perturbation and time intervals between such events. Effectively, this effect results in the scaling of quadrupole coupling constants for a bound state by factors 1.9 for 23 Na and 2.4 for 35 Cl from values in bulk solvent.…”

Section: Concentration Dependences Of R 1 and R 2 For 1 H 2 H 23 Namentioning

confidence: 99%

NMR Relaxation of Nuclei of Buffer as a Probe for Monitoring Protein Solutions Including Aggregation Processes

et al. 2020

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Characterization of protein solutions is of great importance for biophysical research, pharmaceutical industry, and medicine. Particularly, the monitoring of the protein aggregation is crucial at all stages of biotechnological production and in the diagnosis of dangerous diseases. The present work is focused on a study of prospects and possibilities of NMR relaxation of solvent nuclei for monitoring the state of proteins in solutions. The spin-lattice and spin-spin relaxation rates (R 1 and R 2) of solvent nuclei were measured in the solutions of a small globular protein, RRM2 domain of TDP-43 protein. The solvent was either H 2 O-or D 2 O-based buffer with pH 6.5 and contained 20 mM sodium phosphate and 150 mM NaCl. The relaxation rates of the solvent 1 H, 2 H, 23 Na, and 35 Cl nuclei in solutions of soluble and aggregated RRM2 domain of TDP-43 protein were studied. The aggregation was induced by mild oxidative stress, using treatment by hydrogen peroxide. It was found that aggregation of protein could be detected using NMR relaxation of 1 H nuclei. The observed CPMG dispersion for R 2 rates confirms the millisecond timescale for the hydrogen exchange between water and protein sites. The correlation times and binding constants for sodium and chlorine ions were estimated using concentration dependences for relaxation rates (23 Na, 35 Cl). The relaxation rates of solvent nuclei are sensitive to the presence of protein in solution even at low protein concentrations, and the relaxation rates of different nuclei reflect various aspects of the state of the protein.

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A Study of Solvation-Shell Symmetry in Electrolyte Solutions Using Quadrupolar NMR Relaxation of the Nuclei of Monoatomic Ions

Cited by 6 publications

References 7 publications

Proton transfer in a short hydrogen bond caused by solvation shell fluctuations: an ab initio MD and NMR/UV study of an (OHO)⁻ bonded system

Proton transfer in a short hydrogen bond caused by solvation shell fluctuations: an ab initio MD and NMR/UV study of an (OHO)⁻ bonded system

Trimethylglycine complexes with carboxylic acids and HF: solvation by a polar aprotic solvent

NMR Relaxation of Nuclei of Buffer as a Probe for Monitoring Protein Solutions Including Aggregation Processes

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A Study of Solvation-Shell Symmetry in Electrolyte Solutions Using Quadrupolar NMR Relaxation of the Nuclei of Monoatomic Ions

Cited by 6 publications

References 7 publications

Proton transfer in a short hydrogen bond caused by solvation shell fluctuations: an ab initio MD and NMR/UV study of an (OHO)− bonded system

Proton transfer in a short hydrogen bond caused by solvation shell fluctuations: an ab initio MD and NMR/UV study of an (OHO)− bonded system

Trimethylglycine complexes with carboxylic acids and HF: solvation by a polar aprotic solvent

NMR Relaxation of Nuclei of Buffer as a Probe for Monitoring Protein Solutions Including Aggregation Processes

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Proton transfer in a short hydrogen bond caused by solvation shell fluctuations: an ab initio MD and NMR/UV study of an (OHO)⁻ bonded system

Proton transfer in a short hydrogen bond caused by solvation shell fluctuations: an ab initio MD and NMR/UV study of an (OHO)⁻ bonded system